BRITISH CHEMICAL ABSTRACTS
A.-PURE CHEMISTRY
SEPTEMBER, 1927.
General, Physical, and Inorganic Chemistry.
Symmetrical character of the terms corre 5016 Â. increases approximately linearly with the sponding with systems containing similar voltage in the range above 11 kilovolts. Intensities particles, derived by quantum dynamics. F, were measured by comparison with a standard lamp. H und (Z. Physik, 1927, 43, 788— 804).—Mathe R. W. Ltjnt. matical. ' R. W. L u n t . Ionisation potential.and the fine line spectrum Applications of Schrödinger’s theory to the of hydrogen. K. F. N i e s s e n (Z. Physik, 1927, 43, structure of spectra. E. W e i g e r (Z. Physik, 1927, 694—706).—The ionisation potential of hydrogen has 43, 624—652).—Mathematical. The characteristic been calculated by the use of half quantum numbers structure of spectra, in particular the laws of series assigned to the ion H2+ ; it is shown that some of the spectra and the Stark and Zeeman effects, have been fine-line spectrum is attributable to this ion. The derived by application of Schrödinger’s differentia] value calculated for the ionisation potential is equations. R. W. L u n t . — l-216iüA(=15 volts), in good agreement with that calculated by Burrau by wave mechanics — 1-204IÎA Orbits and light-radiation of hydrogen (=15-4 volts) (Kgl. Danske Videnskab. Selsk. math.- E n g s e t electrons. T. (Ann. Physik, 1927, [iv], 83, fys. Medd., 1927, 7, 14). R. W. L t jn t . 903—904).—Extensive mathematical corrections to a former paper (this vol., 601) are given. Under-water spark spectra [of beryllium, gold, molybdenum, tantalum, and tungsten]. (Miss) Number of dispersion electrons for the con E. J. A l l t n and H. J. C. I r e t o n (Trans. Roy. Soc. tinuous spectra and series spectra of hydrogen. Canada, 1927, [iii], 21, I I I , 127—131).—The absorp Y. Sugiura (J. Phys. Radium, 1927, [vi], 8, 310).— tion lines observed were (Â.) : beryllium, 3321-45, A correction (cf. this vol., 494). 3321-08, 3131-06, 3130-42, 2650-94. 2650-31, 2494-87, Hydrogen atom with a spinning electron in 2494-44, 2350-82, 2348-50, 2175-1; gold, 2700-90, wave mechanics. C. F. R ichter (Proc. Nat. Acad. 2641-49, 2387-75, 2376-25, 2352-65, 2129-46, 2126-62, Sei., 1927,13,476—479).—-It is shown mathematically 1938-52 ; molybdenum, 2045-9, 2038-4,2018-2,2013-1 ; that Schrödinger’s wave mechanics in conjunction tantalum, 2274-46, 2261-68, 2261-47, 2253-35, 2196-07, with the Uhlenbeck-Goudsmit concept of the spinning 2193-90, 2193-25, 2182-66, 2141-95, 2119-71 ; tungsten, electron completely represents the fine structure of 2402-43, 2436-61, 2461-60, 2482-21, 2543-43, 2613-07, hydrogen-like spectra. J. S. C a r t e r . 2613-86, 2633-10, 2656-56, 2681-40. Intensities in the helium spectrum produced A. A. E l d r i d g e . by a condensed discharge. L. S. Ornstein and Existence of solid nitrogen in the earth’s H. P. B o u w m a n (Z. Physik, 1927, 43, 839—844).— atmosphere. H. P e l z e r (Ann. Physik, 1927, [iv], The intensities of the helium lines 5016, 4922, 4713, 83, 362—384).—In order to explain the 5577-35 Â. 4686, and 4383 Ä., excited by a damped wave-train line in the spectrum of aurora borealis, Vegard assumes discharge of train frequency 500 per sec., have been the existence of a layer of solid nitrogen in the upper measured as a function of the maximum voltage of the atmosphere. The possibility of a temperature below wave-trains. The discharge was produced by charg the m. p. of nitrogen (36° Abs.) occurring in the ing a condenser through a rectifier connected to a atmosphere with the earth-sun radiation equilibrium high-tension A.C. supply at the frequency 500 cycles has been investigated thermodynamically. It is per sec.; the condenser discharged through an oil- shown that non-selective absorption of all but a immersed spark gap and the discharge tube containing fraction 1 O' 1430 of the earth’s radiation must occur, he.iiurx; -the inductance of this circuit was made very or, even if absorption is confined to the infra-red, small in order to increase the frequency of the oscilla 99-5% must be absorbed in this region by the deeper tory current. In the range 0-5— 36 kilovolts the atmospheric layers. These conditions do not appear intensities of the lines 5016, 4922, 4713, and 43831. reasonable, and therefore Vegard’s hypothesis seems M o r t o n . increase to a maximum at approximately 10 kilovolts, thermodynamically unsound. R. A. immish rapidly to a minimum in the neighbourhood Afterglow of active nitrogen. K. F. Bon- o 11 kilovolts, and rise again to a second maximum h o e f f e r and G. K a m in s k y (Z. physikal. Cliem., nf ^ )rox1^mately 25 kilovolts; the relative intensities 1927, 127, 385—400).—Nitrogen, purified by the nese lines remain approximately constant. The method of Kaustky and Thiele, exhibits no afterglow. ; ensity of the line 4686 Ä. due to He+ appears to the presence of at least 1% of another gas is necessary • Zero UP approximately 11 kilovolts, and then before the effect becomes apparent. The character eases regularly;- its intensity relative to the line istic spectrum of the afterglow is independent of the 3 a o. 802 BRITISH CHEMICAL ABSTRACTS.— A. foreign gas, and the conclusion is therefore reached Spectrum of Si+ n . P. K . K i c h l u (J. Opt. Soc. that the added gas plays no part in the chemilumin- Amer., 1927, 14, 455—459).—The contributions of escence reaction which is responsible for the afterglow. Fowler and Saha to the structure of the spectrum of The homogeneous gas reaction causing the appearance Si+ are discussed and explained on the basis of Hund’s is bimolecular. In the ultra-violet (down to 2100 A.) theory (A.,_1925, ii, 912, 1104); it is shown that the and visible regions of the spectrum, active nitrogen lines 2P—4P are to be expected in the region of 2500 A., exhibits no absorption. Impurities have no influence which therefore needs to be investigated further. on the ratio of the intensities of the atomic and mole R. W. Lunt. cular spectra, as they have with active hydrogen. New lines between 3100 and 2400 A. in the arc H. F. G i l l b e . spectrum of manganese at normal pressure. S. Structure of the arc spectra of the elements of Pina de Rubies and J. Dorronsoro (Anal. Fis. the nitrogen group. J. C. M c L e n n a n and A. B. Quim., 1927, 25, 211—215).—The wave-lengths, M c L a y (Trans. Roy. Soc. Canada, 1927, [iii], 21, frequencies, and intensities of 135 new lines between III, 63—77).—An examination of existing data leads 3025 and 2400 A . in the arc spectrum of manganese to the identification of multiplets in the arc spectra are tabulated. The majority of the lines have already of nitrogen, phosphorus, arsenic, antimony, and been encountered in the spark spectrum. (tentatively) bismuth. The terms 4S2, 2D23, and J. S. Ca e t e r . 2P12 are deep, with *S2 deepest; 4P 123 and 2P 12 are Origin of terms of the spectrum of cobalt. the most important of the higher energy terms, with N. K. S u e (Phil. Mag., 1927, [vii], 4, 36—49),—The iP 12 3 deeper than 2P 12. The results accord with the method employed by Saha (this vol., 705) has been Pauli-Heisenberg-Hund theory. The three outer applied to the detailed examination of the spectrum most electrons of the unionised atom are in each case of cobalt. Only a small number of fundamental bound in n2 orbits; for the most stable of the excited levels and a few levels combining with these have been states two are bound in n2 orbits and one in an found. No Rydberg sequence has been discovered. (n+1)! orbit. " A. A. E l d r i d g e . Final settlement is required as to whether the 9il/3 Origin of the auroral green line in the oxygen state is possible or not, since, although according to spectrum. J. C. M c L e n n a n , R. R u e d y , and J. H. Bohr and to Stoner the TM3—2N1 state is the most M c L e o d (Trans. Roy. Soc. Canada, 1927, [iii], 2 1 , stable configuration of the electrons in the cobalt III, 27—31).—Parallel evidence is adduced to show atom, the terms due to the 8ili*3—1A7j state occur that in seeking to fit the auroral green line 5577-341 A. prominently in the arc spectrum of cobalt. observed in the oxygen spectrum into the system A. E. M itc h e l l . of energy levels provided for oxygen atoms, “ for Magnetic resolution of the arc spectrum of bidden ” as well as “ permissible ” transitions should zinc. E. B a c k (Z. Physik, 1927, 43, 309—320).— receive consideration. A. A. E l d r i d g e . 35 lines of the arcs pectrum of zinc (containing 5% of antimony) in the region 6844-2—2268-92 A . have been Explanation of spectra of metals of group II. resolved in a magnetic field of 39,000 gauss; from the H. P. K. K i c h l u and M. S a h a (Phil. Mag., 1927, values obtained for the broadening factor g the [vii], 4, 193—207).—An extension of the previous p, s, and cl values have been assigned to the lines work of Saha (this vol., 705), in which it is shown that according to the theory of Hund (A., 1925, ii, 1104). the conclusions of Russell and Saunders (A., 1925, ii, R. W . Lust. 911) regarding the origin of the £)-terms are correct Arc and spark spectra of bromine. L. B lo c h for calcium, barium, and strontium, but should not and E. B l o c h (Ann. Physique, 1927, [x], 6, 205— be accepted as generally applicable to the origins of 231; cf. A., 1925, ii, 611).—Using an electrodeless all dashed terms (cf. following abstract). discharge tube containing sodium bromide, som e 1100 A. E. M i t c h e l l . lines have been determined in the region 6700— Spectrum of neon. M. S a h a (Phil. Mag., 1927, 2250 A. ; of these 700 are reported for the first time. [vii], 4, 223—231).—The results of Hund and of In addition to lines due to neutral bromine atoms, the Goudsmit on the spectrum of neon have been utilised lines due to singly and doubly ionised atoms have been according to the author’s method for the examination classified. Some lines are thought to be due t0 of the spectra of the alkaline earths (cf. preceding triply ionised atoms. R. W. Lost. abstract). The theory then accounts not only for the fundamental levels, but also for all the higher levels, Wave-length measurements in the arc a n d the Rydberg sequences, and the order of values spark spectra of zirconium. C. C. Kress (VJ.o. observed in each case. The treatment leads to the Bur. Standards, Sci. Paper 548, 1927, 22, 47—60).— conclusion that whenever from any particular distri The arc and spark spectra of zirconium as emittc bution of electrons in potential orbits, F, D, and P between electrodes of the pure metal have been terms arise simultaneously they must then have the photographed. The arc spectrum has been trace same combining powers, so that if F and P are treated from 4881 into the infra-red up to 9277 A . The arc as ordinary terms then D must be dashed, or if any spectrum consists of (1) band spectra originating two terms be treated ordinarily, then the third must in a molecule, perhaps of zirconium oxide, (2) fine be dashed and the choice must depend entirely on the spectra originating in the neutral atom, (3) fij10 previous knowledge of the spectrum of the element. spectra originating in the singly ionised atom. 1 ie The theory also explains transitions such as AK =2 spark spectrum, measured from 2163 to 6115 A., or 3 which apparently depart from the selection contains, in addition to the foregoing, (4) line» o principle. A. E. M i t c h e l l ! the doubly ionised atom, (5) lines of the treb y GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 803 ionised atom. Tables of wave-lengths of the lines are a?D2 are triplets: 1394-298, 1394-476, 1394-622, given. W. E. D o w n e y . and 1894-967, 1895-168, 1895-342; a?D3 is a quin Influence of the magnetic field on the polaris tuplet^ 3250-00, 3250-15, 3250-31, 3250-49, 3250-71; ation of the resonance radiation of cadmium. and a3P2 and a1^ are doublets: 6227-34, 6227-52, and P. S o l e i l l e t (Compt. rend., 1927, 185, 198—199).— 7394-48, 7394-59. R. W . L u n t . The experiments of Wood and Ellett (A., 1924, ii, Spectrographic junction of the X-ray and 715) on the influence of a weak magnetic field on the ultra-violet regions with the aid of ruled gratings. resonance radiation of mercury have been repeated J. T i i i b a u d (Compt. rend., 1927, 185, 62—64).— for the corresponding ray (3261 A .) of cadmium, and By means of a tangent diffraction grating having the same qualitative results obtained. The depolaris 1800 lines per mm. (A., 1926, 651) the wave-lengths ing effect of the magnetic field, however, is con of the rays FeLa (17-73 A.), OXa (23-75 A.), CXa siderably greater with cadmium. For a zero magnetic (44-80 A.) and MoJlfa (65-0 A.) have been determined field the polarisation is 73% at 115—170°, but falls within an absolute error of 0-5%. The spectro to 35% at 210°. J. G r a n t . graphic junction between the X-ray and ultra-violet Fine structure of the spectrum lines of regions has thus been attained. J. G r a n t . cadmium in the ultra-violet. W. M o h a m m a d and Atomic character of some properties of X-rays. S. B. L. M a t h u r (Phil. Mag., 1927, [vii], 4, 112— E. D e l a u n e y (Compt. rend., 1927,185, 193—195).— 120).—An attempt has been made to analyse the fine It is shown theoretically, and confirmed by ionisation structure of the most prominent cadmium lines over measurements of the intensity of the radiation of the range 4800—2775 A . In general the results are fluorescence produced when mixtures in varying in agreement with those of MacNair (A., 1926, 986). proportions of strontium and barium chlorides were A . E . M i t c h e l l . irradiated with X-rays, that the intensity of the Series in the first spark spectrum of tin. A. L. fluorescence is not an additive property for the two N abayan and K. R . R a o (Nature, 1927,120, 120).— salts. It increases much less quickly in proportion The spectrum of tin in the singly-ionised stage to the amounts of barium chloride present. (Sn n) has been investigated. All the terms required J . G r a n t . by Hund’s theory have been found, together with Direct and indirect production of characteristic 4P, a-D, 2P, and a2S terms. The second ionisation X-rays. D . L. W e b s t e r (Proc. Nat. Acad. Sci., potential of tin is computed to be about 14-5 volts. 1927, 13, 445—456; cf. Beatty, Proc. Roy. Soc., About 30 lines in the first spark spectrum have been 1912, A, 87, 511; Balderston, A., 1926, 767).—The classified. In general, it closely resembles the spec characteristic rays from silver are largely of direct trum of Si n. A. A. E l d r i d g e . origin, the experiments described indicating a ratio of direct to indirect rays equal to 2-4 at all ordinary Electrodeless discharge. Spectra of ionised X-ray voltages. Indirect rays do not appear to any mercury and of iodine. J. K. R o b e r t s o n and appreciable extent in spectra from extremely thin J. H. F i n d l a y (Trans. Roy. Soc. Canada, 1927, [iii], targets, especially when light backing materials are 21, III, 89—97).—Sixteen mercury lines between used. The ratio of the probability that a cathode 1942 and 2848 A . were observed when the discharge ray will remove a X electron from an atom by direct was carried by helium at 0-2 mm. pressure, the most action to the probability that it will radiate a quantum intense being 2848, 2837, 2262, 2260, 2225, 2191, 2052, of energy in the continuous spectrum as great as the and 1942 A . Carroll’s classification of H gn (A., X-ionisation energy, is of the order of unity for silver 1926, 214) is preferred, and is supported by further at 50 kilovolts. The ratio is probably greater for study of the line 1942 A. ; the line 2264 A . probably copper under corresponding conditions and may vary belongs to Hgm (Kimura and Nakamura, A., 1925, with the voltage. J. S. C a r t e r . >i. 726). The spectra of pure iodine, iodine and hydrogen, and iodine and helium were also observed. Efficiency of /{-series emission by If-ionised With hydrogen, hydrogen iodide was probably atoms. L. H. M a r t i n (Proc. Roy. Soc., 1927, A, formed, and the spectrum is unlike that obtained in 115, 420—442).—Relative values for the efficiency helium; no evidence of combination between helium of X-emission have been determined in iron, nickel, and iodine was obtained, although the iodine vapour, copper, and zinc for a series of exciting radiations after discharge, was brown (cf. Boomer, A., 1925, ii, which lie between 0-6 A. and the respective X limits of these elements. In iron, the absolute efficiency 925)- A. A. E l d r i d g e . has been determined and investigated as a function Hyperfine structure of lanthanum lines. W. F. of the frequency of the ionising radiation. A beam Meggers and K. B u r n s (J. Opt. Soc. Amer., 1927, of exciting radiation is totally absorbed in a plate of 14, 449—454; cf. this vol., 602).—An account of one of the above metals placed at right angles to it. preliminary experiments is given in confirmation of The ratio of the energy of the total excited X-radiation he view that some lanthanum lines have a hyperfine to that of the exciting radiation can be readily structure. An interferometric method was used in deduced from the ratio of the ionisations produced ® range 6800—3800 and a grating in the range by the total absorption in oxygen of the exciting beam 0—3800 A. The source used gave sharp and and those excited rays which' escape the radiator, if narrow lines and showed little reversal. In the the absorption coefficients for those radiations, in the spectrum the line is a quadruplet: 2667-96, radiator are known. The low values found for the 2668-30, 2668-42, and a*F, a doublet: efficiency of emission for X-ionised atoms, together '4oo, 3494-633. In the La n spectrum a1D2 and with the results of other related experiments, are 804 BRITISH CHEMICAL ABSTRACTS.— A.
explained by the hypothesis that, in some cases, 273).—An apparatus is described by means of which for reasons not yet understood, the* excited /ir the efficiency of six different elements as emitters of radiation does not escape the atom, but is “ intern soft X-rays can be measured in rapid succession under ally absorbed ” in outer electron shells, giving rise similar conditions without opening up the experi to high-speed electrons. The probability of K -series mental vessel. The apparatus consists of a quartz emission as opposed to its internal absorption is tube in which are mounted two filaments, the struc found to be independent of the frequency of the ture supporting the targets, a pair of nickel condenser exciting radiation, within the limits of experimental plates, a nickel photo-electric plate around which is error. The efficiency of X-emission is a function of a nickel electrode, and a nickel earth shield. The the atomic number of the excited atom, and it seems thermionic current (it) producing the X-radiation probable that similar laws, relating the probability was measured, also the photo-electric current (ip) of absorption with atomic number and wave-length, produced by a definite portion of that X-radiation hold for both “ normal ” and “ internal ” absorption. when it fell upon a nickel plate, and the ratio ip I it L. L. B i r c u m s h a w . was plotted against atomic number for the elements Measurement of the M o/i doublet distances carbon, silicon, chromium, manganese, iron, cobalt, by means of the double X-ray spectrometer. B. nickel, copper, molybdenum, palladium, silver, D a v i s and H. P u r r s (Proc. Nat. Acad. Sei., 1927, tungsten, platinum, and gold. For a given element, 13, 419—422).—Using the double X-ray spectrometer, ip ¡it is approximately proportional to the P.D. considerable separations of the Mo/fa and K$ doublets exciting the X-rays. The efficiency appears to be have been obtained. The observed separations, a periodic function of the atomic number, and not, as 0-0043 and 0-00058 A., respectively, are in good agree previously stated (loc. cit.), proportional to the square ment with those derived from actual wave-length root. L. L. B ir c u m s h a w . determinations. The MoXy doublet could not be Inverse Zeeman effect in neon lines. H. separated. J. S. C a r t e r . N a g a o k a and T. M ts h im a (Proc. Imp. Acad. Tokyo, Intensities of soft X-ray lines as a function of 1927, 3, 205—207).—Spectrograms are given which the exciting potential. A. J o n s s o n (Z. Physik, show the inverse Zeeman effect in a number of lines of 1927, 43, 845—865).—The variation of the intensity the neon spectrum from 5852 to 6533 A . The spectrum of X-ray lines as a function of the exciting was excited in the capillary tubing connecting the potential in the range 0—20 kilovolts has been legs of an H-shaped discharge tube; the field applied measured using the most recent form of Siegbahn’s varied from 1-8 to 5-8 kilogauss. Careful regulation vacuum spectrograph. Intensities were measured by of the neon pressure and electrode potential is Geiger’s method. The lines measured were AlXa, necessary for the production of the phenomenon.
Xa3, /vpj; Ag L o . v Rh-Laj, L$v L$2, Ly 1; MoXaj, R. W. L u n t . L$x; TIM a, and WJfa, Mp. The curves so Zeeman effect of the hyperfine structure com obtained have been compared with the intensities ponents of the m ercury line 2537. W. A. M ao- calculated from the theoretical equations of Bergen- N a i r (Proc. Nat. Acad. Sci., 1927, 13, 430—432).— Davis (Physical Rev., 1918, [ii], 11, 433), and of In zero magnetic field the positions of the hyperfine Rosseland (Phil. Mag., 1923, [vi], 45, 65). The former structure components of the mercury line 2537 are, does not agree with experiment; if however due taking the central one as reference, —0-0256, —0-0103, allowance be made for anticathode absorption in the 0, +0-0116, and + 0-0221 A ., respectively. In application of Rosseland’s equation, then a fairly magnetic field the last four become triplets with satisfactory agreement with experiment is obtained, 3/2 the normal separation. The behaviour of the at least at low exciting potentials. R. W. L u n t . line —0-0256 A . is more complicated. The perpendi X-Ray spectra of the second order. M. J. cular components behave as the perpendicular com Druyvesteyn (Z. Physik, 1927, 43, 707—725).— ponents of a 3/2 normal triplet starting at —0-0256 A., The satellites of the line JTPj, K$", Xp2, and Ap'" but the parallel component increases in wave-length have been measured for the elements from potassium with increasing field strength. The relative intensi to iron; the values of K$"'—K$v expressed as ties of the five lines in zero field are, in order of vR-\ agree well with those calculated from data increasing wave-length, 13, 8, 10, 10, and 9. In a referring to the normal spectra. The satellites of the field of 5000 gauss the relative intensities of the line Lp2, Xp'2 and LPj"2 have been determined for the parallel components are3, 6,18,19, a n d 4,respectively. elements from niobium to lead; the calculated The anomalous behaviour of the line —0-0256 offers a differences L$'2—L$2 and Lp"2—ip 2 show dis possible explanation of the incomplete polarisation continuities at lead and silver and" are always slightly of resonance radiation of mercury in zero magnetic greater than the corresponding experimental values, field. J. S. C a r t e r . which lie on a smooth curve. The satellites of the Transition from ordinary dispersion into line Lyv Ly/ , have been determined for the elements Compton efiect. I. W a l l e r (Nature, 1927, 120, from niobium to tin; the differences Ly\—Ly1 lie 155—156).—A brief account, relating to an atom between the extreme values calculated and so do the containing only one electron, is given of the various differences corresponding with L y ' % 3— Ly.it 3 for the stages of the transformation. A. A. Eldeidge. elements from zirconium to silver, *’ R. W. Lunt. Theory of Compton efiect. II. G. Wentzel Emission of soft X-rays by different elements. (Z. Physik, 1927, 43, 779—787).—The analyse 0. W. R ic h a r d s o n and F. S. R o b e r t s o n (Proc. R o y . previously developed (this vol., 603) h a s been extended Soc., 1927, A, 115, 280—290; cf. ibid., 1926, A, 110, to a consideration of the inner atomic interference o GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 805 scattered radiation whereby a more exact evaluation evaporation thus diminishes abruptly at the m. p. has been made of the intensities of displaced and of these metals, and increases as the temperature undisplaced lines. For the scattering of the /fa-line rises beyond this point. A number of incidental of molybdenum (0-708 A.) the calculated, values of phenomena associated with the occlusion of gases and the ratio of tho normal intensity to that scattered at an with the crystallisation of these metals are also angle 0 agree satisfactorily with those observed by described. R. W. Lunt. Woo (A., 1926, 447) for values of 0 from 60° to 150°. A more satisfactory agreement between experiment Thermionic emission of incandescent platinum and theory obtains for the ifa-line of zinc (1-437 A.). in an atmosphere of iodine. P. J e z (J . Phys. In the case of pure crystal interference of the E'a-line Radium, 1927, [vi], 8 , 244—253).—The emission of ruthenium (0-612 A .) by sodium chloride for behaves in accordance with Richardson’s law of scattering angles from 11° to 60° the analysis leads to thermionic emission. The negative emission in an values of the ratio of the normal intensity to the atmosphere of iodine is considerably greater than the intensity according to classical theory, which ratio is corresponding emission in air. The positive emission identical with the square root of Bragg’s 'form factor, in an atmosphere of iodine is almost zero, it is in good agreement with those obtained experimentally suggested that the reversible reaction Pt-(-2T2 — (Bragg, Phil. Mag., 1921, [vi], 41, 309; A., 1921, ii, Ptl4 takes place on the surface of the platinum, and 477). R. W. Lunt. that a layer of iodide is responsible for the emission. W. E. D o w n e y . Duration of resonance phenomenon. E. F ix e s Application of the equations of chemical (Z. Physik, 1927, 43, 726—740).—The duration of kinetics to the phenomenon of emission of resonance has been analysed by wave mechanics, and electrons from red-hot bodies. J. K. S y r k i n values have been calculated for argon, krypton, and (J. Russ. Phys. Ghem. Soc., 1927, 59, 351—355).— xenon of the same order of magnitude as those given Electrons are assumed to be emitted only from the by Auger. R. W. L u n t . superficial layer of a hard metal; the emission may Ultra-ionisation potentials of mercury. E. 0. therefore be regarded as a heterogeneous chemical L vk r e n c e (J. Franklin Inst., 1927 , 204, 91—94; reaction of the first order, thus allowing the application cf. this vol., 85).—Ultra-ionisation potentials were of the several well-known equations of chemical detected when mercury vapour was bombarded with kinetics to the various deduced thermodynamical electron streams possessing Maxwellian velocity expressions for L, the number of electrons emitted in distributions. J. S. Ga r t e r . unit time from unit area of a hot surface. Thermionic emission from solid and licpiid J. KAYE: metals. II. The thermionic melting diagram Role of circular electrons in paramagnetic phenomena. D . M. B o s e (Z. Physik, 1927, 43, of copper, silver, and gold. A. G o e t z (Z. Physik, 1927, 43, 531—562 ; cf. this vol., 492).-—The method S64—882).—An attempt lias been made to explain is described by which the continuously recording paramagnetic phenomena in terms of quantised electron orbits, thereby avoiding the difficulties device for emission, temperature, and time was associated with the classical theories of Langevin and calibrated; the maximum sensitivity is 1-035 amp./ Weiss. Tho basic assumptions characterising the mm. The data obtained have been employed to analysis now advanced are (1) that of the angular calculate accurately the constants b and b0 in the momenta of an electron moving in a closed orbit Richardson and Richardson-Dushman equations: associated with the s quantum number and the k—1 I=A-\/T xe~b!T and 1 ~ A0T2e-b,'T; from these associated with the k (azimuthal) quantum number, values A and A0 have been obtained. The corre only the former are responsible for paramagnetic sponding values of the work of electron evaporation phenomena, and (2) that, whatever be the orientation $ and
the former has two atomic moments (8 and 14 Constitution of ordinary lead. F. W. Aston magnetons) for two well-defined temperature intervals, (Nature, 1927, 120, 224).—Experiments with lead the latter has one moment (19-5 magnetons) very near tetramethyl yield three principal lines, 206, 207, 208, to the dominant moment (9 magnetons) of the of intensities respectively 4, 3, 7, in good agreement VIV ion. The change in moment in the former case with the at. wt. 207-2. The lines are integral with has been attributed to dissociation of the tetroxide those of mercury to an accuracy of 1—2 in 104. A into the trioxide, since 14 magnetons is the dominant faint line at 209, and possibly lines at 203, 204, and moment of the V111 ion. J. G r a n t . 205 are also present. The presence in mercury of an Weber’s theory of molecular magnetism, and isotope 196 (0-04%) is certain. A. A. E l d r id g e . the internal field. W. P e d d i e (Nature, 1927, 120, At. wt. of scandium. N. H. S m it h (J. Amer. 80—81). Chem. Soc., 1927, 49, 1642— 1650).—Anhydrous Positive-ray analysis of nitric oxide and scandium chloride was prepared by passing carbon tetrachloride vapour diluted with nitrogen over pure collisions of the second kind. T. R. H o g n e s s and E. G. Lunn (Physical Rev., 1927, [ii], 30, 26—30).— scandium oxide at 750—850°. The ratio of the The ionisation potentials for the formation of NO+, fractionally sublimed chloride to pure silver was then N+, and 0 + are 9, 21, and 22 volts, respectively; the determined; the mean of nine analyses gave 45-160 heat of dissociation of the molecule of nitric oxide is as the atomic weight of scandium (Ag= 107-880). computed to be 175,000 g.-cal. per g.-mol. The A special apparatus for filling a weighing bottle with percentages of N+ and 0+ formed by electron impact the chloride in presence of dry air is described. increase with increase in pressure from 4 and 1-5% S. K. T w e e d y . at zero pressure to 9 and 3%, respectively, at 0-01 mm. Fundamental at. wts. III. Revision of the Some of the NO+ ions dissociate spontaneously, and at. wt. of silver. Analysis of silver nitrate. 0. others are disrupted into the atomic ions on collision H o n i g s c h m id , E. Z i n t l , and P. T h il o (Z. anorg. with gas molecules. In presence of argon or helium Chem., 1927, 163, 65—92).—The at. wt. of silver has there is evidence of collisions of the second kind : been redetermined by reduction of silver nitrate with NO+A+=NO++A, and NO+He+=NO++He. hydrogen. In order to eliminate errors due to adsorp tion of air on the silver nitrate and on the reduced A. A. E l d r i d g e . Influence of neighbouring metal walls on the silver, the analyses were conducted in a vacuum. Taking the at. wt. of nitrogen as 14-008, that of silver loss of charge of canal rays. J . K oenigsberger is 107-879. H. F. Gill b e . (Z . Physik, 1927, 43, 883—89S).—The discrepancies between the data of Wien, Kutschevski, Ruttenauer, Fundamental at. wts. IV. At. wt. oi and Ruchardt on the loss of charge and on the mean potassium. Analysis of potassium chloride. free path of the particles comprising canal rays are 0. H o n ig s c h m id and J. G ottbeatt (Z. anorg. Chem., discussed at length with special reference to the 1927, 163, 93—104).—The ratios KCl:Ag and effects produced by metal surfaces for which in the Ag : AgCl have been determined by a nephelometric particular case of iron capillaries an analysis is method, giving for the at. wt. of potassium 39-104. developed. Examples are given showing how this H. F. Gillbe. analysis leads to values of the concentration of H+ Fundamental at. wts. V. At. wts. of silver, particles before and after passing through a steel tube chlorine, and potassium. E. Z i n t l and J. G ou (2-5 cm. x 0-8 mm.) which are in good agreement with b e a tt (Z. anorg. Chem., 1927, 163, 302—314).—By experiment. heating potassium nitrate in hydrogen chloride, the The corrections necessary to evaluate the ratio, w, ratio KN03 : KC1 has been found to be 1-356111 ± of the number of positively charged particles to the 0-000010. Taking the at. wt. of nitrogen as 14-008, number of neutral particles in a beam 6f canal rays the ratio AgCl : Ag as 1-328668, and the ratio are discussed in detail and examples are given. It is KC1: Ag as 0-691149, the following at. wts. are •shown that foraecelerationpotentialsof approximately calculated: silver, 107-879^0-0011; potassium, 35 kilovolts for H + ions in hydrogen the corrected 39-104±0-0007; chlorine, 35-456±0-0003. values of w of Ruttenauer and Ruchardt agree R. CtlTHILL. approximately. This is because at such potentials Fundamental at. wts. VI. At. wt. of chlorine. the effect of metal capillaries on w is small; at lower 1. Complete synthesis of silver chloride. 0. potentials the effect is more marked, and in this is to H o n i g s c h m id and S. B . C h a n . II. An incomplete be sought the explanation of the discrepancies in the synthesis of silver chloride. 0. H o n icsch m iu data of the two workers just mentioned. and L. B i r c k e n b a c h (Z. anorg. Chem., 1927, 163, R. W. Lunt. 315—344).—A weighed amount of liquid chlorine was Helium compound. D. M . M o r r is o n (Nature, reduced to hydrogen chloride by means of ammonium 1927, 120, 224).—If orthohelium has one electron arsenite, then caused to react with the equivalent, relatively far removed from the nucleus with respect weighed amount of silver, dissolved in nitric acid, to the other, it might be expected to resemble and the silver chloride formed weighed. In this way, hydrogen in forming a gaseous compound with the ratio C l: Ag was found to have the value 0-328668, bismuth or its radioactive isotopes. Experiments from which, assuming the value 107-880 for the at. wt. in which helium is passed over a strong radioactive of silver, the at. wt. of chlorine is 35-457. Since the source of radium-i? and radium-C and excited by weight of silver chloride was equal to the sum of the means of an electrodeless discharge indicate that such weights of the constituent elements to within the a gaseous compound is formed. A, A. E l d r i d g e . limits of experimental error, the doubts cast by Guye GENERAL, PHYSICAL, AND IN ORGANIC CHEMISTRY. 807 on the purity of at. wt. silver (A., 1918, ii, 40) seem thesis of progressive increase in the light absorption unfounded. of the material. The rate of destruction of active Ail attempt was made to alter the proportions of centres is 6—9 times that of the ionisation of inactive the isotopes of chlorine in carbon tetrachloride by molecules, and in the new material 20—50% of the fractional distillation. The chlorine in the two molecules are in the active state. J. S. G. T h o m a s . extreme fractions was converted into hydrogen New scheme for atom-building. M. N. Saha chloride by passing the carbon tetrachloride over (Physikal. Z„ 1927, 28, 469—473; cf. ibid., 221; glowing quicldime, precipitating the calcium with this vol., 705).—The principles laid down in the ammonium carbonate, and distilling the concentrated earlier paper are given a new graphical form. The filtrate with sulphuric acid. The acid was then used optical, X-ray, and periodic properties of the atoms to precipitate a weighed amount of silver. In neither are co-ordinated in terms of the new scheme. case was the result different from that obtained using W. E. D o w n e y . ordinary hydrochloric acid. R. C u t h i l l . Wave mechanics and atomic structure of Special effects of polonium, solar radiation, matter and of radiation. L. de Broglie (J. Phys. and high tension on lead. ( M l l e . ) S. M a r a - Radium, 1927, [vi], 8, 225—241).—Schrödinger’s GNEANU (Compt. rend., 1927, 185, 122—124; cf. A., mechanics represents dynamic phenomena by con 1926, 879; this vol., 710).—The ionisation-currents tinuous waves. It is shown that these continuous obtained from a lead strip 0-1 mm. thick on the back solutions give only a statistical view of dynamical of which polonium had been deposited, were deter phenomena. For a more exact description of the mined before and after exposure to positive or negative phenomena, it is necessary to take into account tensions of 120,000 volts, and to the sun, with or singular solutions. This conception gives a clear without the high tension. In all cases the ionisation view of Schrödinger’s equation. W. E. D o w n e y . was small at first, increasing rapidly to a maximum Hypothesis that light quanta and electrons are and slowly falling off exponentially. The unexposed discrete elements. G. B e c k (Z. Physik, 1927, 43, strips and those exposed to high tension only produced 658—674).—The Compton and photo-electric effects, greater ionisation-currents than those exposed to solar diffraction, polarisation, interference, and the general radiation with or without exposure to a high tension, theory of electrodynamics are analysed and discussed the effects of the high tension (especially of the from the point of view of the following hypothesis : negative type) and of the sun being to lower and raise matter and radiation are to be conceived as discrete the ionisation-currents, respectively. The radiation elements; to each fundamental characteristic of which is not due to the polonium itself is of the radiation there is a corresponding characteristic of a-particle type, although exposure to a negative matter. R. W. L u n t . tension causes the appearance of a (3-radiation also. Quantum mechanics of magneton electrons. The phenomena are attributed to the formation of a W. P a t j l i , jun. (Z. Physik, 1927, 43, 601—623).— new radio active substance in the lead. J. G r a n t . The characteristic-function method of Schrödinger [Special effects of polonium, solar radiation, and the Dirac-Johnson transformation theory have and high tension on lead.] H. Deslandres (Compt. been employed to derive the quantum mechanics of rend., 1927, 185, 124— 125).—The a-particles of electrons responsible for magnetic phenomena. polonium may give rise to a more penetrating radia R. W . L u n t . tion of protons when they are stopped by the lead, Application of wave mechanics to the quant the effect of which may be modified by the nature of ising of black-body radiation. E. G u t h (Z. the subsequent exposure. J. G r a n t . Physik, 1927, 43, 653—657).—Mathematical. L u n t . Vaporisation of polonium. P. Bonet-M aury R. W. (Compt. rend., 1927, 185, 204—206).—By means of Radiationless quantum changes. G. W e n t z e l the apparatus previously described (this vol., 606) it (Z. Physik, 1927, 43, 524—530).—The probability of has been shown that the curve obtained when the a radiationless change has been analysed by wave percentage of polonium vaporised is plotted against r/d mechanics for the special case in which an electron follows the cosine law to within 2%. The ratio r/d is from an L-orbit is transferred to a üT-orbit which is known as the “ reduced ray,” r being the radius of the previously ionised : the calculated ratio of the number circle enclosing the number of polonium atoms con of Ka. quanta emitted to the number of L electrons cerned, and d the distance between a centre of transferred is in good agreement with the data of symmetry situated on the normal to the emitting Auger (A., 1926, 1188) and of Robinson (Proc. Roy. surface, and the centre of the disc bearing the deposits. Soc., 1926, A, 113, 282). R. W . L u n t . J. G r a n t . Magnetic hydrogen atoms and non-magnetic Theory of luminescence in radioactive molecules. W. A. N o y e s (Proc. Nat. Acad. Sei., luminous compounds. J. W . T. W a l s h (Proc. 1927, 13, 377—378).—The magnetic character of Physical Soc., 1927 , 39, 318—333).—Determinations hydrogen atoms and the non-magnetic character of of the brightness curves of radioactive luminous hydrogen molecules suggest the following possibilities: compounds over a period of about 4000 days show Isolated hydrogen atoms may orient themselves hat the brightness-time relationship is of the form loosely in pairs with the rotation of their electrons in H{BI{b+B)}+kt+a=0, where a, b, and k are the same direction, but wall be prevented from com constants, and B is the brightness after time t. The bining by the repulsion between the nuclei and also faults are i11 accord with Rutherford’s theory of the between the electrons. Under the catalytic effect of es ruction of active centres combined with a hypo a metal the orbits of the electrons may be assumed to 808 BRITISH CHEMICAL ABSTRACTS.— A.
take opposite directions, with the two nuclei between band spectrum value of Witmer (A., 1926, 552) and the planes of the two orbits. There will bo magnetic of Dieke and Hopfield (this vol., 89). J. S. C a r t e r . repulsion between the orbits, but the electrons will be held to their orbital positions by their attraction Energy computations in a simple four-body for the nuclei and will fall closer to these since there system. K. P. N i e s s e n (Z. Physik, 1927, 43, are now two nuclei instead of one. This accounts 675—693).—The energetics of a simple four-body for the large dissipation of energy when two hydrogen system have been analysed by classical mechanics with special reference to the application of half atoms unite to form a molecule. The formation of helium atoms is possible by the approach of two quantum numbers to the excited hydrogen molecule. hydrogen molecules with the four nuclei between the R. W. Lunt. planes of two electrons, which will fall very close in, Absolute intensities in the hydrogen chloride rotation spectrum. R. M. B a d g e r (Proc. Nat. whilst the two other electrons 'will assume orbits at Acad. Sci., 1927, 13, 408—413).—The absorption of a greater distance. Since the mass of a helium atom is less than that of four hydrogen atoms, the energy hydrogen chloride in the region of 80 ¡j. has been deter evolved in such a process will be of a different order mined at four pressures and the absolute absorption from that involved in the formation of a hydrogen curves have been obtained. The value of BStS calculated from the absorption coefficient as indicated by Tolnran molecule. J. S. C a r t e r . and Badger (A., 1926, 451, 555) and using the a priori “ Pendulum ” orbits in atomic models. R. B. probabilities for the respective quantum states given L i n d s a y (Proc. Nat. Acad. Sci., 1927, 13, 413— by the new theories is 4-7 x 1016, whilst that demanded 419).—Although “ pendulum ” orbits are usually by the new quantum theory is 1-12 x 1018. The lack nded out of the systems of actual orbits since they of agreement between the experimental and theoretical apparently involve collision of the electron with the transition probabilities suggests that, whilst the nucleus, such orbits are, however, plausible on the predictions of the new quantum theory may apply assumption of a repulsive force operative only in the to some ideal system, they do not describe the con immediate vicinity of the nucleus. Assuming this ditions observed with hydrogen chloride. force to obey an inverse cube law, it is shown that the J. S. Ca r te r . calculated distances are of a not unreasonable order Absorption of ozone in the visible spectrum. of magnitude. J. S. C a r t e r . G. C o l a n g e (J. Phys. Radium, 1927, [vi], 8, 254— 256).—The values of the absorption coefficient of Structure of the helium atom. I. J. C. ozone between 4350 and 6400 A. have been deter S l a t e r (Proc. Nat. Acad. Sci., 1927,13, 423—430).— mined by photographic photometry. The maximum The success of the method of perturbations in the value of the coefficient occurs at about 6070 A. calculation of spectra depends entirely on finding a W. E. D o w n e y . soluble problem to serve as the unperturbed solution Absorption and emission spectra of nitric oxide which is itself a sufficiently close approximation to in the ultra-violet. M. L a m b r e y (Compt. rend., the actual case. A method of finding such an 1927, 185, 382—384).—The spectral data of pure approximation is presented and applied to helium, nitric oxide have been determined by the method where even the soluble, unperturbed problem gives previously described (this vol., 489). Under a feeble results in good agreement with experiment. The dispersion the absorption spectrum appeared as a applicability of . the present method to various other series of narrow doublets (1948—2207 A.), but with problems is indicated. J. S. C a r t e r . greater dispersion the components of the first two Coupling of electronic and nuclear motions in doublets were found to be double. The moment of inertia of the NO molecule was calculated and found diatomic molecules. E. U. C o n d o n (Proc. Nat. Acad. Sci., 1927, 13, 462— 466).—The new quantum to be 0-22 X10-39 c.g.s.u. and the distance apart of mechanics offers at least a qualitative explanation of the constituent atoms 0-45 xlO*8 cm. An electrode- phenomena conditioned by the quantum mechanical less discharge produced a mauve illumination the coupling between the motion of the nuclei and emission spectrum of which included the first two of the electrons in diatomic molecules. absorption doublets and contained numerous rays in the visible and ultra-violet spectra (2348—2S55 A.). J . S . Ca r t e r . Wave mechanics and the normal state of the An analogy is indicated between nitric oxide and carbon monoxide. J. G ra n t. hydrogen molecule. E. U. C o n d o n (Proc. Nat. Acad. Sci., 1927, 13, 466—470).—Burrau’s data Band spectrum of water vapour. D. J a c k (Kgl. Danske Videnskab. Selsk. math.-fys. Medd., (Proc. Roy. Soc., 1927, A, 115, 373—390; cf. Watson, 1927, 7, 14) for the energy of an electron moving A., 1925, ii, 349; Dieke, ibid., 927).—A summary is under the influence of two fixed centres of Coulomb given of the‘work of previous investigators on the attraction as a function of the distance apart of these water-vapour bands 3064, 3122, 2811, a n d 287o. centres are used to give a semi-quantitative discussion Experimental evidence as to the nature of the emittex of the neutral hydrogen molecule. On the assump is discussed and shown to be in favour of the h yd roxy l tion that the electrons have no mutual influence, the ion. Details are given of the band 260S, which is moment of inertia and the heat of dissociation are similar in structure to the others. For any definite 2-7 X10-11 g.cm.2 and 24-36 volts respectively. On value of m, it gives the same final value for the correction for electronic interaction these quantities moment of inertia as the bands 2811 and 3064, whilst become 4-26 X10"41 g.cm.2 and 4-4 volts respectively. the initial value is the same as that for the band The latter value agrees to within 0-1 volt with the 2875. The scheme of bands suggested by Dieke GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 809
(loc. cit.) has been extended, and the addition of the of these metals. The inductance of the leads was band 2608 allows of the scheme being verified by 34 microhenries, and the resulting frequency 4-54 X taking differences of the wave-numbers of tho null 104 cycles persec.; the maximum instantaneous current lines in the various bands. The band at 3428 also was computed to be 9-4 xlO 3 amp. Numerous lines fits into the scheme. The doublet separations are are emitted during the first half cycle, others at a found to be the same for bands giving, the same final later stage, and some persist for 10~4 sec. The value for the moment of inertia. The possibility of magnesium line 2852 (15—IP) is reversed from the explaining the formation of the doublets by the initial stage and increases in width to 60 A., which is application of the Kratzer-Kramers-Pauli theory is thought to be due to the formation of magnesium discussed. A series of single lines near the head of oxide. The lines 3337, 3332, 3330 (Ip—2s), initially tie band 2811 has also been measured, and found faint, become stronger; 2942, 2939, 2937 (lp—3s) are to fit reasonably well into a parabolic formida. The strong and broadened to 12 A .; 2782, 2778, 2776 series hears a strong resemblance to the singlet series (Tp—4s) show weak reversal; the triplet 3838, 3832, measured by Watson. L. L. Bircumshaw. 3829 shows initial reversal, and 3097, 3093, 3091 Interpretation of molecular spectra. III. shows sharp reversal. The mean line from ionised Rotational and vibrational spectra of molecules magnesium 4481 (28—3
complex cyanides in aqueous solution have been in thé engine under detonating conditions, the spectra determined in the range 5000—2000 A. : K4[Fe(CN)6], of all four quarters have the same length and inten Na,[Fe(CN)5,H20], Na-tFeiCNUNH.], sity. From lead tetraethyl, lead emission lines appear Naj[Fe(CN)gN0 2], Na^Fe(CN) 5As0,], only in the first quarter. C h e m ic a l A b s t r a c t s . Na5[Fe(CN)6S03], NaKo[Fe(CN)5N02], Absorption spectra of naturally occurring Na2[Fe(CN)5,H20], Na2[Fe(CN)5NH3], benzopbenone derivatives. T. T a s a k i (Acta Na2[Fe(CN)5NO], and KgFefCNJg. The changes in Phytochim., 1926, 2, 199—205).—The absorption the absorption of a solution of Na»[Fe(CN)5,H20] hi spectra of certain naturally occurring benzophenone acid and alkaline solution are thought to corre derivatives have been investigated. Maclurin, hydro- spond with the equilibrium [Fe(CN)5,H20]'"+ O H '= cotoin, methylhydrocotoin, protocotoin, and methyl- [Fe(CN)50H ]""+ H 20. R. W. L e n t . protocotoin all show similar absorption, with a single Absorption spectruni of bromine in solution. wide band with maximum at 3250 A. Protocotoin Bovis (Compt. rend., 1927, 185, 57—59).—Solutions is regarded on spectrochemical grounds as 6-liydroxy- of bromine in water, carbon tetrachloride, chloroform, 2 : 4-dimethoxy-3' : 4'-methylenedioxybenzophenone. ethyl alcohol, and carbon disulphide always show two L. M. C l a r k . absorption bands (in the violet and ultra-violet). Absorption spectra of coumarin derivatives. Their sizes and positions are practically constant, the T. Tasaki (Acta Phytochim., 1927, 3, 21—29).—The former being 0-106 and 0-036 ¡x, and the latter 0-414 absorption spectra of the following derivatives of and 0-260 ¡x for the violet and ultra-violet, respectively. coumarin in 0-0001üf-alcoholic solution have been Comparison with the absorption spectra of gaseous determined for wave-numbers (X-1 in cm.) from and liquid bromine (A., 1924, ii, 712) shows that the 2000 to 5000 : coumarin, hydroxy- and methoxy- band 0-414 ¡x is obtained in all cases, whilst the band coumarin, dihydroxycoumarin, æsculin, æsculetin, 0-260 ¡x is characteristic of bromine in solution only. acetylcoumarin, diacetylæsculetin, and methylene- The opacity of liquid bromine increases regularly from dioxyphenylcoumarin. Coumarin shows two absorp the radiation 0-350 ¡x (where its optical density is a tion maxima in this region at 3200, 3600 A. When minimum) towards the radiation 0-240 ¡x. The one or two hydroxyl groups are introdùced into the observations are complicated by the presence of benzene nucleus of coumarin the substance shows only impurities and by changes in the strengths of the one absorption maximum. E. A. Lxmr. solutions. J. G r a n t . Impact fluorescence of zinc. J. G. Winans Continuous and band spectra of mercury. (Physical Rev., 1927, [ii], 30, 1—10).—The fluor H. Volkringer (Compt. rend., 1927, 185, 60—62). escence radiation obtained when a mixture of zinc —The author has extended his method (this vol., vapour at 16 mm. and mercury vapour at 0-28 mm. 178) to the study of the ultra-violet portion of the pressure is illuminated by light of various wave spectrum obtained when mercury vapour at 240° is lengths from the hot and cold quartz mercury arcs excited by an electrodeless, oscillating discharge, the and the aluminium spark contains several zinc lines intensities (calculated by the method of Chalonge and which require more than 4-9 volts for their excitation Lambert) being plotted against the wave-lengths. (cf. A., 1926, 102, 768). It is assumed that mercury The continuous spectrum comprised a large band atoms in the 21P1 and 23S^ or 3ZD states are effective (0-37—0-30 ¡x) with a maximum intensity at 0-336, in impacts of the second kind ; a collision between an and a smaller band with a maximum at 0-265 ¡x. A excited mercury atom and a normal zinc atom appears minimum was obtained at 0-260 ¡x followed by a sharp more likely to be one of the second kind if the energy rise to 0-2537 (x (the resonance ray) when the spectrum of the excited mercury atom only slightly exceeds that ceased sharply. The wave-lengths of the maxima needed to excite the zinc atom. A band at 2770 A. of the numerous diffuse bands between 0-305 and may be due to an HgZn molecule. A. A. Eldridge. 0-265 (x have also been determined. The distribution Transition of fluorescence into phosphor of energy as a function of wave-length is similar to escence. E. G r a v i o l a and P. P r in g s h e im (Z. that of the radiation from a black body at 2233°. Physik, 1927, 43, 384—393).—With a rotating phos- As with cadmium, the wave-lengths of the maxima phoroscope and a Graviola fiuorometer the time of are almost 2 and 4/3 times that of the resonance ray duration of the luminescence of the following substances for the visible and ultra-violet regions, respectively. has been determined (time in 10"9 sec.) : rhodulin- J. G r a n t . orange in sugar 4±0-7, in gelatin 4-5±0-4, in glycerol Ultra-violet spectroscopy of engine-fuel 4-3±0-4, in gelatin at —180° with a green filter flames. G. L. C l a r k and A. L. H e n n e (J. Soc. 4-9±0-7, with a red filter 6-2; uranin in glycerol Automotive Eng., 1927, 20, 264—269).—The spectra 4-4; rhodamine-i? in gelatin 4-6±0-2, in glycerol 4-2 ; of radiation during the four quarters of a stroke were ruby >15; uranium glass >15, uranyl nitrate 5-1, observed for straight-run petrol under detonating uranyl sulphate in sulphuric acid 1-9. A ll these sub and non-detonating conditions for the same fuel stances, except ruby and uranium glass, which exhibit using lead tetraethyl, aniline, and iodine as knock- only phosphorescence, show a momentary fluorescence suppressors, and for cracked-petrol blends. During followed by a weaker and relatively slowly diminishing detonation the first-quarter spectrum extends far phosphorescence. After a review of the s u b ject, it into the ultra-violet, and the second-quarter spectrum is concluded that the phenomena of photolumm- a smaller distance; the third and fourth quarters are escence can be classified as follows : (1) Pure fluor characterised by very little radiation energy. During escence in which the time interval is of th e order o normal explosion, or when knock suppressors are used 3 x 10~9 sec. If the exciting light is polarised, the GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 811 secondary radiation is impolarised, or only partly Measurements have been carried out with mixtures polarised according to the nature of the solute and of gases. Using mixtures of hydrogen and neon and solvent. (2) Fluorescence followed by phosphor a copper cathode, b falls from 1-86 for 100% hydrogen escence in which the time interval is of the order at first slowly to 1-7 for 75% neon and then rapidly to of 10-s sec. For polarised incident light, the 1-06 at 100% neon; a is 0-125 at 100% hydrogen, fluorescent and phosphorescent emissions are either about 0-12 at 25% neon, and 0-024 at 100% neon. both unpolarised, or both equally polarised. (3) Pitre In the case of hydrogen-nitrogcn mixtures, using phosphorescence in which the polarisation of the an iron cathode the results differ widely : a at 100% secondary radiation does not depend on that of hydrogen is 0-14 and at 100% nitrogen 0-325, and the incident beam, but is determined by the crystal between the limits 25% and 100% nitrogen it is structure of the phosphorescent substance. It is greater than 0-325, reaching a maximum at values also concluded, in agreement with the results of roughly given by a=0-55, 65% nitrogen. The mag Vavilov and Pringsheim, that no transition of fluor nitudes V„ and b show minima in the same region of escence into phosphorescence is to be observed. gaseous composition, whilst dn shows a less pronounced R. W. Lunt. minimum near 75% nitrogen. Luminescence phenomena during oxidation All of the results apply only to cylindrical cathodes reactions in aqueous solutions. L. M a l l e t 3 mm. in diameter. They are even more complicated (Compt. rend., 1927, 185, 352—354).—Numerous than would have been expected, but a more ex oxidation reactions, even in dilute solutions, are haustive discussion will be possible if accurate values, accompanied by the production of visible light, or for the cathode-fall can be obtained. R. A. M o r t o n . by a radiation detectable photographically, or made visible by the addition of fluorescent substances. A Electron affinity of some stable molecules at number of such reactions are described. J. G r a n t . high temperatures. G. P i c c a r d i (Z. Physik, 1927,. 43, 899—920).—A stationary potential is established Dissociation of hydrogen by electrons. A. L. between a platinum gauze and plate by allowing a Sdghes and A. M. S k e l l e t t (Physical Rev., 1927, Bunsen flame of constant length to burn through the [ii], 30, 11—25).—Dissociation of hydrogen by elec gauze and impinge on the plate mounted above the trons begins when the electrons have an energy gauze. This potential, which arises from a difference corresponding with 11-5 volts. With 100-volt and between the electron emissions of the gauze and plate 20-volt electrons, the rate of diminution of pressure due to a constant difference in temperature, causes a (the atomic hydrogen produced being condensed on constant current to flow through a reflecting galvano the walls of the tube which was immersed in liquid meter which connects the gauze to the plate; since air) is directly proportional to the pressure ; hence the its resistance is low' compared with that of the flame dissociation is probably produced as a direct result it serves as an ammeter. When a bead of a volatile of the impact of an electron on the molecule. salt on a platinum wire is introduced into the flame A. A. E l d r i d g e . between the gauze and plate the galvanometer regis Current density in the normal cathode-fall. ters an increased current due to the ions formed from R. S e e lig e r and M. R e g e r (Ann. Physik, 1927, the volatilised salt. From the observed current [iv], 83, 535—564).—With different cathode-metals increase and from the rate of loss in weight of the- but the same gas, the normal current density (j„) in bead the equilibrium constant K of the dissociation a discharge tube is smaller as the normal cathode-fall A — 7- A^-j-e can be calculated, K =[A + ]Z[Aj^1= (^n) is greater; with different gases but the same [e]2[yl]_1. Data, referring to sodium, barium, and metal jn increases as the normal cathode-fall increases. lithium salts, are given to illustrate that K is sensibly With plane cathodes j„ varies as the square of the constant over a wide range of concentration of metal pressure, but with cylindrical cathodes of small atoms in the flame. diameter j n varies directly as the pressure. Using an By assuming that the ionisation potential U is improved technique, jn has been determined for 21 independent of the temperature, the integrated form different cases, the variables being (a) hydrogen, of the van’t Hoff isochore, log K— — nitrogen, neon ; (6) Aluminium, iron, zinc, copper, has been used to calculate the ionisation potentials silver, gold, platinum ; (c) pressure : 3— 10 mm. of the following metals from the values of log K lhe resiilts are expressed by means of the relation determined . in the Bunsen flame : csesium 3-89, in which a and b are constants characteristic potassium 4-32, sodium 5-13, calcium 6-09, barium of each metal and each gas : the values for a vary 5-19, strontium 5-67, thallium 6-04, silver 7-54, and between 0-006 and 0-350, whilst those for b vary copper 7-69 volts. In a similar way the ionisation between 1-00 and 2-05. A comparison is made potentials of the rare earths have been determined. ctween the results with the normal current density The following values were obtained : lanthanum 5-49, and other processes with wdiich the cathode is con cerium 6-91, praseodymium 5-76, neodymium 6-31, cerned, viz. the normal cathode-fall Fn and the thick- samarium 6-55, gadolinium 6-65, terbium 6-74, dys ttfss dn of the cathode dark space. Reasons are prosium 6-82, ytterbium 7-06. given against the validity of quantitative relationships It is shown that the electron affinity of the anions, j,. “ave been suggested for these magnitudes, but or their decomposition products, liberated by the os regarded as legitimate to group the results in series salts used for the above determinations are too low j ' 7», Al< Zn < Fe < Pt § Ag < Cu < Au. to have any appreciable effect on the galvanometer A»
are based wholly on Stock’s experimental results, and Crystal system of a-thallium. G. A s a h a r a and it is contended that diborane-diaramine does not T. S a s a h a r a (S ci. Papers Inst. Phys. Chem. Res. exist, and that the compound isolated is monoboran- Tokyo, 1926, 5 , 79—81).—Comparatively perfect ammine, BH3,NH3. The confusion arises from the crystals of thallium were prepared by the electrolysis formation of the ammine during the determination of of a saturated solution of thallous sulphate using a the mol. wt. of diborane in liquid ammonia. current density of 0-05 amp./dm.2 at 3 volts. The J . G r a n t . crystals appear to belong to the hexagonal holohedral Relation of the octet of electrons to ionisation. class, isomorphous with magnesium, and have an W. A. N o y e s (Proc. Nat. Acad. Sci., 1927,13, 379— axial ratio of 1-63. C. J. S m it h e l l s . 380).—According to the octet theory the atom of an Crystal structure of a-thallium. T. S a s a h a ra ion assumes a noble gas structure but with the differ (Sci. Papers Inst. Phys. Chem. Res. Tokyo, 1926, 5, ence that in an ion the positive nuclear charge is 82—94).—The crystal structure of a-thallium pre greater or less than the number of electrons in the pared by electrolysis (preceding abstract) has been shell by a whole number of units. In solution, in determined from Laue and rotating-crystal photo spite of the static attractions between ions of opposite graphs. The crystal is hexagonal close-packed, sign, the external shells of electrons exert so great a space-group D^h; the unit cell contains 2 atoms repulsion on close approach that ions will separate arranged at -J, §, |; §, f ; its dimensions are a= and maintain their independent existence after 3-415, c=5-540 A ., c/a=l-622. C. J. S m it h e lls . collision. The fact that hydrogen compounds are ionised to a much smaller extent than the corre Crystal structure of a-manganese. A. J. sponding alkali metal compounds is doubtless due to B r a d l e y and J. T h e w l i s (Proc. Roy. Soc., 1927, A, the fact that the hydrogen ion has no external electron 1 1 5 , 456—471).—The crystal structure of a-man and may approach much closer to a negative ion and ganese has been investigated by the powder method, may even be actually included within the orbits of a using the precision camera of Westgren and Phrag- pair of electrons belonging to the negative ion. m6n (A., 1925, ii, 1035). The specimen contained J . S . C a r t e r . 0-4% Al, 1-3% Fe, and 1-5% Si, and was alloyed with Electron-sharing ability of organic radicals. 0-35% C. The number of atoms in the unit cell is 58, not 56 as stated by Westgren and Phragmen. By R . M. H i x o n and I. B . J o h n s (J . Amer. Chem. Soc., 1927, 49, 1786— 1795).— On the electron theory of a lengthy process of elimination, the only atomic valency, the properties of any polar group must arrangement capable of explaining the experimental depend on the electron-sharing ability of the radical results has been selected from 21 alternative structures. or element to which it is attached. It is shown The space-group is probably Tf,, and there are four that the dissociation constants and free energies groups of equivalent positions, containing respect of ionisation in the series R-NH2, R-C02H, ively 2 X, 8 A , 24 Dv and 24 D2 atoms. The exact R-CH2-C02H, R • CH2• CH2• C0 2IT, can be expressed as positions of the atoms are defined by five parameters, exponential functions of such an electron-sharing 0-317, 0-356, 0 042, 0-089, and 0-278, respectively. ability, and that an exponential equation of the same The structure is based on a single body-centred cubic general form holds for the change in dissociation lattice, but each lattice point is represented by a constant brought about by the interposition of suc cluster of 29 atoms with tetrahedral symmetry. The cessive •CH2i groups between the radical R and the interatomic distances range from 2-24 to 2-96 A., polar group. The bearing of this relationship on indicating that the electrons are distributed unequally Langmuir’s results (A., 1917, ii, 525) is discussed. between the various atoms. This implies the pre sence of something more closely related to a com F. G. W i l s o n . pound than to a true element in the a-manganese minium, the new rare earth. B. S. H o p k i n s structure. L. L. B ir c u m s h a w . (J . Franklin Inst., 1927, 2 0 4 , 1—11).—A rdsume of the American investigations which led to the discovery Crystal structure of ammonium fluoride. W. of the element 61. J . S. C a r t e r . Z a c h a r i a s e n (Z . physikal. Chem., 1927, 1 2 7 , 218— 224).—The crystal structure of ammonium fluoride Eka-manganese. N. S e l j a k o v and M. K o r s it n - has been determined by means of the Laue and Debye s k i (Physikal. Z., 1927, 28, 478—479).—Polemical diagrams, and is of the zinc oxide type; u is § approx. against I. and W. Noddack’s work on rhenium (this The hydrogen atoms are arranged in a manner which vol., 532). W. E. D o w n e y . permits the easy decomposition of ammonium fluoride Improvements in the Debye-Scherrer tech into ammonia and hvdrogen fluoride. nique. G. K u r d j u m o v (Z. Physik, 1927, 43, 921— “ H. F. G il l b e . 933).—Following an analysis of the relation between Precise measurements of the lattice c o n s t a n t s the shape of an object, the divergence of the incident of magnesium oxide, sulphide, and s e le n id e X-ray beam, and the line width of the X-ray spectro and manganous oxide and selenide. E. B r o c h gram, a modified form of slit is described to be used (Z. physikal. Chem., 1927, 1 2 7 , 446-454).—D» in conjunction with a cylindrical object whereby a lattice constants of magnesium oxide, sulphide, and line width of 0-15 mm. is readily obtained. Thus, selenide, and of manganous oxide and selenide, for example, a steel wire 1 mm. in diameter gave lines mixed with sodium chloride, have been determine with a width of 0-16 mm. The exposure necessary, by the powder method. The values of aw are. however, is approximately three times that corre magnesium oxide 4-208 ±0-001 for one preparation sponding with the usual procedure. and 4-207+0-002 A . for a second, magnesium sul R. W. Lunt. phide 5-190±0-002 and 5-190±0-003 A ., magnesium GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 815 selenide 5-452¿0-002 A., manganous selenide 5-448± trioxide (J. pr. Chem., 1 8 47, 42, 3 5 9 ) is a mixture of 0-002 A. These results are obtained using the Ka. the metal and the dioxide. Attempts to prepare copper line of wave-length 1-539 A. Employing the crystalline cobaltic oxide have proved futile, the Ka. iron line of wave-length 1-934 A., the figures methods described in the literature giving either obtained are: magnesium selenide, 5-451 ±0-001, cobaltocobaltic oxide or cobaltous oxide. manganous oxide, 4-435±0-002 A. The method of R. C u t h i l l . calculating the limiting error of the measurements is Atomic structure of AuSn. G. O. P r e s t o n and given. H. F. G i l l b e . E. A. O w e n (Phil. Mag., 1 92 7, [vii], 4, 133— 147).— X-Ray examination of the compound AuSn by the Zinc blende-wurtzite lattice and ionic lattices. powder and Laue methods show that the compound G. von H evesy (Z. physikal. Chem., 1927,127, 401— crystallises on a hexagonal lattice of side 4 -3 0 7 A . ; the 414).—The electrical conductivity of substances in the axial ratio is 1-276, which requires two'molecules of crystal and in the molten states may be employed to AuSn per unit cell. The space-group is D‘h, C*w, differentiate between lattices composed of ions or of or Di/„ it being impossible to differentiate further. uncharged particles. Both lands of particles are The intensities of reflexion are in agreement with a usually present in one and the same crystal, as is structure having the gold atoms at the points (0, 0, 0) indicated by quantum theory considerations. For and (0, 0, |) with the tin atoms at the points (£, §, £) beryllium oxide the X-ray diagram gives no indication and (§, J, I ) . A. E. M i t c h e l l . as to whether the lattice is atomic or ionic, but con ductivity measurements demonstrate, in agreement Grating deformation in precipitated mixed with Grimm and Sommerfeld and with Goldschmidt, crystals. L. V e g a r d (Z. Physik, 1927, 43, 2 9 9 — the existence of uncharged particles in the crystal 3 0 8 ).—Earlier work (this vol., 5 0 4 ) on the grating lattice. The a-Agl lattice is ionic, whilst that of the deformation in mixed crystals of mercurous chloride fs-form is atomic; the apparent invalidity of Grimm and bromide has been extended to a quantitative and Sommerfeld’s considerations to the ease of silver determination of the deformation. In mixed crystals iodide is thus explained. The appearance of metallic the grating constants a and c increase linearly conductivity is due to the presence of uncharged from 6 -3 2 0 to 6 -5 8 5 and from 10-907 to 1 1 -12 2 A., lattice particles. The relationship between the respectively, as the molecular percentage of mer breaking down of the crystal lattice and the appear curous bromide is increased from 0 to 100. The ance of polymorphic transition is demonstrated. mixed crystals are formed either by mixing concen H. F. G i l l b e . trated solutions of mercurous nitrate, potassium Compounds of the lattice type of pyrrhotine bromide, and potassium chloride, or by dropping (FeS). W . F. d e J o n g and H. W . V. W il l e m s mercurous nitrate solution slowly into the solution (Physica, 1927, 7, 74— 79).-—The following lattice of potassium bromide and chloride; in both cases a is data are recorded: CrS : a 3-44, c 5-67 A., 4-85. greater than the values corresponding with the mixed CrSe: a 3-59, c 5-80 A., dai^ 6-74. CrAs (solid crystals formed in the solid state, and c is less except solution): a 4-14, c 5-51 A., c£eaic. 7-08. MnS and in the range 3 0 — 7 0 % mercurous bromide when pre MnSe are regular. MnAs : a 3-74, c 5-75 A., d^ , 6-20. cipitated from concentrated solutions. The deviation MnSb, which can dissolve much manganese or anti in the case of slowly precipitated crystals is small. mony: a 4-14, c 5-90 A., dc!llc_ 6-71. FeS : a 3-43, R. W. Lunt. c 5-71 A., dcaic 5-01. FeAs, rhombic. FeSb : «4-06, Chemistry of solid substances. Forms of c 5-13 A., dcaIc. 8-05. CoS : a 3-37, c 5-14 A., d ^ 5-98. mercuric sulphide and sulphur. H. W. K o h l - CoSe: a 3-60, c 5-27 A., dcalo 7-78. CoTe : a 3-89, s c h u t t e r (Koll. Chem. Beihefte, 1927, 24, 319 — c 5-36 A., deaic. 8-85. CoSb : a 3-91, c 5-20 A ., ticalc 3 6 4 ).—The characteristic features of reactions of 8-72. NiS : a 3-42, c 5-30 A ., (Z<,aIc 5-61 NiSe : a solids are discussed, and the transitions of poly 3-66, c 5-33 A , dauc 7-41. NiTe : a 3-95, c 5-36 A., morphic substances are regarded hs ideal cases of change to the red variety more rapidly than do the (Ann. Physik, 1927, [iv], 83, 418—426).—The X-ray smaller crystals. When the red crystals are heated at pattern of the nematic phase of ^j-azoxyanisole in a 129— 130°, they change suddenly throughout the magnetic field consists of two diffuse interference entire crystal to the yellow form. The accepted maxima in a direction at right angles to the direction transition temperature of 127° has always been of the field. The molten aggregates are arranged so determined on the finely divided material. The that the long axes of the molecules are parallel to the accelerating influence of light on the change from the force-lines. The X-ray diagram of a polycrystalline yellow form to the red was also found to depend on the preparation shows complete orientation of the state of subdivision of the particles. Tammann’s crystallites when care is taken to avoid the effect of observations (A., 1920, ii, 315) on a white form of the walls of the containing vessel in influencing the mercuric iodide were confirmed, but it was not possible growth of crystals from a magnetically oriented fluid. to establish this as a definite allotropic modification. The crystal of ^-azoxyanisole is monoclinic with On the other hand, a definite tetragonal orange modifi p 107° 34', a 10-18, b 7-74, c 16-72 A . There are 4 cation of striking stability appears to be formed by molecules in the unit cell. The axial ratios are slow cooling of the vapour. This retains its colour 1-32 : 1 : 2-21. R. A. M o r t o n . even at the temperature of liquid air. By similar X-Ray diffraction patterns from liquids and methods, Muthmann’s sulphur (Sm) was prepared colloidal gels. G. L. C l a r k (Nature, 1927, 120, in the dry way and the transition to rhombic sulphur 119—120).—For unstretched rubber latex films the observed. E. S. H e d g e s . spacings calculated by the Ehrenfest formula from Crystal structures of «-octane, n-hexane, and the two principal rings are 6-03 and 14-76 Á.; n-pentane. J*. C. M c L e n n a n and W. G. P l u m m e r for purified caoutchouc the spacings are 5-97 (Trans. Roy. Soc. Canada, 1927, fiii], 21, III, 99— and 11-15 A . Bragg’s formula n\=2d sin. 0 is pre 113; cf. Müller and Saville, A., 1925, ii, 367).—A ferred to Ehrenfest’s expression. Values for the modified Debye-Scherrer apparatus was employed. spacings of the inner and outer rings in cellulose Each hydrocarbon exists in one of two forms, nitrate, fresh, aged by light, and aged by heat, are according to the conditions of solidification, both tabulated. Swelling or combination of molecules sets of spacings usually appearing in the photo with solvent or oil has a much greater effect than graphs. n-Octane, orthorhombic, has a 3-50, b 4-36, ageing. Percentage changes, referred to the spacings c 15-0 Ä., d 0-S2 g./c.c.; monoclinic, a 3-87, b 4-72, of raw, liquid china-wood oil, are tabulated for the oil c 14-4 Ä., ß 120°. w-Hexane, orthorhombic, has a on polymerisation and drying. No indication has 3-51, b 4-26, c 11-6A., d 0-80 g./c.c.; monoclinic, been found of long spacings such as are obtained with a 3-87, b 4-61, c 12-0 A., ß 120°. w-Pentane, ortho solid carbon chain compounds and liquid primary rhombic, probably has a 3-35, b 4-31, c 10-3 A., d normal alcohols. Similar results have been obtained 0-90 g./c.c.; monoclinic, a 3-86, b 4?61, c 10-0A., with cumar, resins, and varnishes. ß 120°. Calculated values of the smallest number of A. A. E l d r id g e . mols. per unit cell are, respectively, 0-98, 0-99; Unusual micro-structure in iron and tungsten. 0-98, 1-04; 1-00, 1-03. The respective “ long C. J. S m i t h e l l s and H. P. R o o k s b y (Nature, 1927, spacings ” for the rhombic forms of w-octane (15-0 A.), 120, 226—227).—An unusual micro-structure, re w-hexane (11-6 A.), and w-pentane (10-3 A.) corre sembling that observed by Tritton in cast electrolytic spond with that of a straight chain of carbon atoms iron, has been observed in tungsten. The small terminating with hydrogen atoms. grains formed by the sub-boundaries have a nearly A. A. E l d r i d g e . uniform orientation in each crystal. The sub Dielectric investigations on anisotropic molten boundaries may be formed under the influence of j>-azoxyanisole. W. K a s t (Aim. Physik, 1927, [ivj, stresses set up during the rapid cooling of the metal, 83, 391— 417; ef. this vol., 498).—Particles of fluid A. A. E l d r id g e . anisotropic p-azoxyanisolc are oriented in a magnetic Recrystallisation phenomena in aluminium. field, so that their axes arc parallel to the field. This A. E. v a n A rkel and M . G. v a n B r u g g e n {/- corresponds with anisotropy in dielectric properties. Physik, 1927, 42, 795—806).—An extension of pre It is known from optical experiments that the particles vious work. The number of new' crystals formed m adhere to the walls of the containing vessel. New aluminium after stretching is greatly diminished, for experiments are interpreted in terms of this adhesion the same percentage stretching, at 500°. The resulta effect and it is found that the magnetic moment of are discussed at length with reference to th e mechanical iJ-azoxyanisole is about 105 Bohr magnetons, whilst properties of aluminium. R - W- Lukt. the dielectric anisotropy (e1—e3) is —0-112 at a Heat-motion of crystal atoms in relation to temperature near the m. p. (119°) ,~i as the temperature the intensity, position, and sharpness of approaches the clarifying point this magnitude rapidly spectral lines. I. W a l l e r (Ann. P h y sik , 1927, decreases. The size of the elementary particles in [iv], 83, 153— 183).—Earlier work on the Doppler the nematic state may be determined from the effect (Z. Physik, 1923, 17, 39S) is in a greem en t with magnetic moment. It is shown that a close relation the results of von Laue (Ann. Physik, 1926, [iy], o > ship exists between crystal structure and the structure 877). It is shown that a fraction amounting o of the units in the nematic phase (cf. following several % of the whole measured intensity o a abstract). R. A. M o r t o n . spectral line corresponds with scattering due to hea. X-Ray investigations on solid crystalline and motion. This deduction throws light on • molten anisotropic p-azoxyanisole. W. K a s t relation between temperature and the sharpne GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 817 of X-ray spectral lines. The cubic term is evalu sputtering, on glass. When the image of a 300 ated in the expression for the potential energy of candle-power filament lamp is focussed on such films, the lattice in atom displacements. Both classical voltages of the order of 10~7 volt were observed with statistical mechanics and quantum considerations silver and of 10~5 volt with bismuth and antimony. lead to the same result for the connexion between R. W. L h n t . temperature, heat expansion of the lattice, and the Physical properties of molybdenum at high shift of X-ray lines. In the special case of a lattice temperatures. C. Zwikker (Physica, 1927, 7, with free marginal atoms the assumption that each 71-—74).-—Determinations were made between 1200° atom is influenced only by its six nearest neighbours and 2400° Abs. of the following physical properties : enables the heat expansion to be expressed as a spectral emissive power (X 0-652), black temperature homogeneous distortion of the lattice. The treat (X 0-652), emissive power (X 0-541), pseudo-emissive ment is extended theoretically in other directions. power, colour temperature, specific resistance, total R. A. M orton. radiation, light emission, heat conductivity, and Relation between tbe surface of crystals and linear expansion coefficient. Expressions are given their mass and volume. K. Hrynakovski (Bull. for the thermo-electric emission, rate of evaporation, Soc. amis sci. Poznan, 1927, 1, 49—53).—The ratio and vapour pressure. The Thomson effect is between the actual surface area and the area of the negligible. The heat of vaporisation is 154,000 g.-cal. equivalent sphere is constant during the growth of a per g.-atom, and the sublimation point at 1 atm. is crystal. It decreases as the crystal symmetry 47S0° Abs. Chemical Abstracts. increases. The relative rate of growth of the faces is dependent on the mass of the crystal. Vibration frequencies of binary compounds. W. H e r z (Z. anorg. Chem., 1927, 163, 221—224).— Chemical Abstracts. Scattering of electrons from single crystals The vibration frequencies of a large number of binary compounds have been calculated from existing data of nickel. A . L. P a t t e r s o n (Nature, 1927, 120, 46—47).—In Davisson and Germer’s investigations and the results compared with the sum of the vibra (this vol., 492) the alteration in intensity, with vary tion frequencies of the atoms composing the molecule. ing voltage, of the reflexion with maximum at 50° In all cases the latter bears a simple numerical relation ship to the vibration frequency of the compound. in the (111) azimuth for 54-volt electrons can be explained by the control provided by a second cross H. F. G i l l b e . Electric differential method for measuring the grating beneath the first, the position of the maximum specific heat Cv of gases. M . T r a u t z (Ann. requiring the spacing between the gratings to bo Physik, 1927, [iv], 83, 457—497).—The principles &i/V3, where 7f=0-66 or 1-16 and a /V 3 is the underlying the differential method for measuring normal spacing of the (111) planes of a face-centred Gv are considered in detail and equations are deduced cubic lattice of constant a. Calculated and observed and expressed in such a form that experimental data maximum intensities for voltages in the neighbour can be conveniently inserted. On the assumption hood of 54 are compared. The variation of intensity that the experimental technique and the theoretical with azimuth has also been calculated. The assump considerations are mutually consistent it is shown that tion of the existence of faces (111) would explain the C„ may be measured to within 0-04%. Various reflexion in the (111) azimuth. A. A. E l d r i d g e . sources of error are discussed. The high degree of Mechanism of the electrical conductivity of accuracy attainable by the method opens up a new metals. N . S. N a z a r o v (Bull. Univ. Asie Centrale, field for investigation. By measuring Cv accurately 1926, No. 12, 83—87). Chemical Abstracts. for mixtures, it is possible to evaluate Gv for any material the vapour pressure of which is a few mm. of New theory of crystal detectors. W. O g a w a mercury at 0° or the ordinary temperature, if nitrogen (Radio-nonihon [Japan], 1927, 4, 114— 115, 270— or argon is first saturated with the vapour. The 272).—The rectifying action of a crystal detector is specific heats of vapours determined in this way are ascribed to (1) difference of electron emissions from likely to be trustworthy to within 1—5%, a degree of eaeh electrode, and (2) an appropriate resistance to accuracy which has been hitherto attained only with minimise metallic conduction at real contact points pure gases. R. A. M o r t o n . and make electron emission possible through the adjacent narrow free space. The activation of Specific heat of the hydrogen molecule. D. M. synthetic galena by silver sulphide is ascribed to the D e n n i s o n (Proc. Roy. Soc., 1927, A, 115, 483— formation of metallic silver. 486).—The values for the moment of inertia of the Chemical Abstracts. hydrogen moleculc and the ratio of the weights of the mi 1‘ e^ect a bismuth crystal. C . W. H e a p s symmetrical group of states to the asymmetrical (physical Rev., 1927, [ii], 30, 61— 65).—The Hall group, obtained by Hund (this vol., 495), are not in spect was measured in plates cut in different diree- agreement witli the observed features of the band ions from a single crystal of bismuth. spectra of hydrogen. On the assumption that the T A. A. E l d r i d g e . time of transition between a symmetrical and an thermo-electric phenomena with thin metallic asymmetrical rotational state of the hydrogen 7—^ - T- Terada, S. Tanaka, and S. Kijsaba molecule is very long compared with the time in inoe. Imp. Acad. Tokyo, 1927, 3, 200—203).—A which the observations of the specific heat are made, premnnary account of the thermo-electric effects a specific heat curve is obtained which follows the mutt!1 ^ local heating of thin films of silver, bis- observed curve within the limits of experimental > and antimony, deposited chemically, or by error. Moreover, the constants I (moment of inertia) o H 818 B r i t i s h c h e m ic a l a b s t r a c t s .— a . and p (proportion of symmetrical to asymmetrical joined a long side tube leading to a bulb, and bent molecules) are in good agreement with the values of into the form of an inverted and an upright U-tube. these constants as found in the band spectrum of The bulb is almost filled with mercury, and a small hydrogen. L. L. Bircumshaw. weighed amount of substance inserted through the Relation between specific heat, thermal ex inlet, which is then sealed. The substance is com pletely vaporised by immersion of the bulb in a pansion, and velocity of sound in liquids. B . 3ST. Sreenivasaiah (Indian J. Phys., 1927, 1, 255—266). suitable liquid, and the levels of the mercury in the —Theoretical. An extension of Ray’s work (Physical bulb and graduated tube are noted. A calculation is given for the determination of the vapour density, Rev., 1920, [ii], 15, 24). W. E. D o w n e y . due allowance being made for the mercury remaining Connexion between heat of fusion and specific in the bulb. , Satisfactory results were obtamed for a heat. K. Lichtenecker (Physikal. Z., 1927, .28, number of simple organic liquids. J. G r a n t . 473—475; cf. Skaupy, Verh. Physikal. Ges., 1916,18, 302) —It is shown that the heat of "fusion of ice is equal Germanium. XIX. Vapour pressure of ger to the integral of the specific heat from —273° to 0° manium tetrabromide. F.'M. B r e w e r and L. M. plus the heat of compression due to the change in D e n n i s (J. Physical Chem,, 1927, 31, 1101—1105).— The vapour pressure of germanium tetrabromide volume at the m. p. W. E. D o w n e y . determined over the range 0° to b. p. by the method Physico-chemical studies on tin. IX. Trans of Laubengayer and Corey (A., 1926, 931) gives the ition temperature grey tin === white tin. E. vahie of 186-5° forthe b. p. L. S. T h e o b a ld . C o h e n and K. D . D e k k e r (Z. physikal. Chem., 1927, 127, 178—182).—The transition temperature of grey Vapour pressure of acetone at low temper tin into white tin lies between 12° and 14-3°, the atures. E. H. A r c h i b a l d and W. U r e (Trans. most probable temperature being 13°. Roy. Soc. Canada, 1927, [iii], 21, III, 133—144).— Values of the vapour pressure of acetone between H. F. G i l l b e . Metastability of elements and compounds as —105° and 20° are tabulated and plotted (e.g., a result of enantiotropy or monotropy. X. 74-92 mm. at 0°, 185-57 mm. at 19-89°). The True specific heats of chemically and physically results accord with the equation : log P = —(o/T)t b log T-\-cT-\-dT2-\-e, where the logarithms of the pure white and grey tin. E. C o h e n and. K. D. constants a, b, c, d, and e are, respectively, 4-4022197, D e k k e r (Z. physikal. Chem., 1927,127, 183—217).— Chemically pure grey tin has been prepared from white 2-9123338, 0-2140094, 3-07S4S42, and 3-2374543. tin of known purity. The physical purity of the grey An equation expressing the variation of the latent modification was controlled by density measurements heat with the temperature has also been obtained. with the pykuometer and by X-ray observations. An abnormal maximum value at 4-6° indicates For pure white tin d'f. is 7-285, and for the grey form association followed by dissociation. 5-765. The true specific heats of pure grey and white A. A. E ld r id g e . tin have been determined by means of the electric Theory of the state of matter. K. M. Sta k - adiabatic calorimeter of Cohen and Moesveld. The horski (Bull. Soc. chim., 1927, [iv], 41, 775—787).— specific heat between 8° and 13° of grey tin is 0-0493 ± The molecular pressures, i.e., the quantity ajv- in 0-0002, and of white tin 0-0537;£0-0003. Further van der Waals’ equation, at 0-507V and 0-64Tc, i.e., evidence has thus been obtained for the untrustworthi temperatures in the vicinity of the f. p. and b. p., ness of physical data given in the literature, since the respectively, of a number of normal liquids have been measurements have in many cases been made on calculated by three methods, and the relation 5= physically impure substances. H. F. G i l l b e . IcyT¡Tc, where B is the molecular pressure, y the surface tension, and Tc a constant, has been confirmed. Determination of transition points with the Theoretical relationships between the molecular aid of a thermocouple. D. Cannegieter (Chem. pressure and various physical constants, e.g., speeihe Weekblad, 1927, 24, 350—-351).—The two transition cohesion, vapour pressure, latent heat, ebullioscopic points, at 60° and 180°, found dilatometrically for constant, etc., are derived and it is shown that lead by Travers andHouot (A., 1926, 893) have been Trouton’s rule, the f.-p. and b.-p. capillary relations investigated, using a lead-copper thermocouple. of Walden (A., 190S, ii, 1014) and Kistiakovski (A., The transition point at 60° could not be confirmed, 1906, ii, 655), respectively, and Beckmann’s expression and the second one was found to be at 182-5° after .for the ebullioscopic constant, ¿ = 0-00096ili2\ where -the metal had been heated for 36 hrs. or longer at M is the mol. wt., are all particular cases of muca 240°. S. I. L e v y . more general relationships. J. S. Ca r t e r . Density of carbon dioxide. S. W. P a r r and Theory of the state of matter. VIII. In te r n a l W. R. King, jun. (Univ. Illinois Eng. Exp. Sta. pressure and the theorem of corresponding Circ., 1926,13,1—21).—The earlier table (A., 1909, ii, states. F. Schtjster (Z. Elektrochem., 1927, ^ 234) is revised, values having been recalculated from 244—245; cf. this vol., 103).—The internal pressure. more accurate data. Between 10° and 30° the revised Pi, has been calculated for various substances by values are 0-0004—0-0016 mg. per c.c. smaller than relation 25t=94-47T(.T(log Pclp)IV('^c~^-'\’ w^'ere the former values. Chemical Abstracts. is any temperature, p the corresponding vaP,0 , Method for measuring vapour densities. P pressure, V the molecular volume in c.c., Tc the cn l B l a c k m a n (Chem. News, 1927, 135, 97— 100).—The temperature, and pc the critical pressure. ; apparatus consists of a short graduated tube drawn coefficient dprfdT at the b. p. has a value betueen - off and open, at one end, to the other end of which, is and 3 for many normal substances, but it decreas GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 819 with increasing Tc for compounds of a given type. Viscosity of liquids above their b. p. II. Higher values arc obtained for associated substances T. T i t a n i (Bull. Chem. Soc. Japan, 1927,'2,161— 171; and substances with unsaturated subsidiary valencies, cf. this vol., 616).—The usually-accepted definition of so that this coefficient may also be related to tpc, which molecular viscosity is held to be inadequate. The is high in such cases. H. J. T. E l l i n g h a m . distance between the sliding and stationary surfaces Solution of the ammonium chloride problem. should be taken as y 1/3, V being the molecular volume, A. Sm its (Rec. trav. chim., 1927, 4 6 , 445— 452).— and not as unity. According to the new definition The vapour pressure of ammonium chloride is lowered the true molecular fluidity Clausius-Mosotti formula. For the first five solutes at 1000° is due to a change in the molecular structur the molecular polarisation is proportional to the and to partial dissociation of the gypsum. mol. fraction in the solution. The electric moment H. F. G il l b e . of each solute is calculated; in the case of carbon Solubility of chromic hydroxide in aivans tetrachloride and p-xylene it is zero. R. B. C o r e y (J . Chem. Education, 1927, 4, 532—533) S. K. T w e e d y . —The view that chromic hydroxide and excess o: Electrical resistance of molten metals and aqueous alkali form a colloidal solution and not a alloys. Y. M a t u g a m a (Sci. Rep. Tôhoku Imp. chromite is supported by the observation that aftei Univ., 1927, 16, 447— 474).—The specific resistance segregation of the chromic hydroxide from such a of mercury, tin, bismuth, cadmium, lead, zinc, “ solution,” the liquid fails to respond to a test for antimony, aluminium, and silver, and of binary chromium. C h e m i c a l A b st r a c ts . alloys containing tin, bismuth, cadmium, lead, zinc, antimony, and copper has been determined at various Sucrose crystallisation. I. A . K u k h a r e n x o temperatures. The resistance of the pure metals and G . S. B e n i n (Zapiski [Russia], 1926, 4, 75—77, increases linearly with the temperature, but with 86— 91; cf. B ., 1927, 567).—The solubility of sucrose mercury the increase is more rapid. The resistanee- in aqueous potassium sulphate solutions^O-5—2-0%) at concentration and temperature coefficient-concen 50° diminishes with increase in the salt concentration. tration curves of alloys are smooth when there is no The speed of crystallisation of sucrose at 50° is compound formation, but otherwise breaks are not affected by the potassium sulphate, which is found at points which correspond with the com a negative molasses former. pounds formed. Increased dissociation of a compound C h e m ic a l A bstracts. in the liquid phase with rise of temperature is Lactic acid. IV. Partition of lactic acid said to be indicated by a negative temperature between water and ether, and between water and amyl alcohol. R. D i e t z e l and E. R osen coefficient. F. S. H a w k i n s . b a u m (Biochem. Z., 1927, 185, 275—286).—The Electrical and thermal conductivities of carbon observed partition coefficients are corrected for the steel and cast iron. H. M a s u m o t o (Sci. Rep. degree of dissociation of lactic acid. For water: ether Tôhoku Imp. Univ., 1927, 16, 417— 435).—'The at 20° the coefficient varies from 11-3 to 8-7 between measurements were made by an improved Kohlrausch 0-931 and 0-201 mol. per litre and for water: amyl method (A., 1925, ii, 503). The specific electrical alcohol it varies from 2-13 to 2-42 according to the resistance and the thermal conductivity can be concentration. Variation in temperature from 0° expressed as linear functions of the amounts of to 25° has little effect. In the case of amyl alcohol impurities by the equations a = l ,044+0,548C+ and water, the presence of 30% of anhydride (lactyl- 1-572Si+0-718Mn; l/X=5-744+2-432C+5-087Si+ lactic acid) in the lactic acid used lowers the partition 2-461Mn, when the total impurity is small. Withcoefficient a to about 1-75. C. R. H aringtok. larger carbon content, the rate of decrease of the two conductivities becomes smaller, and the ratio of Adsorption of carotin by charcoal and in thermal to electrical conductivity slowly increases. organic salts. S. G . W i l l i m o t t (J. Biol. Chem., Measurements made on chill-cast iron before and after 1927, 73, 587—592).—The discrepancy between the annealing show that the conductivities increase after results of Palmer (“ Carotinoids and Related Pig treatment, but further annealing causes no change ments,” 1922, 270) and those of Stephenson (A., 1921, until graphite separates, when a considerable increase i, 295) is explained by the varying capacity of different in both the conductivities and their ratio occurs. samples of charcoal to adsorb carotin. The amounts Measurements were also made on K.S. magnet steel required to adsorb the carotin from 100 g. of butter fat ranged from 3-5 g. with Norit (vegetable charcoal) and gold. F. S. H a w k in s . to 40 g. with ordinary decolorising charcoal. Various Solid solubility of antimony in lead as deter inorganic compounds were found to be poor adsorbents mined by conductivity measurements on cold- for carotin, but red antimony trisulphide was as worked alloys. E. E. Schumacher and G. M. active as the poorer grades of charcoal, whilst black B o u t o n (J. Amer. Chem. Soc., 1927, 49, 1667— 1675). antimony trisulphide was quite inactive. —The solid solubilities of antimony in lead were C. R- H arin g ton. determined by conductivity measurements on severely Heat of adsorption of gases by charcoal. S. J- cold-worked alloys : 146°, 0-70% ; 100°, 0-52% ; G r e g g (J .C .S ., 1927, 1494— 1512).—For the adsorp 70°, 0-48%; 40°, 0-32%; and 25°, 0-24%. Cold tion of nitrous oxide, acetylene, ethane, carbon working causes the précipitation of excess of antimony monoxide, sulphur dioxide, carbon dioxide, ethylene, from the supersaturated solution in a few hours; and nitrogen by charcoal, measurements have been normally, this process takes years. A revised phase made of the heat change, the equilibrium pressure, diagram for the lead end of the lead-antimony system and the quantity adsorbed. Most of the expenmen s is given. S. K. Tweedy. were conducted at 0°, employing the Bunsen ice Solubility of natural hemihydrate of gypsum calorimeter, whilst others were carried out at 40-o» , after heating at various temperatures. A. J. using phenol in the calorimeter. For the mte§^a S w o r y k t n (Z. anorg. Chem., 1927, 163, 178— 184).— heat of adsorption Q, the relationship ho s> The solubility of the natural hemihydrate of calcium where z is the quantity of gas adsorbed, and k an a sulphate, determined by measurements of con are constants. For all gases except those with a mg ductivity, decreases with rise of temperature of critical temperature, the Williams-Henry equatl° ignition. An increase in the solubility after ignition log x/p=A0—A lx is valid, p being the equihbnu GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 821 pressure and A0 and A x constants which depend on the acid and sucrose, and possibly the water also, the temperature. With the same restrictions, the are “ bound ” in some manner. Tho adsorption of modified Iljin equation Q =B log (p/a.+l)+A is also acids does not imply a high concentration of hydrogen applicable; in this a is a constant which increases as ions around the adsorbent, the adsorbed acid being the van der Waals constants a and b decrease. probably in an undissociated and unoriented state. H. F. G i l l b e . S. K. T w e e d y . Sorption of hydrogen by palladium on various Adsorption. XIX. Adsorption of electrolytes carriers. T. Sabalitschka (Arch. Pharm., 1927, by manganese dioxide. Freundlich adsorption 265,416—424; cf. Sabalitschka and Moses, this vol., formula. M. N. C h a k r a v a r t i and N. R . D h a r 427),—The absorption of hydrogen by palladium (J. Physical Chem., 1927, 31, 997— 1033).—The deposited on blood, bcech, sponge, and bone charcoals, adsorption of various cations by a sol of negatively barium sulphate, and kieselguhr has been examined. charged manganese dioxide during coagulation has All the carriers, freshly cleansed, were loaded with been measured, and shows that, contrary to the views palladium to 2-5% of their weight. No distinction is of Bancroft (A., 1915, ii, 424) and Weiser (A., 1925, drawn between hydrogen simply absorbed and ii, 855), but in agreement with the work of Ghosh and hydrogen taken up as palladium hydride. The Dhar (A., 1925, ii, 511) and others, the higher the carriers alone show a definite saturation capacity on valency of an ion the less is the adsorption, the order repeated treatment, thus : blood charcoal, 1-35 c.c. of decreasing adsorption being silver, potassium, per g.; bcech, 0-94; sponge, 0-84; bone, 0-72; copper, lithium, barium, strontium, cerium, aluminium, barium sulphate, 0-00; kieselguhr, 0-26, but when the and thorium. The high adsorption observed for sols palladium is present the absorptive capacity is not of manganese dioxide and of ferric, aluminium, and constant but rises to a maximum and then (after the chromium hydroxides is due more to the adsorption third or fourth treatment, with interposed exhaustion of electrolytes by the freshly coagulated mass than to at 300°) shows a decline. For the various systems, charge neutralisation, and the interpretation of the the figures (at this maximum) are 7-49, 2-20, 10-46, Schulze-Hardy law (that the greater is the valency the 5-27, 8-18, and 1-91, respectively. These correspond less is the adsorption) should be strictly applicable only with the following when referred to the palladium to cases in which adsorption is due to charge neutralis present: on blood charcoal, 2924 c.c. per g. Pd, ation. Experiments on the adsorption of cations by beech, 867; sponge, 4581; bone, 2167; barium a sol and by freshly precipitated manganese dioxide sulphate, 3895, kieselguhr, 910. These results agree give results in agreement with this interpretation. with such earlier ones as can be compared. The Manganese dioxide, being acidic, adsorbs hydroxyl rise of the absorptive activity to a maximum and the more readily than hydrogen ions. The value of the subsequent decline are due to the gradual conversion constant in the usual Freundlich equation depends of the palladium from the amorphous into the on the strengths of the organic acids adsorbed by crystalline form. W. A. S i l v e s t e r . the hydroxides of iron, chromium, and aluminium. When the adsorbent remains the same or chemically Adsorption isothermals. H. B r a d l e y (Nature, similar, the value of the exponent changes little when 1927, 120, 82).—The formula a = [f(T )p TI2nx]/[ 1 + the substances adsorbed are similar. With electro '¡i(T)pTmx], where a is the amount adsorbed,/(T) and lytes, however, it varies with concentration. ji[T) are functions of T°Abs., and p is the equilibrium The chief factor in adsorption with a positively pressure of the gas, is in good agreement with various charged sol of manganese dioxide is the chemical series of experimental results when x is unity, or a affinity of the coagulum, and in this case the ratio of small integer. When combined with Gibbs’ adsorp positive to negative ion adsorbed is always greater tion^ formula a— — (clRT)da-/dc, an equation is than unity and decreases with a decrease in con obtained which reduces to Szyszkowski’s empirical centration of the sol. formula for T=273 and x —1. A. A. E l d r i d g e . The whole investigation supports the view that Adsorption from solution by ash-free adsor chemical affinity is the preponderating factor in bent charcoal. IV. Non-inversion of sucrose adsorption phenomena. L. S. T h e o b a l d . by adsorbed acids and its significance for theories of adsorption and catalysis. E. J. Effect of inorganic salts on the adsorption of M iller and S. L. B a n d e m e r (J. Amer. Chem. Soc., inorganic acids and bases. L. It. P a r k s and 1927, 49, 1686—1697; cf. A., 1925, ii, 656).—Inor P. G. B a r t l e t t (J. Amer. Chem. Soc., 1927, 49, ganic, aliphatic dicarboxylic, and aromatic acids 1698— 1709).—The adsorption of 0-01iV-hydrochloric irreversibly adsorbed on ash-free charcoal are unable and -nitric acids by pure active sugar charcoal . mvert sucrose at 80°. This is an extreme example increases rapidly with increasing concentration of the °‘ negative catalysis in which both reactants are corresponding sodium salt until the latter reaches adsorbed. Experiments on the adsorption of dextrose 0-75N, after which the amount of acid adsorbed is a rom sucrose solutions indicate that strong adsorption linear function of the salt concentration. A maximum 0 the reaction products is not the cause of this is never attained. Nitric acid is adsorbed to a greater negative catalysis. Inversion always occurs when the extent than hydrochloric acid. Similar relationships lv ttf reversibly adsorbed and a portion is displaced hold for O-OlN-sulphuric acid except that, contrary J ne sugar, the change being produced by the dis- to the results of Michaelis and Rona (A., 1920, ii, 1 , e<~ Part- Charcoal containing acid and water 168), the adsorption diminishes with increasing con ^sorbed from salt solutions (A., 1924, ii, 664) is centration of sodium sulphate. Experiments with apable of inverting sucrose, suggesting that both salts having no common ion are also described. 822' BRITISH CHEMICAL ABSTRACTS.— A. Mixtures of two acids show an adsorption which lies Adsorption and surface charge. I. Metallii between the values for the separate acids. Experi oxides. P. B a r y (Rev. g6n. Colloid., 1927, 5, 517- ments with blood charcoal gave results similar to the 522).—It is supposed that the phenomena of adsorp above; sodium hydroxide is more strongly adsorbed tion and of surface electric charge have a commoi as the sodium chloride concentration rises and the origin, and are due to the chcmical action of th< adsorption of sodium hydrogen sulphate is rapidly medium on the solid particles in contact with it depressed by the addition of sodium sulphate, which The view that the oxides of multivalent metals are in is contrary to the results of' Michaelis. The pheno general polymerised is discussed, with special reference mena of adsorption from solution arc explained on the to ferric and aluminium hydroxides. The electric basis of the attraction of ions by colloid particles. charge which the oxides assume in contact with water Neutral inorganic salts are not hydrolytically adsorbed and aqueous solutions, no matter whether the oxides in presence of inorganic acids or bases. are hi colloidal solution, in suspension, or present as S. K. T w e e d y . a porous mass, arises from the electrolytic dissociation Adsorptive properties of cellulose. H. T a m iy a of a complex compound formed between the oxide and N. I s h u j c h i (Acta Phytochim., 1926, 2, 139— and the solvent. The hypothesis of adsorption is 192).—Pure filter-paper adsorbs cations'from a solu thus avoided, and the question may now be considered tion of electrolyte, whereby the acidity of the solution as consisting of a simple hydration of the oxide, using is correspondingly increased. If the cellulose itself the primary valencies of the new compound formed by contains electrolytic impurity, cations are transferred the rupture of molecular chains. Tho oxides of this to tho solution, with consequent decrease in acidity. type must be regarded as never absolutely pure, These two opposed cfleets lead to amphoteric be every molecule, whatever its length, having polar haviour of cellulose and filter-papers therefore show groups, such as H and OH, or H and Cl, or N il and variation in their reaction towards j)n indicators. OH, at its extremities. L. L. Bircumshaw. The ps tests thus give valuable information as to the purity of filter-papers. The adsorption of dyes on Effect of water on the formation and spreading cellulose is influenced by the amount of electrolyte of fatty oil films. L. A l te r (Koll.-Chem. Beihefte, both in the cellulose and in solution. Enzymes are 1927, 24, 268—318).—The process of the drying of adsorbed on cellulose in very different amounts. fatty oils is discussed. When exposed to air, absorp Diastase, urease, emulsin, and invertase are but tion of oxygen and water takes place, and the oil little if at all adsorbed, whereas trypsin, pancreatin, increases in weight. The curves obtained by Weger, catalaso, and pepsin are strongly adsorbed. This connecting the increase of weight of the oil with time, provides evidence for the difference in sigh of the are not true adsorption curves, since a simultaneous electric charge carried by the enzyme colloid. Non loss of weight occurs, due to the formation of volatile electrolytes arc apparently not adsorbed on cellulose, products. From experiments with the oil spread on even when they possess strong surface activity. The plates of glass contained in a series of desiccators kept presence of the electric double layer on the cellulose at constant temperature, each desiccator containing micelle surface, to which the adsorptive power of the a different mixture of water and sulphuric acid, giving cellulose is to be ascribed, was demonstrated by an a definite pressure of water vapour, it is concluded electric endosmose apparatus. The electro-potential that the apparent adsorption curves of Weger cannot on the cellulose surface is affected by electrolytes in be resolved into two independent curves, representing solution, the effect being determined by the valency of the absorption of oxygen and of water vapour, as the ions concerned and by the j)a of the solution. formerly supposed. The effect of water appears to L. M. Cl a r k . be entirely physical, the irregularities in the vapour- Surface phenomena and adsorption at the pressure isotherms being ascribed to secondary com contact of two liquid phases. R. D u b r i s a y (Rev. plications. The experiments performed in a vacuum gen. Colloid., 1927, 5, 533—539; cf. this vol., 618).— gave results in best agreement with those expected An account is given of previous experiments on in a swelling process. The gas coagulation theory adsorption at benzene-soap solution surfaces (using and the adsorption theory are regarded as working sodium laurate and sodium glycoeholate) in presence hypotheses which arc not free from objection. of 1% of sodium chloride (cf. A., 1926, 672), which E. S. Hedges, support the hypothesis that electrolytes which Reactions in the solid state. B. G arbe (Z. diminish the concentration of the soap increase the anorg. Chem., 1927, 163, 43—iS).—The compactness amount adsorbed at the interface. This receives of compressed powders, both before and after heating further support from measurements of the adsorption at a moderately high temperature, has been studied. of various dyes from aqueous solution by sand, cotton, Dry quartz powder cannot be compressed into a kieselgulir, etc., in presence of small quantities of pellet under the conditions employed, but with in coagulating substances. The author’s theory that creasing percentages of water the compactness ot a the less soluble of two substances, dissolved at the pellet, formed under a constant pressure, increases. same molecular concentration in the same solvent, If the pellet be heated at 500°, in which case tie is the more strongly adsorbed is discussed, and shown water is replaced by air, the compactness decreases to follow from the thermodynamic adsorption theory with increase of the initial water content; heating a of Gibbs. A summary is given of earlier work 900° reverses the effect owing to change of crys a (A., 1918, ii, 368; 1923, ii, 741; 1924, ii, 154, 731), structure. The weight of quartz in a pellet of con and applications of the results to colloid-chemical stant dimensions decreases with increase of wa e problems are indicated. L. L. B ir c t t m s h a w . content. The binding power of the water is thus e» GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 823 than the reduction of compactness caused by the Mainly theorotical. T h e conception of sediment decrease of density. Similar results have been ation equilibrium is discussed with reference to the obtained for a number of other powders : the com work of previous investigators. Additional data pactness of organic powders, formed under constant on a mercury sol support the conclusions of Burton pressure, increases very rapidly with temperature (A., 1924, ii, 459) and of Porter and Hedges (A., as the m. p. is approached. H. F. G i l l b e . 1923, ii, 743). L. S. T h e o b a l d . Friction of solids. A. M a l l o c k (Nature, 1927, 120, 44—46).—Tho coefficients of friction between Rôntgenographical investigation of inorganic various metals and alloys and sapphire for pressures colloids. J. B ö h m (Kolloid-Z., 1927, 42, 276— up to the limiting pressure (except for steel) are 284).—The theory and practice of tho Debye- tabulated. Tho differences between the values for Schcrrer method of investigation are discussed, and the various metals are small. When the pressure its applicability to. tho study of colloidal systems is high, the presence of a lubricant nearly always is considered, with special reference to colloidal gold, increases the coefficient of friction. silver, platinum, and stannic acid, and aged sols of A. A. E l d r i d g e . ferric hydroxide and vanadium pentoxide. Natural rotatory dispersion in the ultra L . L . B i r c u m s h a w . violet of. aqueous solutions of the neutral tartr Increase of Brownian movement by light. ates of sodium, potassium, and ammonium. W- P o s p î s i l (Atm. Physik, 1927, [iv], 83,735—752).— R. D e sca m p s (Compt. rend., 1927,185, 116— 119).— Experiments on the dependence of the Brownian The dispersion of solutions of . tartaric acid has been movement on the intensity of the applied illumin determined at various stages of neutralisation by ation show that in the case of substances which do alkali hydroxides, for wave-lengths of 5780—2536Ai not absorb the light (e.g., mastic), no detectable The Darmois lines were found to intersect at points change is observed when the intensity of tho illumin which lie on a straight line, and not in a single point ation is varied a thousandfold. In the case of light- absorbing substances (carbon, gamboge) the move as is indicated by Vellinger’s measurements in the ment increases appreciably with increasing intensity visible spectrum (this vol., 500). J. G r a n t . of illumination. The observed phenomena cannot Colloidal iodine. W. L. C h a n d l e r and E. J. be explained on the basis of the kinctic theory. It M ille r (J. Physical Chein., 1927, 31, 1091— 1096; is suggested that the assumption of a photoelectric cf. Am arm, A., 1912, ii, 751).—Stable suspensions or a radiation effect offers a plausible explanation. of colloidal iodine have been prepared by rapidly J . S. C a r t e r . acidifying with concentrated hydrochloric acid a SoltLbility and particle size. IV. D. B a l a r e v dilute solution of sodium hypoiodite in the presence [with A. Kovandjiev and K. Kuleliev] (Z. of gum arabic at 0°. The colour varies with the anorg. Chem., 1927, 163, 213—216).—Colloidal conditions of formation from brick-red, light brown, barium sulphate has been prepared from barium or chocolate. The size of particles is approximately chloride or acetate in aqueous alcoholic solution by 0-2 (i. The iodine is probably in tho form of an the addition of sulphuric acid. Tho size of the emulsion in water. Concentration of the emulsion smallest particle is about 0-1 and a saturated to a dry condition can be effected by the addition of aqueous solution at 25° has a conductivity of 3-3— sufficient dextrose or gum arabic. Re-dispersion in 3-5 XlO'6 ; the conductivity of a saturated solution water is unaffected by this treatment. of the ordinary form is about 2-86 X 10~6. Electro The possible uses and advantages of colloidal iodine lytes adsorbed on the sol particles have a large as an antiseptic are indicated. L. S. T h e o b a l d . influence on the stability of the sol and therefore on Aerosols. V. K ohlschutter (Kolloid-Z., 1927, the apparent solubility. Fine crystals of barium 209—223).—A general survey of the properties and sulphate having a minimum particle size of about conditions of stability of aerosols. The points of 0-2 n have been prepared by the addition of dilute resemblance and the differences between aerosols sulphuric acid to a boiling dilute solution of barium and hydrosols are discussed. A distinction is drawn chloride; the conductivity of a saturated solution of between true aerosols and dust clouds, based on the this form is 2-89—3-0xl0~G. electrical properties of the latter. The aggregation Temperature fluctuations in the neighbourhood of particles in smokes is considered, together with of 20° cause the rapid disappearance of the smallest methods for measuring their size and density. Ex particles from an aqueous suspension of finely- periments are described dealing with the behaviour divided gypsum, whilst at 38°, at which temperature o£ oxide smokes and the formation of smoke gels. the solubility curve of gypsum is nearly horizontal, L. L. Blrcumshaw. temperature fluctuations have no effect. The ratio Atmospheric disperse systems and their of the rate of crystallisation to the rate of dissolution physico-chemical and electrical properties. A. of gypsum in the neighbourhood of the saturation S ta ger (Kolloid-Z., 1927, 42, 223—229).—Various point at 25° is about 8 :1 . The determination of atmospheric disperse systems are described, and both velocities is affected considerably by the in methods for investigating them are outlined. The fluence of temperature changes on the disappearance origin of the electric charge on ionised air particles of the smaller particles. The long period required and dust particles, etc., is discussed. for equilibrium to be attained in the system, finely- L. L. Bircttmshaw. divided gypsum-water cannot be entirely explained Sedimentation of colloidal particles. F. W. by the differences in the surface tensions of the UlRB (J- Physical Chem., 1927, 31, 103^-1049).— different-sized particles. Stirring a suspension of 824 BRITISH CHEMICAL ABSTRACTS.----A. gypsum in water causes at first an increase in the slowly transformed into platinum amalgam hydrosol number of the smallest particles, and only after pro and free hydrogen. H. W r e n . longed stirring is a suspension obtained in which the Non-liquid disperse systems of the fatty oils. smallest particles are larger than those existing in L. A u e r (Kolloid-Z., 1927, 42, 288—292).—Systems the suspension before stirring. containing no non-oily constituents are considered. Neither by breaking down crystalline particles nor Cases of “ film ” formation and of the solidification by precipitation from colloidal solution can exact of the oil to a jelly are discussed. For some oils determinations be made of the solubility of very small (e.g., wood oil), a disperse phase and dispersion particles. H. F. G i l l b e . medium are already present, but in many raw, un boiled, fatty oils a disperse phase must be formed, or, Optical behaviour of protein solutions. C. V. if present, must be concentrated before gel-formation R a m a n (Nature, 1927, 1 2 0 , 158).—The variation of can occur. The action of gases in film-formation is the Tyndall effect in gelatin solutions with pa and explained on the assumption that they not only temperature is explicable according to the general thermodynamic theory of light scattering, whereby behave as coagulators, but are also responsible for the formation of the micelles of the disperse phase. the scattering power of a colloidal solution is connected with the osmotic pressure P of the L. L. B ir c u m s h a w . particles by the relation [7r2i?T/2iVx4][£(S£/8fc)2p/ra]/ Whetham’s law and the law of mass action, and their application to the coagulation of (SP/Sk), where k is the concentration of the dis colloidal platinum. S. W. P e n n y c u i c k (Austral. persed material, s is the optical dielectric constant J. Exp. Biol., 1927, 4, 99— 112).—By the application of the solution, and p/m is practically unity for a of the mass law to the coagulation of colloids by dilute solution, for the osmotic pressure becomes very small at the isoelectric point. electrolytes it is shown that Whetham’s law, and also the law of mass action when based on similar A . A . E l d r i d g e . principles to those on which Whetham’s law is Dispersoidological investigations. XII. Cel lulose dispergation in concentrated aqueous based, lead to quantitative relations which are not in accord with experimental facts, and it is concluded solutions of calcium iodide. P. P. v o n W e i m a r n that Whetham’s law is theoretically unsound. and H. H o r i . XIII. Strontium iodide. P. P. Assuming that coagulation occurs when the charge v o n W e i m a r n and K. J u n a . XIV. Barium on the colloid is wholly or partly neutralised by iodide. P. P. v o n W e i m a r n and S. K a t o k a . XV. combination with an ion carrying the opposite Potassium, sodium, and lithium iodides. P. P. charge, the proportionality^:^ : p3= l : 1 /Cj:(Í/Cr12) v o n W e i m a r n and K. J u n a . XVI. Lithium is deduced, p v p2, p3 being the coagulating powers of bromide. P. P. v o n W e i m a r n and T. Y o n e d a uni-, bi-, and ter-valent ions, and Gx the corre (Rep. Imp. Ind. Res. Inst. Osaka, 1926, 7, No. sponding coagulating concentration. The deduction 17, 7— 18, 19—26, 27—36, 37—44, 45—51; cf. of Whetham’s law on comparable lines leads to the A., 1926, 576).—Dispersions of cellulose (3%) same relation. By adopting Robertson’s assumption prepared by boiling filter-paper with saturated that one colloid particle combines with one univalent calcium iodide solution for 10 mm. gelatinised, on ion, and two colloid particles with one bivalent ion, cooling, at a higher temperature than when calcium etc. (cf. “ The Physical Chemistry of the Proteins,” thiocyanate was used. Thus calcium iodide has a 1920, 116), the relation p x : p2 : p3= l : Q : Qi is smaller dispergating power than calcium thiocyanate, deduced, Q being the colloid concentration. A large but greater than that of calcium bromide. Alkalis number of coagulation experiments were made, retard and acids accelerate the dispergation. Stron using very pure colloidal platinum and a series of tium salts are in the descending order: thiocyanate, electrolytes with uni-, bi-, and ter-valent cations, iodide (< calcium iodide), bromide, chloride. but none of the above relations could be confirmed. Barium iodide is intermediate between the bromide The theoretical and observed results differ so and thiocyanate. The alkali iodides are in the greatly as to suggest that the theoretical relations descending order of dispergating power : lithium, give no quantitative indication of the relative sodium, potassium. The lithium salts are in the coagulating powers. L. L. B ir c u m s h a w . descending order : iodide, bromide, chloride. C h e m i c a l A b s t r a c t s . Physico-chemical properties of Japanese acid Platinum hydride hydrosol and its dehydro clay. I. Ultramicroscopio observations. K. genation by metallic mercury. C. P a a l and C. K o b a y a s h i and K . Y a m a m o t o (J. S o c . Chem. Ind. A u e r s w a l d (Ber., 1927, 6 0 , [5], 1648— 1654).—A Japan, 1927, 3 0 , 431— 435).—Ultramicroscopio solid, colloidally soluble preparation of platinum photographs of several acid clays, colloidal carbons, (33-88% Pt) protected by sodium lysalbate is dis silica gels, etc., have been taken by means of a ear- solved in water and the solution is alternately dioid ultramicroscope and the sizes of the particles saturated with hydrogen and exposed for varying determined by using a slit ultramicroscope. The acid periods to the air. The largest quantity of hydrogen clay is composed of extremely minute particles com is absorbed by the original material which, during pared with other clays; the radius of the particles the process of drying, is freely exposed to the air which remain in suspension after centrifuging at 4000 during several days. Under these conditions it revolutions per minute fell between 1X 10~5 and appears to absorb 2-03% of oxygen, equivalent to 2 x l0 "5 cm. The acid clay when calcined at 300^ 305 vols. of the gas per vol. of metal. If the platinum shows no perceptible change of structure, but at 500 hydride hydrosol is shaken with mercury it becomes the colloidal character disappears. K. K a s h i m a . GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 825 Influence of concentration of colloidal solutions obtained for the amount of swelling at equilibrium on the quantity of electrolyte necessary for in terms of the elastic constant of the gelatin. flocculation. A. B o u t a r i c and ( M l l e . ) G. P e r r e a u W. O. K e r m a c k . (J. Chim. phys., 1927,24, 496—506).—The minimum Swelling of isoelectric gelatin in water. II. quantity a of different electrolytes which produces Kinetics. J. H. N o r t h r o p and M. K u n i t z (J. Gen. flocculation in ferric hydroxide and arsenious Physiol., 1927, 10, 905—926).— On the basis of the sulphide sols of a definite concentration has been mechanism for the swelling of isoelectric gelatin determined. The ratio of the values of a for two previously described (see preceding abstract), different electrolytes varies with the concentration equations are deduced for the kinetics of swelling of the sol when the coagulating ions differ in valency, which agree well with experiment. The effects of but remains practically constant for ions of the same the size and the shape of the block of isoelectric valency. Schultze’s rule is obeyed qualitatively but gelatin can in this way be accounted for, and the not quantitatively. Kruyt’s theory is discussed, and permeability of gelatin to water, calculated indirectly it is shown that the results, in the case of ferric from swelling experiments, has been verified by hydroxido sols, are in direct contradiction to it. direct experiment. Equations are also deduced The limiting quantities of electrolyte necessary for which describe the secondary swelling which occurs flocculation per g. of colloid have been compared. as a result of elastic fatigue of the gelatin, and these In the case of ferric hydroxide coagulated by a salt equations are also found to agree with the experi with a multivalent anion, the curve connecting the mental facts. W. O. K e r m a c k . time t with the quantity q of electrolyte has three Cataphoresis in mixed solvents. Theory of branches with asymptotes at q=a, b, and c, and two coagulation. J. J. B i k e r m a n (Kolloid-Z., 1927, zones of precipitation, one for values of q between 42, 293—295; cf. A., 1925, ii, 522).—Measurements a and b and the other for values of q greater than c. have been made of the cataphoresis of colloidal The ratios of a, b, and c to the concentrations C of sol solutions of arsenic trisulphide in water-propyl for the coagulation of ferric hydroxide sol by sodium alcohol mixtures in presence of calcium nitrate phosphate, sodium citrate, and potassium ferro- solution. The viscosity and dielectric constant of cyanide have been determined. Whilst a¡C and the mixtures varied in the ratio 1:3-5 and 1 : 4, i/C increase as G increases, c/C diminishes. respectively. Precipitation occurs at a critical M. S. B u r r . potential which is practically independent of the Hofmeister series. E. H. B u c h n e r (Rec. trav. solvent and of the concentration of the sol. This chim., 1927, 46, 439—444).—The salting-out in confirms the results previously obtained by the fluence of various salts on gelatin sols has been author (loc. cit.). L. L. B i r c u m s h a w . determined, and the variations of the salting-out eSect with temperature and sol concentration have Diffusion of water into lecithin-collodion mem been measured. All inorganic univalent ions pro branes. H. A . A b r a m s o n and S. H. G r a y (J. Biol. mote the swelling of gelatin, whereas the majority Chem., 1927, 73, 459— 462).—The rate of diffusion of multivalent ions have the reverse effect. of water into collodion sacs containing solutions of sodium sulphate or calcium chloride was not H. F. G i l l b e . Behaviour of alcohol-soluble proteins in mixed affected, between pa 2 and 12, by the presence of solvents. III. Denaturation of wheat gliadin. 50% of lecithin in the collodion. C. R . H a r i n g t o n . M. J. Gottenberg and C. L. A l s b e r g (J. Biol. Chem., 1927,73, 581—586).—The critical peptisation Effect of hydrogen- and hydroxyl-ion concen temperature, i.e., the temperature at which turbidity tration on water transport through a collodion fet appears on cooling the solution, is raised on membrane. P. J. JuRi&id (Biochem. Z., 1927,185, keeping solutions of gliadin in 20— 30% alcohol for 423—426).—The rate of transport of water across a some days at temperatures of 4—58°, and is lowered collodion sac, containing sodium sulphate solution by keeping the solution in 70—90% alcohol under and dipping into water, is delayed by addition of acid similar conditions. Solutions in intermediate con and accelerated by addition of alkali, in concentra centrations of alcohol undergo no change. tions of N 120,480 and upwards, to the sodium sulphate solution, the maximum effect being reached at N/80. C. R. H a r i n g t o n . Swelling of isoelectric gelatin in water. I. The potential difference set up between inner and outer solutions is increased by addition of acid and «phhbrium conditions. J . H . N o r t h r o p (J . jjen. Physiol., 1927,10, 893—904).—Experiments on reduced by addition of alkali. C. R. H a r i n g t o n . ae swelling of isoelectric gelatin confirm the view that Capillary action of filter-paper. L. J e n d r a s - 1 c.onsists of a network of insoluble elastic fibres s i k and A . C z i k e (Biochem. Z., 1927, 185, 470— enclosing a more soluble material, the osmotic 476).—Rapid stroking of the surface of an aqueous pressure of which causes the elastic fibres to expand solution with a piece of filter-paper raises the surface i equilibrium is reached (cf. A., 1926, 1098). If tension, if this was originally lower than that of aW Tu 'Si ^ar8e s? that the expansion is consider- water. Prolonged contact of the filter-paper with e the elastic limits may be exceeded and a the solution lowers the surface tension, the effect ■i01} swelling then occurs which may go on being due either to impurities in the paper (which hWi- f i A ^oss elasticity is also observed if a may be removed by extraction with alcohol), or, hi wtio t° , • a^n> after attaining equilibrium in water, the case of such solutions as those of alkaloid salts, swell;6 m air anc^ replaced in water, when secondary to the acid-binding power of the paper. ng occurs. A mathematical expression is C. R. H a r i n g t o n . 826 BRITISH CHEMICAL ABSTRACTS.— A. Influence of the orientation of the molecules Hydrodynamics and the kinetic theory of in the clogging of filters and ultrafilters. G. gases. Y. R o c a r d (Ann. Physique, 1927, [x], 8, G é n i n (Rev. gen. Colloid., 1927, 5, 523—532).—The 5— 120).—A brief description is given of the classical results obtained by Wilson and Barnard (cf. B., 1922, method which leads to equations for the motion of 929A) in their investigation of the influence of the the particles of a perfect gas according to the kinetic nature of the capillary wall and of the liquid on the theory. Adopting the results obtained by Chapman rate of flow of liquids through capillary tubes are (Phil. Trans., 1916, A, 211, 337) and Jones (ibid., explicable on the basis of the Langrauir-Har kins 1922, A, 223, 1) in their work on the function for the orientation hypothesis. The phenomenon of clogging distribution of the velocities, the equations of the in ultrafiltration may be explained in the same way. motion are given in an explicit form. The first The rate of flow of a given oil through a cellulose approximation gives the equations of viscous flow, nitrate membrane is found to decrease rapidly when whilst the following approximation yields the com a laboratory ultrafilter is used, whereas with an plementary terms which, among other properties, industrial ultrafilter the decrease is much less marked. contradict Lagrange’s theorem. An analogous study Moreover, the effect is much greater in the case of is-made for gaseous mixtures, and in the equations vegetable oils than with mineral oils or aqueous for the motion a new term is inserted which expresses liquids. It is assumed that the pores of the filter the influence on the complete motion, or on that of become lined with layers of oriented molecules of each constituent: considered separately, of variations fatty acids (supposed to be always present in the of composition of the gaseous mixture by diffusion oil, however highly purified it may be), which decrease processes. An attempt is made to construct a ‘ ‘ hydro the size of the pores and eventually, in some cases; dynamics ” of compressed gases on the basis of the cause complete obstruction to the passage of the kinetic theory. The calculations are possible only in liquid. The fact that with the industrial apparatus the case of gases which obey van der Waals’ criteria. the effect is only slight is attributed to the more An analysis is made of the new terms which appear in rapid circulation of the oil, which might prevent the equations of the motion of a compressed gas, orientation of the molecules and their consequent and express the influence on the motion of inter- adsorption, on the filter surface. The influence of molecular forces and of molecular impacts. The clogging in ordinary filtration is considered, and the former give a precise meaning to the.terms SP/S.r, application of the orientation hypothesis to a number SP/8y, SPlSz, of classical hydrodynamics; the latter of filtration problems is discussed. deaTwith the viscous properties, and are, in effect, a L. L. Bibottmshaw. correction to the coefficient of viscosity, for which a Law of capillary flow in the case of colloids. rigorous expression is obtained as a function of the A. W. P o r t e r and P . A. M. R a o (Trans. Faraday Soc., specific volume. For the hydrodynamic treatment 1927, 23, 311—314).—Determinations have been of this problem it is necessary to know, besides the made by the capillary tube method of the flow, equations of motion and the equations of state, the under various pressure-gradients, of starch sols of equations of heat transfer. In simple cases this different concentrations. An equation has been reduces to the adiabatic hypothesis, but in the case deduced connecting flow with longitudinal pressure- of compressed gases new terms appear which lead gradient, the radius of the tube, and the viscosity, and to a rigorous expression for the coefficient of thermal also an expression showing approximately the depend conductivity as a function of the specific volume. ence of viscosity on concentration. M. S. B u r r . The results obtained are obviously only remotely comparable with the experimental data, but by Electro-endosmosis of aqueous solutions considering an arbitrary molecular model, consisting through a diaphragm of sintered glass powder. of a molecule having a very intense force of attraction F. Fairbrother and H. V a r l e y (J.C.S., 1927, acting over a very small range, satisfactory compari 1584— 1589).—Electro-endosmosis experiments with sons with experiment are obtained for the variation a diaphragm of sintered glass in water and in dilute in the coefficient of viscosity of carbon dioxide with hydrogen chloride solution show that in water, after pressure. L. L. Birotjmshaw. an initial period, the amount of electro-endosmosis decreases with time, the glass becoming less negative; Dissociation of carbon dioxide at high tem in 001Ar-hydrogen chloride solution reversal is peratures. R. W. P e n n i n g and H. T . T izakd observed. The permeability of the glass to water (Proc. Roy. Soc., 1927, A, 115, 31S—333).—A simple also decreases with time. The suggestion is made relation is shown to exist between the composition ot that these effects are due to swelling of the glass the carbon monoxide-air mixture giving maximum surface, whilst to account for the reversal it is sug pressure on explosion and the dissociation of carbon gested that the distribution of potential at the inter dioxide at the maximum explosion temperature, n face is that described by Freundlich (“ Kapillar- the initial composition and the composition at the chemle,” 1922,. 342). H. F. G i l l b e . maximum temperature a re represented by the express' Kinetics of osmosis. J. H. N o r t h r o p (J. Gen. ions 2(l+a)C0+02+6Na and 2(l-*)C02+2(fl+ Physiol., 1927, 10, 883—892).— By combining the a:)C0+a;02+iN 2, respectively, then x—a/b when laws for osmotic pressure and rate of diffusion, an Pe, the maximum pressure observed after explosion, expression is obtained for the rate of osmosis, and is a maximum. Thus the dissociation of carbon this has been verified experimentally in the case of a dioxide at high temperatures may be determined by collodion membrane containing a solution of egg- adding carbon monoxide in varying quantities to a albumin or of gelatin. W . 0. Kermack. standard mixture of nitrogen and oxygen, an GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 827 measuring tho pressures reached on exploding the Second law of thermodynamics. E . D e n i n a different mixtures. The value of a when the explosion (Gazzetta, 1927 , 5 7 , 415—451).—The analyses ad pressure is a maximum is read off from the curve vanced in tho author’s recent contributions to"thermo representing the results, x is given by a/b, and Kv dynamics (cf. this vol., 314,316) have been summarised by the equation Kp=\{a-\-x)l(\ —x)]2xx/(2-\-2a+ and co-ordinated. The fundamental concept is the x-\-b)X.Pf By varying tho proportion of nitrogen to definition of the second law in the following form : oxygen, the dissociation has been determined over a that for any reversible cycle associated with a change wide temperature range, and the constants found from of energy, dW, there exists a quantity P such that the explosion experiments by this method agree the integral JP~ldW throughout the cycle is zero. closely with those deduced from the same experiments P is termed the potential factor of the system. by a method which, in principle, has been previously Alternatively, P^dW is a function of a quantity used by Bjerrum and others. The results obtained C, termed the capacity factor of the system, and is a for the dissociation of carbon dioxide at high tem complete differential. The application of this form peratures are considerably lower than the accepted of the second law, for which unification and simpli values. The reasons for this are discussed. It is pointed fication are claimed, is discussed at length for all out that the relation o:—a/b at the maximum temper types of systems. R. W. Lttnt. ature applies also to flames. L. L. B i r c u m s h a w . Dissociation of carbon dioxide at high tem Influence of concentration and the activity of the hydrogen ions on the rotatory power of peratures. W. T. D a v i d (Nature, 1927, 120, 157). —Penning and Tizard’s assumption (cf. preceding aqueous solutions of electrolytes. (M l l e .) J. abstract) that chemical equilibrium is established by L i q u i e r (Ami. Physique, 1927, [x], 8 , 121—203).— the time the maximum pressure is reached in explo An electrometric investigation of aqueous acid or sions is considered to be erroneous. Investigations basic solutions of weak optically active electrolytes- indicate that even with pure gases (carbon monoxide (nicotine, quinine, and asparagine) shows that the and hydrogen) chemical equilibrium is far from being rotatory power may be expressed as a function of the fu of the solution. The variation of the rotatory attained at maximum pressure. A. A. E l d r i d g e . power, and the anomalous dispersion observed in Soret effect. A. W. P o r t e r (Trans. Faraday certain cases, may be explained by the hypothesis of Soc., 1927, 23, 314—316).—Theoretical. Mathe the superposition of the rotatory dispersions of two matical expressions are deduced connecting the con or more active constituents (i.e., neutral molecules centration gradient of a solution with the temperature and the ions formed on dissociation). The experi gradient, and applied to Tanner’s data (this vol., mental curves, [a]=/(j)H)> have the S-shape of the 204) for electrolytes. M. S. B u r r . curves which are associated with saturation o f weak Formation of a complex ion in aqueous solu acids or bases by strong bases or acids, and they tions of silver nitrate and phenol. K . E n d o coincide with the theoretical curves obtained by (Bull. Chem. Soc. Japan, 1927, 2, 147— 155).— applying the classical laws governing dilute solutions Measurements of the partition of phenol between of weak electrolytes to the substances under con benzene and aqueous solutions of silver nitrate show sideration. The relation between the dissociation that silver nitrate differs from the salts previously constants and tlie degree of acidity or basicity shown studied (this vol., 729) in that it increases the solvent by the electrolytes may be determined with great power of water for phenol. Measurements of f.-p. accuracy from the curves [a]=/(pH). The degree of depression show- that this abnormal behaviour is due hydrolysis of the salts formed may also be accurately to the formation of the complex ion [Ag,G6H80]+. calculated. J. S. C a r t e r . The measurements of rotatory power have been Titration curves of taurine and of cysteic acid. extended to solutions of asparagine in presence of S. A n d r e w s and C. L. A . Schmidt (J. Biol. Chem., strong electrolytes. From a consideration of the 1927, 73, 651—654).—Titration curves are given for rectilinear diagrams of Darmois (cf. A., 1923, i, 2-99, taurine and cysteic acid; taurine has Ka 1-SX 10_0, 535, 751) for the visible and ultra-violet spectra, it is Kb 3 X 10~13 ; cysteic acid has K„ 1-3 X10-2 (assuming concluded that the active constituents of these salt Kb to be 2 x 10-13), and K„, 2 x lO“9. solutions are the same as those of aqueous solutions C. R. H a r i n g t o n . of variable acidity, i.e., the neutral asparagine mole Influence of adsorbing materials on chemical cule and corresponding anion and cation. The equilibria in solution. R. D u b r t s a y and J. properties of asparagine are thus, both in salt and Bravard (Compt. rend., 1927, 1 8 5 , 385—386).—The aqueous solution, a function of its degree of dis effects of kieselguhr (treated with hydrochloric acid sociation. The law of mass action is applicable to and washed with hot and then cold water till neutral), these solutions, provided that it is generalised by of Fontainebleau sand, silica, and china and other the introduction of the coefficients of activity of clays on the solubility of calcium carbonate in contact the ions present in the solution. Knowing the with a solution of ammonium chloride, have been rotatory power and the activity of the hydrogen determined at 17°, 41°, and 35° in solutions of various ion for a given salt solution, the coefficients of activity concentrations (4jV- to N /16-ammonium chloride), of the ions formed by dissociation may be calculated. the adsorbing material increases the solubility of the It is proved that these coefficients vary in the direc calcium carbonate according to the equation 2NH4C1+ tions indicated by the Debye-Huckel theory of strong at03 (NH4)2C03+CaCl2, the effect being less electrolytes. The facts observed constitute a qualit •narked in warm than in cold solutions. J. G r a n t . ative verification of this theory, and it is shown in 828 BRITISH CHEMICAL ABSTRACTS.----A. particular that they may be interpreted in terms of Soc., May, 1927. Advance copy. 14 pp.).—Recent the diminution of the dielectric constant of the solvent work on the activity coefficients of electrolytes in due to the addition of salts. L. L. B i r c u m s h a w . solutions of non-electrolytes is reviewed and the theoretical treatment of such systems discussed. Recent advances in the ionisation theory as H. J. T. E l l in g h a m . applied to strong electrolytes. V. K. La M e r Ionic partition coefficients. I. N . B j e r r u m (Amer. Electrochem. Soc., May, 1927. Advance and E. L a r s s o n (Z. physikal. Chem., 1927, 127, copy. 54 pp.).—In a review of the anomaly of strong 35S—384).—The partition coefficients of a number electrolytes, the theory of Debye and Hiickel is of ions between water and ethyl alcohol have been presented and discussed at length. The influence of determined by E.M.F. measurements. The partition the mathematical approximations in the present form exponent P, defined as the logarithm of the partition of the theory is shown to be most marked for ions of coefficient, is composed of an electrical term Pe small size. This question and its relation to Bjerrum’s dependent on the ionic charge, a term Pu due to hypothesis of ion association (A., 1926, 1101) are molecular forces, and a third term P, dependent on developed in some detail. Most of the discrepancies the different degrees of solvation of the ion in the between theory and experiment vanish when the two solvents. Pc may be calculated if the valency mathematical development is extended to include the and radius of the ion and the dielectric constants of case for ions of small size and high valency. Bron- the two solvents be known, and Pu may be con sted’s principle of specific interaction (A., 1924, ii, sidered to be of the same magnitude as the partition 94) is discussed and the significance of the true degree exponent of a similar but neutral molecule. Ps is of dissociation of strong electrolytes is considered. equal to the logarithm of the equilibrium constant It is claimed that the extension of the Debye-Hiickel of the solvation in the two media. The calculated theory to concentrated solutions, as given by Hiickel values of the partition exponents and the extent of (A., 1925, ii, 513), assuming that the dielectric con the agreement with the experimental figures are dis stant is a linear function of the ionic concentrations, cussed. The application of the partition exponent is not justified. The agreement with Hiickel’s in the analytical treatment of the Soret phenomenon equation found by Scatchard (A., 1926, 911) and by and of thermoelectric forces in solutions of electro Harned (A., 1926, 354) is stated to be illusory and lytes are discussed. H. F. Gill b e . values of the dielectric constant required by Hiickel’s equation do not agree with the experimental data of Factors influencing the solubility of strong Walden, Ulich, and Werner (A., 1925, ii, 773). Gron- electrolytes. I. Reciprocal solubility effects of wall and the author have shown that values of the homoionic alkali salts. I. J. F. H ollota and dielectric constant chosen so as to fit in with vapour S. M a u t n e r (Z. physikal. Chem., 1927, 127, 455— pressure and E.M.F. data in concentrated solutions 475).—The influence of sodium chloride and of are in agreement with Walden’s results. It is potassium nitrate on the solubility of potassium claimed that- a thermodynamic error is involved in chloride, of potassium chloride on that of sodium the derivation of Huckel’s equation and an equation chloride, and of potassium chloride on that of potass derived by Gronwall and the author is put forward ium nitrate, in aqueous solution at 18-5°, have been in its place. H. J. T. E l l i n g h a m . measured up to the highest possible concentration of the added salt. A series of equations, which Electrochemistry of solutions of mixed electro hold only for non-electrolytes and assume complete lytes. H . S. H a r n e d (Amer. Electrochem. Soc., ionisation of all strong electrolytes, have been applied May, 1927. Advance copy. 34 pp.).—The deter to the results; discrepancies are discussed, and a mination of the activity coefficient of an electrolyte general relationship is proposed between the magni in solutions of other electrolytes is discussed and tude of the solubility effect and the solubility and recent work on the subject is reviewed. The thermo chemical nature of the two salts concerned. Equa dynamic behaviour of hydrogen and hydroxyl ions is tions are given for calculating the solubility effect at compared with their catalytic effects in the light of any concentration of the added salt. recent experimental measurements. Rothmund’s equation for the reciprocity of the H. J. T. E l l i n g h a m . solubility effect has been tested ; on the assumption Transference number and activity of sodium of complete ionisation, discrepancies of considerable hydroxide in aqueous solution. A. L. F e r g u s o n magnitude exist between the theoretical and experi and A. W. S c h l u c h t e r (Amer. Electrochem. Soc., mental figures. H. F. G il l b e . May, 1927. Advance copy. 11 pp.).—The activity coefficient of sodium hydroxide in aqueous solutions Mol. wt. determinations and solubilities in ranging from 0 01 to 2-8 g.-mol. per kg. of water has liquid chlorine. K. H. B u t l e r and D. M c I n t o s h been determined by measuring the E.M.F. of the (Trans. Roy. Soc. Canada, 1927, [iii], 21, III, 19— concentration cells, H2|NaOH(C1)|NaiHg|NaOH(C,2)| 26).—The following anhydrous compounds produce H2 and H2|Na0H(01)|Na0H(C'2)|H2. From the data no rise in the b. p. of, and are consequently insoluble obtained transference numbers have been calculated in, liquid chlorine : Potassium aluminium sulphate, over the given concentration range. The value for aluminium acetate, ammonium chloride, sulphate, the cation varies from 0-203 in the most dilute to and thiocyanate, antimony trichloride and oxide, 0-153 in the most concentrated solution. barium chloride, bismuth nitrate, boric acid, cadmium H. J. T. E l l i n g h a m . chloride, cæsium chloride, calcium carbonate and Mixed solutions of electrolytes and non fluoride, chromium sulphate and trioxide, cupric electrolytes. G. S c a t c h a r d (Amer. Electrochem. sulphate, cuprous chloride, ferric chloride and GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 829 sulphate, iodine trichloride, lead chloride and sulphate, give a looped curve which is attributed to the exist lithium chloride, mercuric iodide, mercurous chloride, ence of a second form of pyramidone (p-pyramidone), nickel chloride, potassium chloride, chlorate, di- which has not been isolated. The transformation chromate, ferricyanide, ferrocyanide, iodate, iodide, a— > P is said to account for the rapid increase in the and nitrate, phosphorus chloride, selenium dioxide, solubility at 65—70°. J . G r a n t . silver nitrate, sodium arsenate, arsenite, hydrogen Equilibrium between the hydrates of calcium sulphite, bromide, phosphate, and stannate, stront sulphate. D. B a l a r e v [with A. S p a s s o v ] (Z. ium chloride, uranyl acetate, zinc chloride and anorg. Chem., 1927, 163, 137— 140).—The process of sulphate. The following hydrated salts have no dehydration of the hemihydrate of calcium sulphate influence on the b. p. : cadmium sulphate, ferrous above 80° is reversible, but the dehydration does not sulphate, magnesium chloride and sulphate, stannic take place spontaneously. Below 80° the water- chloride, stannous chloride. Silver, copper, zinc, vapour pressure of the system lies below 2 mm. of sulphur, and arsenic are unaffected by boiling liquid mercury. The decomposition of the hemihydrate chlorine, although attacked by the gas; aluminium into a mixture of dihydrate and anhydrous salt is reacts readily, tin and iodine violently, and phosphorus therefore thermodynamically impossible, as the re explosively. The most probable value of the ebullio- generation of the hemihydrate could not take place. scopic constant is 1-73, corresponding with a latent Such a decomposition is possible only if two forms of heat of 66-0 g.-cal. per g. Bromine molecules appear the soluble anhydrous salt exist, viz., an a. form stable to dissociate in, but not to form a compound with, below 72° and incapable of existence in equilibrium liquid chlorine. A. A. E l d r i d g e . with the hemihydrate, and a p form stable above 72° Solubility of acids in salt solutions. I. E. and stable in the presence of hemihydrate. Dilato- Larsso n (Z. physikal. Chem., 1927,127, 233—248).— metric measurements confirm the existence of the two The solubility of benzoic, cinnamic, hippuric, o-nitro- forms; the transition a^±=(5 occurs at 82°, and is benzoic, benzilic, and salicylic acids in dilute salt rendered evident also from the nature of the heating solutions has been determined and the results have and cooling curves, the (3 form being produced from been compared with those obtained by Loven for the a with the evolution of heat. the solubility of a sparingly soluble monobasic acid Contradictions in the literature concerning the in a solution of a salt of another monobasic acid. crystal form of anhydrous calcium sulphate may In dilute salt solutions the ion activity coefficients do most probably be referred to the existence of the not influence the solubility when both acids are two forms. H. F. G i l l b e . monobasic. At higher concentrations it would be Systems : CoCl2-MCl or MC12-H20. A. B e n - expected that the activity coefficients of the molecules r a t h (Z. anorg. Chem., 1927, 163, 396—404).—The would influence the sparingly soluble acid, but equilibria in the above ternary systems at 25° have measurements of the solubility of benzoic acid in been studied. Together with the evidence obtained solutions of sodium acetate, sodium formate, and by Mazzetti (this vol., 22) and by Foote (ibid., 313) sodium monoehloroaeetate at concentrations up to M the results indicate that the blue colour of cobalt show that no such effect takes place. The ions chloride solutions containing chlorides of sodium, present, therefore, appear to have opposing influences potassium, ammonium, or the alkaline-earth metals on the activity of the benzoic acid molecule. More cannot be ascribed to the existence of complex com probably, sodium benzoate increases the solubility of pounds. The colour cannot be due to the formation benzoic acid, whilst the other three salts act as of lower hydrates of cobalt chloride, since the lowest salting-out agents. The solubility of benzoic acid hydrate obtained under the experimental conditions in sodium chloride solution is smaller, and in sodium was the dark violet dihydrate. It seems probable benzoate solution greater, than in water. Equations that the compound CoCl2,RbCl,2H20 reported by are proposed by which the solubility of a monobasic Foote was a mixture. A blue compound, acid in a solution of a salt of a po'lybasic acid may CoCl2,4LiCl,10H20, has been obtained. From the be calculated, but these are applicable only at red solutions of cobalt chloride containing zinc infinite dilution. H. F. G i l l b e . chloride and cadmium chloride, the compounds Influence of neutral salts on acid-salt equi 2ZnCL„CoCl2,12H20 and 2CdCl2,CoCl2,12H20 have libria. I. Standard value for calculating the been isolated, and it is probable that mercuric chloride activity exponent of the hydrogen-ion con yields a similar compound. R. C u t h i l l . centration. I. M. K o l t h o f f and W . B o s c h (Rec. Complex chemical behaviour of beryllium. trav. ehim., 1927, 46, 430—438).—It is suggested V. R . F r i c k e and O. R o d e (Z. anorg. Chem., 1927, . at Pan of the standard solution 0-01AT-HCl-f 163, 31—39).—The thermal diagram of the system v 'KC1 be taken as 2-075, whence ;paH=2)H+0-037. beryllium chloride-isohexonitrile shows the exist -Neutral salts decrease the hydrogen-ion activity in ence of three eutectics, viz., at about 154°, 125°, hydrogen chloride solutions, but at higher and —53°, and of three compounds containing 2, 3, concentrations have the reverse influence. The effect and 4 isohexonitrile groups combined with one mole produced is independent of the anion. cule of beryllium chloride. Beryllium chloride- Q . H. F. G i l l b e . propionitrile and beryllium chloride-^-toluonitrile nh i ^ ty ^ water of 4-dimethylamino-l - both yield complexes containing 2, 3, 4, 5, and 7 frnoT* -d ' ^'(^ n:iethyl-5-pyrazolone [pyram id- nitrile groups per molecule of beryllium chloride. 9oJ' Oo“; Charonnat (Compt. rend., 1927, 185, The results for p-toluonitrile are confirmed by con -86). The solubility data between 0° and 200° ductivity measurements. H. F . G i l l b e . 830 BRITISH CHEMICAL ABSTRACTS.— A. Organic binary equilibria. System glyceryl than 45% of copper is present two liquid layers are trinitrate-trinitrotoluene. V. T a m b u r r i n i (Annali formed. Cliim. Appl., 1927, 17, 275—282).—The cooling The maximum susceptibility of Heusler’s alloys curvo for this system with initial separation of solid lies at the point of intersection of Cu3A1 and AlMn3. trinitrotoluene shows scarcely any supercooling, but Alloys containing more than 30% of manganese, this phenomenon is clearly marked when glyceryl which have not been previously investigated, are also trinitrate, separates first as solid. With eutectic magnetic. The increase and decrease of magnetic crystallisation pronounced superfusion occurs. The properties are accompanied by changes of structure, existence of a compound is improbable. which have been studied by the aid of photomicro T. H. Pope. graphs. Binary pharmaceutical mixtures. A. Angel- In contradistinction to Heusler’s alloys, which e t t i (Annali Chim. Appl., 1927, 17, 269—275).— attain their maximum magnetic susceptibility after Examination by Rheinboldt’s method (A., 1926, 25) being heated at 144° for a long period, alloys of has given the following eutectic points. Acetanilide- • high manganese content exhibit their maximum pyramidone, 58-5°, 41% acetanilide; acetanilide- magnetic properties after ageing at a high temper phenacetin, 82-5°, 58% acetanilide; pyramidone- ature, wrhereas ageing at 144° causes all magnetic phenacetin, 78-5°, 68% pyramidone; salol-benzo- effects to vanish. H. F. G il l b e . naphthol, 34°, 86-9% salol. In the last case, mixtures Ternary system methyl benzoate, methyl containing 80—90% of salol would undergo partial alcohol, water. E. C. G i l b e r t and B. E. La top. fusion in hot weather and are hence “ incompatible.” (J. Physical Chem., 1927, 31, 1050—1052).—The T. H. P o p e . solubility isotherms for 15°, 25°, and 35°-have heen System : iron-silicon. T. M u r a k a m i (Sci. Rep. determined by the method of Walton and Jenkins Tohoku Imp. Univ., 1927, 16, 475—489).—The (A., 1924, i, 156). An equation of the type X/T’!=7i magnetic transformation which occurs at 450° in alloys is shown to hold at the lowest-temperature, but there containing more than 16% of silicon is not due to a is increasing divergence from experiment with a change of phase, and the evolution of heat at 1020° rise of temperature. Methyl benzoate and water is due to the formation of Fe3Si2 from the a phase are practically immiscible at the ordinary temperature, and FeSi. The existence of a compound melting at and a large proportion of methyl alcohol is required 1225° is confirmed by X-ray analysis, and it is found to produce a one-phase mixture. The solubility to dissolve up to 1% of silicon, forming a solid solution surface rises abruptly. L. S. T h e o b a ld . which gives a eutectic point with FeSi at 1220°. This is so close to the m. p. of FeSi2 that discrimin Systems uranyl sulphate, alkali sulphate, ation of-the two changes by means of cooling curves water, at 25°. A. C o l a n i (Compt. rend., 1927,185, is impossible. Silicon forms a solid solution 'which •273—-275).—Solubility data for the systems, uranyl sulphate and water, with ammonium, potassium, may contain up to 4% of iron. F. S. H a w k in s . and sodium sulphates at 25° show the existence of a System: iron-cobalt-nickel. T. I y a s e (Sci. number of complex salts. The following have not Rep. Tohoku Imp. Univ., 1927, 16, 491—513).—The been previously described : (NH4)2(U0o)o(S04)3,5H20, system has no ternary eutectic and there is no evidence K2(U02)2(S04)3,5H20, and Ka4(U02)(SQ4)3>3H20. All of compound formation. The relations suggest a the compounds obtained behave as true double salts, continuous series of solid solutions, except for a but anomalies are shown by the sodium sulphate small range on the iron side, where there is a dis system. J. G r a n t . continuous change from one solid solution to another. Solubility of silver halides in concentrated .Magnetic, dilatometric, scleroscopic, and microscopic halide solutions. L. D e d e and T. W a l t h e r (Z. observations indicate the occiu-rence of one magnetic anorg. Chem., 1927,163, 185— 194).—The solubilities and two polymorphic changes in the solidified alloy. have been determined of silver chloride in concen The polymorphic change on the iron side is the trated solutions of the chlorides of potassium, ammon transition from y- to a-solution, and that on the ium, sodium, calcium, lithium, and hydrogen, and of cobalt side from y-solution to a hexagonal lattice silver bromide in concentrated solutions of potassium, solution. The magnetic change involves no change calcium, and hydrogen bromides, at 20°, 40 , oO , of phase. F. S. H a w k i n s . and 80°. In all cases the temperature coefficient is Three-component system copper-aluminium-- large. The increase of solubility produced by the manganese, and its magnetic properties. W. presence of the various salts is in the o r d e r ,given, KniNGSjand W. O s t m a n n (Z. anorg. Chem., 1927, being greatest for potassium halides and least for'-the 163, 145— 164).—The: system shows no ternary com hydrogen halides., This order is not t h e s a m e as tha pound, nor could the existence of the eompoimd of the activity coefficients of the salts. AlsMn be confirmed; Al4Mn, however, is present. H. F. G il l b e . The ternary diagram may be divided into three Systematic doctrine of affinity. XXXIX. regions: (1) the triangle A 1-CuAl,-Al4Mn in which Indium halides. II. Heats of formation o there exists at 536° a ternary eutectic which contains indium chlorides. W. K le m m and M. B r a e t ig a j -29-6% of copper and 3% of manganese; (2) an area (Z. anorg. Chem., 1927, 163, 225—234; cf. A., lJ-b. of ternary mixed crystals, which undergo transition 669).—The heats of formation of the solid 1I1C“U'‘|J in:the solid state and-may be isolated by rapid cool- chlorides from the metal and g a s e o u s chlorine a (3) a polyphase area lying between (1) and (2), are: monochloride,44-6 +0-1; dichloride,86-8±v •>> which has not been investigated further. When less trichloride, 12S-5±0-l kg.-cal. Cuthill. GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 831 Systematic doctrine of affinity. XL. Indium of the oxide, the latter composition corresponding halides. IV. Ammines of indium halides. W. with the solubility of uranoso-uranic oxide in the Klemm (Z. anorg. Chem., 1927, 163, 240—252).— dioxide. Beyond this point, the volume increases Isothermal decomposition experiments indicate the regularly, the crave showing no discontinuity At the existence of compounds of indium trichloride with composition corresponding with uranoso-uranic oxide 15( ?), 7, 5, 3, 2, and 1 molecules of ammonia. The (cf. preceding abstracts). R. C u t h i l l . tribromide forms compounds with 15( ?), 7, 5, and 3 molecules of ammonia, and the tri-iodide with 21( ?), Relation between unit electrolytic conductivity 13, 9, 7, 5, 2, and 1( ?) molecules. For a few of the and Faraday's law. M. E p p l e y (J. Franklin Inst., compounds, the dissociation pressures at various tem 1927, 204, 95—;96).—The relation is expressed in the peratures have been determined, and the results used statement that: “ When the conductivity of a solu to calculate the partial heats of formation. In some tion is unity, a current of 1 amp. passed through it cases, the. heat of dissolution in hydrochloric acid has between electrodes 1 cm.2 in area and 1 cm. apart been determined, and the total heat of formation will deposit one electrochemical equivalent per calculated from it. From these measurements, second.” J. S. C a r t e r . assuming the heat of formation of indium trichloride Temperature coefficients of electrical con to be 128-5 kg.-cal., the heats of formation of the ductivity for concentrated solutions of calcium tribromide and tri-iodide are found to be 97-1 and chloride, with precision measurements of con 564 kg.-cal., respectively. Addition of ammonia ductivity for the higher concentrations. M. to the monochloride causes it to decompose into the C r o w e (Trans. Roy. Soc. Canada, 1927, [iii], 21, III, metal and the ammonia compounds of the trichloride, 445—-156).—Tabulated values and curves are given but on removal of the ammonia the triammine of the conductivity and density of solutions of calcium passes directly to the ammonia-free monochloride chloride containing 29—46 g. per 100 g. of solution without formation of a diammine or monammine. at 10°, 15°, 17-9°, 20°, 25°, and 30°. The specific R. C u t h i l l . conductance at 18° and the temperature coefficient, Systematic doctrine of affinity. XLI. Uran respectively, are: 29-60%, 0-1661, 0 0216; 37-30%, ium oxides. W. B i l t z and H. M ü l l e r (Z. anorg. 0-1202, 0-0241; 38-36%, 0-1124, 0-0249; 40-73%, Chem., 1927, 163, 257—296).—The relation between 0-0934, 0-0284; 41-98%, 0-0868, 0-0286; 45-95%, the valency of uranium in its oxides and their energy 0-0576, 0-0330. A. A. E l d r i d g e . contents has been investigated. For preparations varying in composition from U 03 and U30 8, the Conductivity and transport numbers of cadm dissociation isotherms between 438° and 650° are ium salts in acetamide. L. B e l l a d e n (Gazzetta, continuous, so that the solid phase, the X-ray diagram 1927, 57, 412—415).—The molecular conductivity of of which shows the lattice of uranoso-uranic oxide, cadmium chloride, bromide, and fluoride has been consists of a solid solution. The pressures actually determined at 90° in molten acetamide at «=10—1200. observed are apparently not quite equal to the true It is found that the iodine transport number for solu equilibrium pressures. This is probably due to the tions of cadmium iodide increases from 0-68 to 1-41 as great chemical resistance to the passage of part of the concentration of the salt increases from 1-9 to 15%. the amorphous trioxide into mixed crystals. Under These values are slightly greater than those of Hittorf ordinary conditions, the reverse transformation of for aqueous solutions, in agreement with the smaller uranoso-uranic oxide: into the trioxide does not occur, dissociating power of acetamide. R. W. L u n t . although it seems to have occurred in some minerals, Conductivity of electrolytes in fused acet and does actually take place with very finely-divided amide. L . B e l l a d e n ■ (Gazzetta, 1927, 57, 407— preparations such as are obtained by ignition of 411).—Acetamide was purified by careful drying and umyl oxalate (ef. Lebeau, A., 1922, ii, 302). From repeated fractionation at 220 mm.; the substance so the tensimetric data, the heat of the reaction 2U308+ produced had a specific conductance of 1-5 X 10~6 mho Uj~6UO, is calculated by means of Nernst’s approx at 90°. Data are given for the molecular conductivity imate equation for the dissociation pressure of oxides of sodium chloride, bromide, and iodide in molten to be 32 kg.-cal. In the passage of uranoso-uranic acetamide at 90° for v = 10—720; the values observed oxide into the dioxide, the equilibrium pressure is are of the same order of magnitude, although only rapidly established, and the process is completely the bromide and iodide are known to form complexes reversible. Between the compositions U 02.oi arid with the solvent. Data are also given for calcium , the pressure at constant temperature is con- and barium chlorides and for potassium iodide for s ant, corresponding with the existence of conjugate ,u = 10—960. The conductivity of the barium salt is At uranoso'uranio oxide and the dioxide. slightly greater than that of the calcium salt, which iwO , the mixed c^stals have an appreciable forms a complex with six molecules of the solvent. apour pressure, and sublimation occurs. Neither The author’s data for potassium iodide are compared t tension curves nor X-ray diagrams j'ield any with Walker’s, which show a maximum at «=54900, rr? f lc® *or the existence of the pentoxide, U205. whilst the former increase regularly to infinite dilution. i the react,ion 3U02+: 02=U 30 8 is calculated The - discrepancy is attributed to inadequate puri 77 V kg.-cal. by the van ’t Hoff isochore, and fication of Walker’s solvent. R. W. LtiiiT. L °-'ca'- hy Nernst’s equation. The densities at W i T 11 oxides between UO,.069 and U O ^ , Moving-boundary method for determining I g f e Between U02 and V 0 2Z, transference numbers. VI. Further develop ° 11 ls taken up without any change in the volume m en ts in experimental technique. D. A. M a c - 832 BRITISH CHEMICAL ABSTRACTS.— A. I n n e s , I. A. Cowterthwaite, and T. C. H u a n g (J. sociation of a complex formed between the ether and Amer. Chem. Soc., 1927, 49, 1710—1717).—The form bromine. H. F. G i l l b e . of the cell and the method of measuring the time Electrochemistry of solutions of aluminium intervals have been improved. The effects of vibra bromide in nitrobenzene. V. A. P l o t n ik o v and tion are eliminated by suspending the thermostat M. A. B e n d e t z k y (Z . physikal. Chem., 1927, 127, with springs. Boundaries must always descend, i.e., 225 — 232).— Measurements have been made of the solution of lower conductivity must always be the conductivity of solutions of aluminium bromide uppermost; otherwise, heat effects and mixing occur. in nitrobenzene at concentrations between 0-27 and An improved method of viewing the boundary is 58-6% over the range 0—80°. The specific conduct described and some factors governing “ adjustment ” ance-concentration curves, at all temperatures, rise (i.e., of the indicator concentration) are discussed. to a maximum and then fall to very low values. With these improvements, the transport number of At 10° and 50° the maxima correspond with 16 and ■■ silver in 0-05iV-silver nitrate is 0-4664 at 25°. 24%, respectively. For a solution containing 28-3% ' S. K. T w e e d y . of aluminium bromide the specific conductance at Space charge in electrolytes. D. R o l l e r (Proc. 50° is 252 X l0-5 mho. The conductivity at constant Oklahoma Acad. Sci., 1927, 6, 290—293).—Measure concentration increases at first with rising tem ments of the potential differences between two perature, reaches a maximum, and then falls; tie platinum points, 1 cm. apart, placed between two temperature coefficient increases with the concen electrodes (E.M.F. between 5-3 and 26 volts) in tration. Electrolysis of the solution yields bromine 0-005—0-3Ar-hydrochlorie acid indicated that the field at the anode in quantitative agreement with Faraday’s in the electrolyte was unidirectional and normal to law. H. F. G il l b e . the electrodes. Appreciable non-uniform electrical distributions could be explained on the basis of space- Volta effect. E. D u b o i s (Compt. rend., 1927, charges in the electrolyte. Ch e m i c a l A b s t r a c t s . 1 8 5 , 110—111).—A metal electrode heated in air and cooled becomes electronegative in relation to its initial Effect of the concentration gradient on the state. Silver, gold, copper, and platinum become electric field in a conducting electrolyte. D. slightly electropositive after heating at 500°, but R o l l e r (Proc. Oklahoma Acad. Sci., 1927, 6, 294).— change to electronegative after heating at 1000°. In hydrochloric acid solutions the electric field has a The effect is independent of the oxidisability of the maximum value near the cathode. Effects due to metal, and the action of the vapour of an alkali concentration polarisation are important in such chloride is to change an electronegative electrode measurements. C h e m i c a l A b s t r a c t s . back to an electropositive state, which is characterised Electrochemical properties of bromine-ether by a greater degree of stability than the original. G r a s t . mixtures. B . P. B r u n s (Z. anorg. Chem., 1927, J. 1 6 3 , 120— 136).—A simple method is described for Becquerel effect with copper oxide electrodes. varying to a known extent the concentration of a W. J . D . v a n D y c k (Z . physikal. Chem., 1927, 127, solution contained in a closed system. The con 249—301).—The method of Goldmann and Brodsky ductivities have been determined of bromine solutions has been modified to permit of more rapid measure of methyl, ethyl, propyl, tsoamyl, and dichloroethyl ments of the photoelectric effects and the electrode ethers, and methylal. In the methyl ether series has been improved by depositing a layer of cupric the specific conductance decreases with increase of mol. oxide or of a mixture of cuprous and cupric oxides wt., methyl ether, however, having an abnormally on platinum. The dependence of the photo-electric low value. Methylal has a conductivity similar to characteristic on the wave-length of the incident light that of ethyl ether, and is a more convenient substance indicates that the Becquerel effect for cupric oxide with which to work since it reacts more slowly with cannot be explained as a simple Hallwachs ettec . bromine. The photoelectric sensitivities of the two oxides per The curves showing the relationship between mole unit of incident light energy have been measured, cular conductivity and concentration are of the type and a thermopile is described by means of which t e normally given by solvents possessing a low dielectric quantum yield by the Becquerel effect has been constant. With the exception of dichloroethyl ether, determined. With no crurent flow no decomposition all the solutions exhibit a large increase of conduct is caused by the action of light. The capacity o c ivity with rise of temperature. Dichloroethyl ether, surface layer of the oxide has been measured, an l in which the positive character of the oxygen atom influence on the form of the photo-electric curves i is weakened, has a conductivity of only about 0-01 discusscd. of that of ethyl ether, probably owing to the reduced The theoretical significance of the effect is con tendency to complex formation; this is also the sidered. According to this it appears that probable cause of the negative temperature coefficient peculiarities of the crystal structure play a f? of the conductivity. In all cases the current passed part, and the varying stability of the_ lattice by the solution is directly proportional to the applied varying external oxygen concentration is emphasis;• voltage. Electrolysis yields bromine at the anode Thermodynamic considerations suggest the exis e quantitatively, whilst no change occurs at the cathode. of a P.D., above which no effect is to be expec e . Comparison of the molecular conductivity of the H. F. G il l b e . hydrogen halides in ether and of ether in the hydrogen Influence of gelatin on the potential and dis halides with that of the ethers in bromine indicates charge potential of zinc in zinc sulphate so u ■ that the ionisation is most probably due to the dis- N . I s g a r i s c h e v a n d P . T i t o v (Z . Elektrochem., GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 833 33,211—212).—Results obtained by Rabald (A., 1926, 1927, [v], 13,9—27).—Electrolysis of barium carbonate 804) are regarded as extending but not contradicting in suspension in solutions of barium chlorate and the authors’ previous observations (A., 1921, ii, 620). perchlorate -with a mercury cathode gives better yields H. J. T. E l l i n g h a m . than the Siemens and Halske method, in which a Passivity of metals from the point of view of diaphragm is employed between two inert electrodes. the activation process. I. Activation process H. E. G i l l b e . and steady anodic gas evolution. D. R e i c h i n - Theories of unimolecular gas reactions at low stein and W. v o n R e y t e r (Z. Elektrochem., 1927, pressures. 0. K. R ic e and H. C. R a m s p e r g e r (J . 33, 237—244).—Measurements have been made at Amer. Chern. Soc., 1927, 49, 1617— 1629).—Collision various constant current densities of the potential of theories capable of explaining why a gas reaction smooth platinum electrodes acting as anodes in dilute which is unimolecular at high pressures can deviate sulphuric acid solutions. At a given current density from unimolecularity at low pressures are considered. the anode potential eventually reaches a steady value In particular, using the methods of classical statistical which is independent of the acid concentration mechanics and assuming that molecular interchange (between 0-1 and l-8Ar) and of the previous history of energy occurs only at collisions, expressions are of the electrode, but the time required for the attain developed for the reaction rate at low pressures both ment of this steady value is greatly dependent on on the basis of Hinshelwood’s theory (A., 1926, 804) the previous history, previous cathodic treatment and also on the assumption that a molecule is activated making it very long and previous anodic treatment when its total noil-translational energy is at least e0, at a higher current density making it very short. the minimum amount of energy which some par In the latter case, on lowering the current density ticular degree of freedom must possess for reaction the potential falls rapidly and actually reaches as much to occur, and it may redistribute itself between col as 30 millivolts below the steady value corresponding lisions. The data for the decomposition of prop- with the new current density ; it then rises again to aldehyde (Hinshelwood and Thompson, this vol., 26) this steady value. This phenomenon is discussed in fit the theoretical curves of both the above theories connexion with other anomalous activation processes equally well, and more accurate and extensive data observed by one of the authors (A., 1915, ii, 678; 1922, are required for deciding between the theories. ii, 736) and an explanation is suggested on the basis S . K. T w e e d y . of his displacement theory (cf. this vol., 515). The Striated photographic records of explosion steady values of the anode potential at various current waves. C . C a m p b e l l and D. W. Wood h e a d densities from 10~7 to 4-4 X 10~4 amp./cm.2 are recorded. (J .C .S ., 1927, 1572—1578).—An undulatory form of H. J. T. E l l i n g h a m . explosion wave, which in a tube of 15 mm. internal Application of electrometric methods to the diameter has a wave-length of 45 mm., is character study of the oxidisability of organic substances. istic of the mixture 2 C 0 + 0, and of certain dilute II. G. L e j e u n e (J. Chirn. pliys., 1927, 24, 482— mixtures of carbon monoxide and other gases with 495).—The difference of potential between two alkal oxygen or with oxygon and nitrogen. The mixture ine solutions of permanganate of different concen 2 C 0 + 0 2, when saturated with water vapour at trations has been shown to be represented by the ordinary temperatures, exhibits no undulations in the formula Sj—e2=2/3 X 0-0002T log c1/c2. The rate of presence of about 6% of hydrogen. Increase of the change of potential in the presence of readily oxidis- initial pressure up to 3 atm. does not influence the able organic compounds has thus been determined. length of the undulation, which is, however, directly The rate of change of potential does not represent proportional to the internal diameter of the explosion the rate of oxidation of the organic compound, but tube. H. F. G i l l b e . there is evidently some relation between them since the phenomena observed are strictly reproducible and Inflammability of hydrogen. IV. Influence the qualitative classification of the different com of hydrogen selenide on the limits of inflamm pounds studied is exactly the same as that obtained ability of hydrogen-air mixtures. Y. T a n a k a and by purely chemical methods. A method for deter Y. N a g a i (Rept. Aeronaut. Res. Inst., Tokyo Imp. mining the potential of mixtures of cerous and eerie Univ., 1927, 2, 275—282; cf. ibid., 265; this vol., salts has been described. In accordance with the 212).—Hydrogen selenide lowers the upper limit of Kernst_ formula e=e0+0-0002T log Cem/Celv, where inflammability of hydrogen-air mixtures, and it is eo=0-059 volt. The rate of oxidation of various shown that the temperature necessary for the activ sugars has been followed by the rate of change of ation of hydrogen selenide is 1750°, a value equal to potential of a cerous-ceric mixture in the presence that obtained for diethyl selenide; this temperature the sugar. There is a proportionality between is, however, dependent on the negative part of the these oxidation velocities and the maximum oxid- molecule, being 1040° for hydrogen sulphide. 2% ation-reduction potentials as found by Goard and of hydrogen selenide as compared with 1 % of diethyl mdeal (A., 1924, ii, 161) for the aldehydic sugars selenide is required to raise the theoretical flame dextrose, galactose, arabinose, and lactose, but the propagation temperature of hydrogen from the initial ketonic sugar loevulose oxidises much more rapidly value,°1090°, to 1750°. Both hydrogen and hydrogen than is to be expected from its oxidation potential. selenide then behave as if they have the same flame M. S. B u r r . propagation temperature, and they obey Le Chatelier’s -Electrolysis of insoluble alkaline-earth com rule. Unlike diethyl selenide, hydrogen selenide also pounds, and especially of barium carbonate. raises the lower limit of inflammability of hydrogen- I’Oitr and P. M e u n i e r (Bull. Acad. roy. Belg., air mixtures; this difference is attributed to the 31 834 BRITISH CHEMICAL ABSTRACTS.----A. smaller heat of combustion of hydrogen selenide. Explosibility of methane and natural gas. The addition of 4% of hydrogen selenide raised the H . F. C o w a r d , G. W. J o n e s , C. G. D u n k l e , and lower limit to 12% of hydrogen, but further addition B. E. H e s s (Carnegie Inst. Tech. and U.S. Bur. Mines reduced it slightly. G. A. E l l i o t t . Min. Met. Invest. Bull., 1926, 30, 1—42).—The igni tion temperature of Pittsburgh natural gas is almost Lower limit of inflammability of ethyl constant over the whole range of inflammable mix alcohol, ethyl ether, methylcyciohexane, and tures with air; that of methane increases, and of their mixtures. Y. T a n a k a , Y. N agai, and ethane decreases with the concentration. The time K . A kiyam a (Rept. Aeronaut. Res. Inst., Tokyo Imp. lag, and lower and upper limits of inflammability, Univ., 1927, 2, 235—246).—The minimum percentage are less than for methane. The limits can be cal of the combustible substance when mixed with air culated from those of the constituent hydrocarbons which was necessary for inflammability (tested by a and the composition; the lower limit can also be simple spark-ignition method) was measured for each obtained from the ratio between the contraction on of these substances and also for their mixtures. The explosion and the volume of carbon dioxide produced, flame propagation temperature calculated, assuming The limits for upward inflammability for pure hydro that the combustion was complete, from the results carbons are, under quasi-industrial conditions, meth of experiments in which the compounds were used ane 5-24— 14-02, ethane 3-22— 12-45, propane 2-37— singly, was in each case about 1450°. This value is 9-5, butane 1-86—8-41. The speeds of uniform move in good agreement with those of White (A., 1925, ment of flame in tubes of diameter 2-5 cm. in any ii, 4S) for some lower members of the paraffin natural gas-air mixture can be calculated from the series; the presence of the naphthene ring had there composition of the gas and the known flame speeds fore no appreciable influence. The compositions of in mixtures of the individual hydrocarbons and air. the lower-limit mixtures containing two or more The behaviour of flame during the vibratory phase combustibles were in agreement (within 0-5 m ol.-% ) is similar for natural gas and methane. Pittsburgh with Le Chatelier’s rule. Such agreement is to be natural gas is slightly more inflammable than methane. expected for substances having the same flame pro C h e m i c a l A bst r a c ts. pagation temperature. G. A. E l l i o t t . Combustion limits under high pressure of Effect of pressure on the limits of inflamm mixtures of air with inflammable gases and ability and the average life-period of activated vapours. E. B b r l and G. W e r n e r .—See B., 1927, molecules in combustion. Y. N a g a i (J. Fac. 546. Eng. Tokyo, 1927, 17, 89— 105).—The effect of Kinetics of ozonisation under the influence of pressure on the limits of inflammability is explained a-particles. W . M u n d and J. D'O lie sla g e r (Bull. by a consideration of the limited life-periods of the Soc. chim. Belg., 1927, 36, 339—412).—'When radon activated molecules of the combustible gas or vapour. is mixed with pure dry oxygen the equilibrium The average life-periods of the activated molecules 302=== 203 is set up. Experiments are described of methane and ethyl ether are deduced to be of the provmg that, for a given radiation, ozone is formed order of 10~8 see., and that of carbon monoxide of at a constant rate and decomposes at a rate pro the order of 10~9 sec. When measured in a tube of portional to its concentration. The rates of both too small diameter, the effect of pressure on the reactions are proportional to the intensity of the limits of inflammability deviates considerably from radiation. One molecule of ozone is produced for the theoretical value, but the lack of agreement is only apparent, resulting from the difficulty in igniting each pair of ions formed. S. K. T w e e d y . the gaseous mixture at low pressure in a tube of Therm al decomposition of ozone. Ill- Tem small diameter. When the mixture is ignited in a perature coefficient of reaction rate. 0. R. large tube and the flame then travels through the tube W u l f and R. C. T o l m a n (J. Amer. Chem. Soc., of small diameter, anticipated results are obtained. 1927, 49, 1650— 1664; cf. this vol., 631).—The rate Two kinds of activated carbon monoxide molecules of decomposition of ozone at 452-2°, 441-7°, 431-3 , are assumed in order "to explain the inflammability 426-1°, and 420-9° Abs. was determined by a dynamic of comprcsscd carbon monoxide in the absence of method in a new type of decomposition vessel. The water vapour. Those of the first kind either are activation energy is calculated, on the basis of four formed by collision with molecules of water vapour, different reaction hypotheses, to be approx. 30,000 or they burn only in presence of water vapour, and g.-cal. in each case. Assuming the temperature co they are the cause of the “ steam line ” in the flame efficient to be determined by some unimolecular pro spectrum. They have an average life-period of the cess with an activation energy of 30,900 g.-cal., and order of 10'9 sec. Those of the second kind, which neglecting the inhibiting effect of oxygen (or else burn independently of the presence of water vapour, assuming the inhibiting effect to be determined solely have a very short average life-period (about 10~10 by the total pressure), the specific second-order rate sec.). At high pressures, the activated carbon mon of decomposition of dilute ozonised oxygen at oxide molecules of the second kind encounter oxygen approximately 1 atm. pressure is given by 2-04X molecules, and burn, whilst at low pressures the 1020e~30'900//ir, or, if Jahn’s mechanism is assumed (A., probability of their encountering oxygen molecules 1906, h, 225), by (5-S9 X l(fis[Po,)T0'5erw'miBT, an ex‘ while still activated decreases, owing to the lengthened pression which holds approximately for total pressures free path of the molecules; consequently, carbon other than 1 atm. Calculation show's that the Jahn monoxide becomes non-inflammable. mechanism requires more collisions between ozone E. S. H e d g e s . molecules and oxygen atoms than could actual y GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 835 occur, so that, in its original form, the theory is oxidation of alkaline solutions of stannous chloride untenable. S. K. T w e e d y . when air is passed through is independent of the salt Unimolecular decomposition of azomethane ; concentration. The influence of temperature and the adequacy of activation by collision. B. of rate of passage of air is small. The rate of L ew is (Proc. Nat. Acad. Sci., 1927, 1 3 , 546—549).— oxidation initially increases with the concentration The method given by Fowler and Rideal (this vol., of free alkali, is maximal at 0-2JV-alkali, and then 114) for calculating the number of collisions with slowly decreases. For alkali concentrations greater available energy for redistribution, has been applied than 0-2N the oxidation velocity is the same as that to the homogeneous unimolecular decomposition of of alkaline solutions of sodium sulphite under corre azomethane (Ramsperger, ibid.. 425). On this basis, a sponding conditions (this vol., 525) and the same very conservative estimate of the number of effective explanation holds. J. S. C a r t e r . internal degrees of freedom still leaves it possible to account adequately for the rate of decomposition on the Hydrolysis of aromatic acid chlorides and the theory of induced alternate polarities. G. basis of activation by collision. R. A. M o r t o n . B e r g e r and S. C. J. O l i v i e r (Rec. trav. chim., Velocity of decomposition of nitroacetic acid 1927, 46, 516—527; cf. A., 1926, 1239).—A in aqueous solution. K. J. P e d e r s e n (Trans. study of the relative rates of hydrolysis of sub Faraday Soc., 1927, 23, 316— 328).—Nitroacetic acid stituted benzoyl chlorides and benzenesulphonyl decomposes in acid solution according to the equation chlorides indicates that the hydrolysis proceeds more N02,CH2'C02H— >CH3-N02+C 0 2, and the reaction readily when, according to the theory of induced has been followed by measuring the increase in press alternate polarities, the negative character of the ure of carbon dioxide. In hydrochloric acid solution chlorine or the oxygen atom is diminished by the the velocity coefficient decreases as the concentration substituent. In the case of the substituted benzoyl of acid increases. A greater velocity coefficient is chlorides, this requires for the nitrobenzoyl chlorides found in acetate-acetic acid buffer solutions than in p > A , for the chlorobenzoyl chlorides m >A and hydrochloric acid, and this coefficient, 0-0316 (min.-1 m > 2>, for the bromobenzoyl chlorides m >A and m >p, dekad. logs), is independent of changes in the and for the toluoyl chlorides A > p , where A, m, p hydrogen-ion concentration within the range of the are the rates of hydrolysis of benzoyl chloride itself acetate buffer mixtures. Thus the undissociated acid and the appropriate m- and ^-derivatives. The rates is stable in aqueous solution, and one of the three of hydrolysis at 0° in 50% acetone of the substituted possible isomeric univalent ions is decomposed uni- benzoyl chlorides are in accordance with these require molecularly. From the experiments in hydrochloric ments, with the exception that ^-toluoyl chloride has acid the concentration dissociation coefficient has been a higher rate than benzoyl chloride. It is suggested determined. Its variation with the concentration of that the hydrolysis takes place in two stages, viz., hydrochloric acid, and the effect of the addition of the combination of water with the acid chloride, sodium chloride, are in agreement with the theory and the elimination of hydrochloric acid from the of complete dissociation and interionic forces. The additive product formed. The first stage, which dissociation constant in O-lJV-hydrochloric acid is determines the rate of hydrolysis, is accelerated when 0-0340. The effect of a number of salts on the the negative character of the oxygen atom is de velocity of decomposition of the nitroacetate ion has creased by the presence of a substituent, whilst the been studied. Sodium salts and ammonium chloride second stage, which takes place at a much greater produce no effect, whilst potassium salts, cæsium velocity, is retarded under the same conditions. bromide, and hexamminecobaltic chloride cause accel W. J. P o w e l l . eration. Most salts, however, retard the reaction, Kinetic laws of homogeneous catalysis. Inner and the effect is especially marked in the case of mechanism of a homogeneous catalytic reaction. copper salts. The curves representing these effects E. S p i t a l s k y and N. K o b o s e v (Z. physikal. Chem., appear to exhibit discontinuities. No explanation 1927, 1 2 7 , 129—177).—The change with time in the can be offered of the individual salt effects. condition of a catalyst which is to be expected from M. S. B u r r . the theory of the reversible formation of an inter Does the hydrolysis of sucrose by dilute acids mediate compound between the catalyst and a re belong to the unimolecular group of reactions ? actant forms the basis for a method of testing experi H. C o lin and A. C h a u d u n (J. Chim. phys., 1927, mentally the theory of homogeneous catalysis. It 507—511).—Determinations of the rate of inver follows also from the theory that this time change sion of sucrose by 0-1 Absolutions of sulphuric, hydro will be apparent only in those reactions in which the chloric, oxalic, and nitric acids shows that (1/i) log a/ affinity constant of the intermediate compound is is a function of the time t. Hence this cannot large. For these reasons the catalytic decomposition be regarded as a simple unimolecular reaction, nor of hydrogen peroxide by chromic acid has been even as the resultant of n reactions of which n—1 investigated by measuring the conductivity changes ^instantaneous. The result is, however, consistent during the reaction in a special type of apparatus îfb th e view that the reaction is catalysed by both designed for the purpose. e hydrogen ion and the anion of the acid. During the catalysis of hydrogen peroxide by p M. S. B u r r . chromic acid or by acidified solutions of potassium , ect of alkali hydroxide on the oxidation of dichromate the conductivity at first decreases sharply tannous chloride with air. S. M i y a m o t o (Bull. to a value which remains approximately constant • Soc. Japan, 1927, 2, 155— 160).—The rate of during the major part of the reaction and then returns 836 BRITISH CHEMICAL ABSTRACTS.----A. to its initial value as the reaction approaches com and agree fairly well in part with the experimental pletion. These changes are duo to the formation curves. II. F. G il l b e . and decomposition of catalytic intermediate com pounds, and arc, as is the catalysis itself, completely Increase in ionisation of weak electrolytes by reversible, so that for each initial concentration of complex-formation and its importance for the substrate a definite value is obtained for the catalytic processes. H. Meerweih (Annalen, conductivity decrease and for the minimum con 1927, 455, 227—253),—Many organic reactions are ductivity. That the conductivity changes afford a probably ionic even in cases (“ crypto-ionic” reac parallel with the complicated kinetics of the reaction tions) where ionisation cannot be directly measured. in dilute acid solutions is indicated by the coincidence The theory that such reactions are accelerated by of the maxima of the velocity of catalysis and of circumstances which increase ionisation (this vol., the velocity of the conductivity change. From the 568), and particularly by the addition of substances decrease of the conductivity the extent to which the capable of forming large complex ions (cf. Kossei; hydrogen ions are used up in the formation of'inter A., 1916, ii, 243), is shown to throw light on the mediate compounds may be calculated : the flat por mechanism of many catalytic processes. In exten tion of the velocity curves represents the complete sion of Werner’s term “ anhydro-acids,” neutral removal of the hydrogen ions, whilst the velocity molecules which combine with a solvent increasing maximum expresses their liberation near the end of its acidity by forming complex anions are named the reaction. “ ansolvo-aeids.” Alkoxides of many metals give The relationships have been determined at constant acid solutions in alcohols. Aluminium alkoxides are substrate concentration of the reaction velocity and monobasic to sodium ethoxide and form well-defined of the conductivity decrease with (1) variation of salts, [Al(OR)4]M and [Al(OR)6]M3. Similarly salts the dichromate concentration at constant acid con of the acids [B(0R)4]H and [Sb(OR)4]H are obtained, centration; (2) variation of the acid concentration whilst [Sn(OR)G]H., gives salts [Sn(OR)6]HM and at constant dichromate concentration; and (3) vari [Sn(OR)J2H3M, and [Ti(OR)G]H2 gives [Ti(OR)6]HM ation in constant ratio of both the acid and dichromate and [Ti(OR)6]2H3M. Alkoxides of calcium, beryllium, concentrations. In the third case only are the re magnesium, silicon, phosphorus, arsenic, and bismuth action velocity and the conductivity decrease in do not form complex acids with alcohols, although fluenced in the same manner by the concentration salts [Be(OR)4]K2 and [Mg(OR)JK2 are known. Zino changes. The nature of the curves obtained leads to benzyloxide gives an acid ( :i)[Zn(0CH2Ph)^]H. the hypothesis that during the course of the reaction Glycerolboric acid and the alkali salts of aluminium two intermediate compounds M x and M2 are formed hydroxide are compounds of the same type. Alcohols, reversibly, which require no hydrogen ions for their being neutral, cannot be methylated by diazomethane, formation and. possess relatively small affinity con but in presence of one of the above ansolvo-acida stants, together with a third compound Mz which is they are readily attacked. much more stable and requires hydrogen ions for its Dilute aqueous solutions of zinc chloride or bromide formation. From the initial acid and dichromate are neutral; in more concentrated solutions complex concentrations and the decrease of liydrogen-ion con acids of the type [(ZnCl2)m(OII),1]H;l are formed. centration during the catalysis the most probable Sucrose-inversion experiments show that the hydrogen- nature of the more stable compound M2 is ion concentrations of ll-21f-zinc chloride and of given by the equation : 2Cr207"+ 2 H 202+ K '+ H ' = N - hydro chloric acid are equal. The similarity be KII5Cr40 18", the affinity constant of the reaction tween the catalytic action of zinc cldorido and that being 1 x 1013. The courses of the conductivity curves of the strong mineral acids is thus explained. For have been calculated from this value, and agree closely instance, the zinc chloride compound of ¿soborneol, with the observed curvcs. C10HlsO,2ZnCl2, is transformed in the same way as The complicated kinetics of the chromic acid the i-sobornyl esters of strong acids (cf. A., 1924, catalysis have been investigated mathematically hi 1, 186), the reaction velocity depending, as usual, on. the light of the experimental data; on the flat portion the dielectric constant o f the solvent. The halo- of the velocity curve, where, at high concentrations chromy of the zinc chloride compounds of triaryl- of hydrogen peroxide, the more stable additive com carbinols indicates that these also are salts of strong pound M3 is but little dissociated, the catalysis is complex acids. The catalytic effect of zinc chloride effected simultaneously by two intermediate com on the addition of organic acids to defines and pounds, viz., Ms and the compound M v which is the terpenes is explained analogously by the formation active agent in the catalysis in neutral solution. of acids of the type [RC02-(ZnCl2)JH. Liquid zinc Calculation of the lability constants kx and Jc3 from a chloride-acetic acids give crystallme etkerates, number of independent observations give the values 2[ZnCI2-OAc]H,C4H10O and [(ZnCl2)2-OAc]H,C4HJ0O. ¿1=42 and ks= 5-6. Towards the end of the reaction,, They combine readily with camphene, giving equi as. the hydrogen peroxide concentration becomes very librium mixtures containing the zinc chloride com small, M3 decomposes and releases the hydrogen ions; pound of wobornyl acetate. Comparison of the; very active but short-lived intermediate compounds velocity o f addition to camphene o f the acids are then formed, and account for the sharp maximum [(ZnCl2)2-OH]H and [(ZnCl2)*-OAc]H, where x is in the reaction velocity. 2, 4, and 6, indicates that, in agreement with Ivossel a From the affinity constants of M x and il/3, bearing theory, they increase in strength in the order name . in mind the possible existence of another substance When more than 1 mol. of zinc chloride is presen M 2, the reaction velocity curves have been calculated, in a complex acid, the anion (e.g., OH or OAc) 13 GENERAL, ^PHYSICAL, AND INORGANIC CHEMISTRY. 837 regarded as the co-ordination centre. Many other 1215) the activity of hsemin is gradually destroyed compounds, such as magnesium chloride, zinc chlorate, by hydrogen peroxide, the reaction velocity in the sulphur dioxide, boron trioxide, and pyxoboric acetate, initial stages is exactly proportional to the concen increase the ionisation of organic acids. The most tration of haemin. In 0-02i\r- or stronger hydrogen strongly acting ansolvo-acid is, however, boron tri- peroxide the activity of haemin is independent of the fluoride. Boron trifluoride-acetic acid, b. p. 59°/13 hydrogen peroxide concentration. In weaker solu mm. (undecomp.), is as strong as sulphuric acid and tions the activity-[)S]-curve has been calculated using gives the same halochromic colours with triaryl- hasmin concentrations of 7—26 X 10~6Jf. The results carbinols. It combines vigorously with pinene and are in accordance with the law of mass action and camphene. It is shown by simple experiments that yield a value for the affinity-constant (130) of the the strength of the halogen acids may be similarly haemin-hydrogen peroxide complex of the same order increased (a) by adding metallic halides such as as that (40) previously obtained in the same way for stannic chloride, (6) by forming bimolecular acids catalase-hydrogen peroxide (this vol., 793). The such as [HC13]H, and (c) by adding organic acids, latter complex must therefore have a very much the halogen acid then behaving as an ansolvo-acid, greater velocity of decomposition. [RC02-HC1]H. H. E. F. N o t t o n . H. E. E. N o t t o n . Rate of transformation of acetylchloroamino- Mechanism of the catalytic decomposition of benzene into o- andp-chloroanilides as a measure hydrogen peroxide by metallic ions. A. v o n of the catalytic power of hydrochloric acid. Kiss and (Miss) E. L e d e r e r (Rec. trav. chim., 1927, F. G. S o p e r (J. Physical Chem., 1927, 31, 1192— 46, 453—462).—The catalytic decomposition of acid 1196; cf. Akerlof, A., 1926, 125).—The measurement ified hydrogen peroxide solutions in presence of of the rate of transformation of the chloroamine using various metallic ions has been investigated. Ions of potassium iodide gives too high a value for the constant valency, such as those of the alkaline-earth catalytic activity of the hydrochloric acid for con metals, have no catalytic influence, whilst the small centrated solutions. The true catalytic activity of acceleration of the reaction produced by cobalt, the acid should be measured in the presence of sub manganese, and nickel ions is ascribed to the presence stances such as acetanilide, phenol, or 33-cresol which of small quantities of copper or iron. The mechanism remove the chlorine formed in the first stage of the of the reaction in presence of the copper ion has transformation. The catalytic activity of the hydro been explained. The catalytic decomposition pro chloric acid given by the rate of formation of chlorine duced by the ferrous ion cannot be an ionic reaction. is then not proportional to the velocity coefficient of H. F. G e l l b e . the transformation as ordinarily measured. Promoter action in homogeneous catalysis. L . S . T h e o b a l d . IV. Decomposition of hydrogen peroxide by Displacements of equilibria by substances potassium dichromate accelerated by manganese which simultaneously act as catalytic acceler salts. A. C. R o b e r t s o n (J. Amer. Chem. Soc., ators. II. 1ST. ScHLESINGER [with R . M a LKINA- 1927, 49, 1630— 1642).—The catalytic decomposition O k u n ] (Ber., 1927, 60, [.B], 1479—1483; cf. A., 1926, of hydrogen peroxide by potassium dichromate, pro 1109).—The interaction of ethyl alcohol, acetic acid, moted by small quantities of manganous chloride, is ethyl acetate, and water in the presence of hydrogen made up of two superimposed unimolecular reactions chloride, hydrogen bromide, and sulphuric acid at (cf. A., 1926, 917); the reaction in presence of 100° and, in some cases, at 13° has been investigated. manganous chloride alone is autoeatalytic unless all Mineral acids depress the equilibrium constant, the traces of alkali are removed, when it becomes uni effect being proportional to the concentration of the molecular. The primary reaction is not changed in mineral acid; hydrogen bromide is most and sulphuric rate by the promoting reaction. An intermediate acid least active. In the case of hydrogen bromide, compound containing tervalent manganese is pro the effect appears less noticeable as the temperature duced in an amount proportional to the amount of is lowered. H. W r e n . hydrogen peroxide used. The normal reaction: Fifth report of the committee on contact 2 2 2 2 7 2 2KCr04-f H 0 = K Cr 0 + H 0 + 0 2, is probably sup catalysis. E. E. R e i d (J. Physical Chem., 1927, 31, planted by the rapid reaction: 2HMn02+4H Cl+ 1121— 1149; cf. Taylor, A., 1926, 365).—The liter H202=2MnCl2+4H 20-f-02, which occurs because of ature of the subject for the years 1925 and 1926 is the instantaneous reaction: 2KCr04+2MnCl2+ reviewed, prominence being given to papers on the 3H20=Iv2Cr20 7-|- 2HMn02+4HC1. Spectrographic theories of catalysis. L . S. T h e o b a l d . investigations indicate that when the manganese concentration is higher (0-09IV) the reaction involves Catalytic reactions of ethylene. H. W . W a l k e r formation and decomposition of a permanganate. (J. Physical Chem., 1927, 31, 961—996).—The pro The results serve to confirm earlier work. ducts obtained when ethylene is passed over various S . K . T w e e d y . solid catalysts have been investigated. Ethylene is Catalytic decomposition of hydrogen peroxide stable towards heat at 600°; at 615°, decomposition oy hsemin. H. v o n E u l e r and K. J o s e p h s o n commences in a Jena glass tube. Polymerisation to (Annalen, 1927, 456, 111—126).—In spite of the great a colourless and to a brown oil occurs accompanied oitterence in activity between catalase (C .i\>43,000; by decomposition into acetylene, hydrogen, methane, c. this vol., 376) and haemin (G.F. about 5) their and carbon, and by hydrogenation to ethane. aviour towards hydrogen peroxide appears to be Acetylene is less stable than ethylene, decomposing similar. Although (cf. Kuhn and Braim, A., 1926, above 400°. Mixtures of equal quantities of acetylene 838 BRITISH CHEMICAL ABSTRACTS.— A. and ethylene at 600° in contact with Jena glass yield reaction tube, and polymerisation products (mainly a mixture of the polymerised initial constituents. aromatic hydrocarbons) are also produced. Below Silica gel, silica gel and borax, silica gel and calcium 900° there is considerable production of formaldehyde. hydroxide, borax, calcium silicate, and zinc oxide Acetylene and nitric oxide give a slightly higher yield are all inert towards ethylene up to 600°. Complete of hydrocyanic acid than do ethylene and nitric oxide reduction by ethylene of ferric oxide, zinc oxide, and under the same conditions, but there is a greater lead monoxide occurs at 500°, 800—900°, and 600°, production of polymerisation products and of form respectively. Over the range 100—500°, ethylene is aldehyde. With methane and nitric oxide much polymerised by sodium to a colourless oil and is higher temperatures were necessary to give com decomposed to carbon, hydrogen, and methane. parable yields of hydrocyanic acid. The reaction Ethane, carbides, and hydrides are also formed. between nitric oxide and ethylene has been investig With nickel at 400°, no polymerisation occurs but the ated in detail. It was shown to be a surface reaction ethylene is decomposed into hydrogen and acetylene. and various catalysts were examined, a mixture of Rapid carbonisation at 400° and complete decom equal parts of alumina and quartz proving most position at 545° take place in presence of cobalt. No effective, and by its use the production of form liquid polymerides are formed. Iron polymerises aldehyde was eliminated. Mixtures of nitric oxide ethylene at 360° to a colourless oil and decomposes and ethylene with hydrogen and sometimes nitrogen it slowly into carbon and hydrogen. At 425°, decom were passed through a pear-shaped tube containing position is practically complete. A small percentage the catalyst heated at 900° and the amounts of of potassium hydroxide does not increase the poly hydrocyanic acid, ammonia, carbon monoxide, carbon merisation brought about by the iron. Chromium dioxide, methane, water, hydrogen, nitrogen, and oxide does not promote activity of the iron. In carbon produced were determined under various con creased pressure does not permit the continuous ditions. Increasing the proportion of ethylene in the formation of liquid polymerides owing to carbon mixture increases the yields of hydrocyanic acid, deposition. Pressure studies show that methane is methane, hydrogen, and carbon, decreases the produced from ethylene by fission of the two carbon amounts of carbon monoxide and nitrogen, whilst atoms to yield two CH2 groups which are subse the yield of ammonia increases to a maximum and quently hydrogenated. L. S. T h e o b a l d . then falls off. Increasing the proportion of hydrogen Oxidation of ammonia to nitrate at alkaline in the mixture increases the jdeld of hydrocyanic acid, and decreases the decomposition of the ethylene. surfaces. K. A. H o f m a n n [with K. Leschewski, With nitrogen added instead of hydrogen the formation W. Lemme, H. G alotti, K. M a y e n , and W. G u n d e - of hydrocyanic acid is always less, and the ethylene L A c n ].— See B., 1927, 600. decomposition greater. Decreasing the period of Decomposition of hydrogen sulphide. H. A. contact with the catalyst (from 1-3 to 0-7 seconds) T a y l o r and C. F. P i c k e t t (J. Physical Chem., 1927, lowers the yield of hydrocyanic acid but increases 31, 1212— 1219).—The decomposition of hydrogen that of ammonia considerably. The decomposition sulphide on a heated platinum filament lias been of the ethylene and the yield of carbon monoxide fall studied by a dynamic method at 948°, 1041°, 1138°, with decreasing period of contact, whilst the pro and 1269°. The curves obtained by plotting the duction of water increases and that of methane is amount of gas decomposed against the rate of flow practically constant. Raising the temperature over show a general increase in decomposition with in the range 700—1000° causes a rapid increase in the creased flow. The middle portions of the curves for yield of hydrocyanic acid, but the production of the three lower temperatures, however, are parallel ammonia reaches a maximum at about 800° and then to the flow axis, showing decomposition to be inde falls sharply to a very low value. Rise of temper pendent of the rate of flow over a range which ature also increases the decomposition of ethylene and shortens with a rise in temperature. The temperature the production of hydrogen and carbon, but the yields coefficient for these portions of the curves is 1-035 of methane and carbon monoxide are practically in per 10°, and the heat of activation calculated from the dependent of temperature above 700°. With nitric Arrhenius equation is 11,750 g.-cal., which value, at oxide, ethylene, and hydrogen in the proportions these temperatures, is equivalent to the heat of evapor 1:2:2 at 950° with a period of contact of 1-2» ation of sulphur from the platinum surface. seconds, the yield of hydrocyanic acid is 64-8% ana The suggested mechanism of the reaction consists that of ammonia 2-4% (calculated on the nitric oxide of the primary adsorption of hydrogen sulphide used). oriented with the sulphur atom to the platinum, a From a detailed examination of these results it is fission of the adsorbed molecule, the liberation of concluded that the first stage in the reaction is the hydrogen and the subsequent evaporation of sulphur reduction of nitric oxide to ammonia, part of which from the heated filament. L. S. T h e o b a l d . reacts to form hydrocyanic acid, whilst part dis Catalytic synthesis of hydrocyanic acid from sociates into hydrogen and nitrogen. Ethylene nitric oxide and hydrocarbons. E. E l o d and H . decomposes gradually giving methane, hydrogen, N e d e l m a n n (Z. Elektrochem., 1927, 33, 217—236).— and carbon, but acetylene and highly unsaturate Preliminary experiments showed that the reaction hydrocarbon residues (CH2= and CH==) are Pr°ka 7 between nitric oxide and ethylene yields hydrocyanic intermediate products. The formation of by aro- acid in amounts which increase with rising reaction cyanic acid is then completed by the action of le temperature. At 1000°, however, ethylene decom ammonia either on ethylene or on one of these ni er- poses very rapidly, depositing much carbon in the mediate products. Methane and solid carbon nee GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 839 scarcely be considered in this connexion. Carbon this behaviour. Catalytic efficiency decreases with monoxide is probably produced by the interaction of an increase in the rate of streaming of the mixed gases ethylene with the water vapour formed in the reduction through the catalysts, the effect being greatest with of nitric oxide. H. J. T. E l l i n g h a m . the copperised gel. The efficiency of the catalysts is Sintering of active copper catalysts. F. H. inversely proportional to the partial pressure of the Co n stable (J.C.S., 1927, 1578-—1584).—By measure ethylene in the gaseous mixture. Silverised gel has ments of conductivity and of surface area a study has no catalytic effect. L. S. T h e o b a l d . been made of the reduction of catalytic activity and Law of alternating-current electrolysis and of the surface area which occurs when an active copper the electrolytic capacity of metallic electrodes. catalyst is allowed to oxidise in air at 210°. The J. W. S h i p l e y and C. F. G o o d e v e .—See B., 1927, 633. reduction of surface area on sintering at 440° has also been calculated. These results, together with the Poisoning of hydrogen electrodes. I. A. H. W. influence of the decrease of surface area on the A t e n , P. B r u i n , and W. d e L a n g e (Rec. trav. ¿him., catalytic dehydrogenation of alcohol, indicate that 1927, 46, 417—429).—The poisoning of the hydrogen there is a simultaneous collapse both of the centres of electrode by arsenious oxide is influenced by the area activity of the surface and of the coarse structure. and surface condition of the electrode, the presence The conclusions are reached that the theories of of oxygen, the nature of the electrolyte, and the Taylor and of Armstrong and Hilditch attribute to agitation of the solution. The extent of the poisoning the centres of activity a store of latent energy in is increased by decreasing the area of the electrode excess of that whic-h they actually possess, and that and the thickness of the platinum coating, and by Pease and Constable’s theories are more in accordance increasing the rate of passage of hydrogen and the concentration of oxygen. Poisoning takes place hi with the experimental facts. H. F. G i l l b e . two stages, the first behig an acute poisoning from Temperature and activity of nickel catalysts. which the electrode recovers after a short interval, I. F. T h o r e n (Z. anorg. Chem., 1927, 163, 367— and the second a permanent poisoning which in 395).—The relation between the temperature and the creases for several days. Hydrogen sulphide and activity of nickel hi catalysing the reduction by potassium cyanide have but slight poisoning action, hydrogen of ethylene to ethane, benzene to cyclo- whilst mercuric chloride at low concentrations has hexanc, and oxygen to water has been studied by an influence similar to that of arsenious oxide. In following the pressure within a closed vessel contain order to reduce errors due to a poison, when present, ing the reactants and the catalyst when the temper it is recommended that a large electrode, coated with ature is gradually raised. It is found that with rising platinum-black, be used, that the hydrogen be free temperature there is a series of small temperature from oxygen, and that the hydrogen current be intervals in which there are sudden rapid increases in stopped immediately before taking a reading. the reaction velocity, one of which is much the greatest H. F. G i l l b e . and can be regarded as the transition from slow Electro-deposition of chromium from chromic catalysis to rapid catalysis. The temperatures at acid solutions. I. Stscherbakov and O . E s s in which these effects commence are approximately the (Z. Elektrochem., 1927, 33, 245—252).—25% same, independent of the nature of the reaction and chromic acid solutions containing various amounts of the way in which the catalyst is prepared. In of sulphuric acid or sulphates have been electrolysed some cases, the reaction velocity passes through a with a current density of 0*15 amp./cm.2 and a series of minima. If the same catalyst is used for a current concentration of 0-03 amp./cm.3, using a consecutive series of reductions of ethylene or benzene platinum anode and an iron cathode without a not separated by any intervals, the temperature at diaphragm. During prolonged electrolysis frequent which rapid catalysis commences gradually falls. measurements were made of the concentrations of Keeping the catalyst in an atmosphere of hydrogen chromic acid, CCr0,, and hydrogen ions, C'u., and of or using it for the water synthesis has the reverse the current efficiencies of cathodic reduction, tjr, of effect. No complete explanation of the observed anodic oxidation, t}0, and of chromium deposition, phenomena can be advanced, but it is suggested that 7]a. With pure chromic acid solutions, these efficiencies the temperatures at which sudden increases in reaction are zero, all the current being used hi producing velocity occur may correspond with some kind of hydrogen and oxygen, and it is only in the presence of transitions in the catalyst. R. C u t h i l l . an anion other than the chromate ion that reduction Catalytic activity of metallised silica gels. I. occurs. With solutions containing sulphate ions, ?jR Hydrogenation of ethylene. V. N. M orris and is initially 100% but decreases notably during elec L. H. R e y e r s o n (J. Physical Chem., 1927, 31, trolysis, whilst ijo and Vctt which are initially zero, 1220—1229).—The hydrogenation of ethylene by gradually increase : during this stage GClo, and CH. silica gels metallised with platinum, palladium, or decrease. Eventually, a condition is reached in which copper has been studied by the streaming method. the composition of the solution is practically con The first two metallised gels show marked and uni stant, rjs. being also constant and always greater than form catalytic activity over the temperature range Vo, which now increases only very slowly. 7?Cr, which 0—240°, a slightly diminished activity at the higher reaches a maximum just before the condition of con temperatures being due probably to diminished stant composition is attained, should be equal to adsorption. The copper gel shows a variable activity, Vr—Vo : this is found to be so, if it is assumed the ™rch is minimal at 30° and maximal at 240°. chromium results from the discharge of chromic ions. Hydride formation is suggested as an explanation of These effects are quantitatively the same whether the 840 BRITISH CHEMICAL ABSTRACTS.----A. sulphate ion is added as sulphuric acid, potassium and copper hydroxides are produced. Meldrum’s sulphate, or chromic sulphate, but the nature of the acid-resisting metal produces less hydroxide. The effect cation has some effect on the physical character of of attaching a metal spiral to electrodes of this metal the deposited chromium. Increasing the sulphate in coppcr sulphate solution is described. concentration changes the . conditions in the constant G. A. E l l i o t t . composition stage, Coo, being lowered and rjR, ij0, Electrolytic reduction of acetone and the and i/cr increased. With 14 g. of sulphuric acid per theory of electrolytic reduction. E. Müller (Z. litre, the steady value of CCl0i is about 70% of its Elektrockem., 1927, 33, 253—259).—Solutions of original value and the maximum i/cr is about 12%. acetone in 40% sulphuric acid have been electrolysed With high concentrations of sulphuric acid, -qCc does hi a diaphragm cell under various conditions and not exhibit a maximum but falls gradually throughout using various cathode materials (cf. Tafel, A., 1912, the electrolysis. Breaking the circuit for a time i, 8). The cathode potential was measured and the produces a notable but only temporary increase in i?Cr. gaseous reduction products were collected and analysed. A fresh non cathode substituted for the chromium- The current efficiency for the production of propane coated one acts similarly, but to a smaller extent. was determined as well as the efficiency of total Reducing the current density had no effect except cathodic reduction. Rise of temperature or increase to give smoother and brighter deposits. The low of current density (from 0-1 to 0-25 amp./cm.2) values of r)K in the condition of constant composition tends to increase both current efficiencies. The total suggest that an invisible film on the cathode is prevent current efficiency of reduction decreases with change ing reduction of chromic acid. In pure chromic acid of cathode material in the sequence, amalgamated solutions, the film is probably so continuous that only zinc, cadmium, mercury, lead, silver, becoming hydrogen ions can penetrate it, but its density is less zero with copper and platinum. The sequence of when sulphate ions are present. Under such con current efficiencies of propane formation is the same ditions, the film begins to be effective only when a except that silver and lead are interchanged. The notable concentration of chromic sulphate has been cathode potential, however, decreases in the order, produced ; chromium deposition increases as chromic lead, mercury, amalgamated zinc, cadmium, copper, ions accumulate. On continued electrolysis the film platinum, silver, showing that the progress of reduc becomes so dense that discharge of chromic ions is tion is determined not only by the cathode potential also hindered, i;Cr falls again, and hydrogen evolution but also by specific catalytic effects of the different increases. The increasing denseness of the film is metals. Propane is the principal reduction product attributed to colloidal substances hi the partly except at mercury cathodes. Other products are reduced solution being carried to the cathode by isopropyl alcohol and pinacone, but at mercury and cataphoresis. By electrolysis with a diaphragm, lead cathodes metal alkyls are also produced and at between the electrodes a visible cathode film is pro these two metals the cathode potential is actually duced. In order to obtain a high current efficiency more negative than in the electrolysis of pure 40% of chromium deposition, the accumulation of colloid sulpluiric acid under similar conditions. With other at the cathode must be kept down; this can be metals a small depolarising effect is produced by the achieved by using a low current concentration, by presence of the acetone. In the chemical reduction stirring the electrolyte, or by occasional interruption of of acetone, propane has not been hitherto recorded the current. H. J. T. E l l i n g h a m . as a reduction product, but it is obtained by chemical Electro-deposition of chromium from chromic reduction with amalgamated zinc. A heavier hydro carbon, which seems to be essentially propylene, is acid baths. H. E. Haring and W. P. Barrows.— See B., 1927, 607. also produced, however, whereas electrolytic reduction gave no such product. Electrolysis of copper in presence of gelatin. In a discussion of the theory of electrolytic reduc C. M a r i e and A. B u f f a t (J. Chim. phys., 1927, 24, tions, it is suggested that the mechanism in the pre 470—481).—When a solution of copper sulphate is sent case involves the formation of surface compounds electrolysed in the presence of gelatin the weight of according to equations such as (CH3)2C(OH)2+M-r copper deposited is apparently greater than corre Q =(C H 3)2C(OH.) . . . M +OH' and (CH3)2C(OH)3+ sponds with the current passed. The excess is due 2M +2Q = (CH3)2C. . .2M +20H ', where M is an to a mixture (2:1 approx.) of gelatin with adsorbed atom of the cathode metal. These surface com copper sulphate. The amount is independent of pounds are supposed to have a single electron shared the current density, but depends on the gelatin between each metal atom and the acetone residue. concentration of the bath. The relation between The former compound can then react according the excess weight S and gelatin concentration C may to the schemes, (CH3)2C(OH) . . . M+©==M+ be expressed by the equation S=KCi, where K is a (CH3)2C(OH)', or (CH3)2C(OH) . . . M=M + constant. S appears to be approaching a limiting (CH3)2C(OH)'; similarly the latter gives (CH 3)20 . value in the neighbourhood of 5%. M. S. Burr. Reaction of the former ion with a hydrogen ion Couple deposition of metals. R. S a x o n (Chem. gives isopropyl alcohol or with acetone gives pinacone News, 1927, 135, 33; cf. this vol., 322).—When iron and a hydroxyl ion, whilst reaction of th e latter ion and carbon electrodes are placed in copper sulphate with two hydrogen ions gives propane. Some sue solution and connected outside the liquid, copper is mechanism is necessary in order to account for t e deposited principally on the iron, but also to a smaller observed specific effects of the different metals; t e extent on the carbon. With copper nitrate as formation of metal alkvls can also then be exp lau iec, electrolyte, considerable quantities of colloidal ferrous H. J. T. Ellingham. GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 841 Decomposition of som e organic substances by is concluded that 103 silver atoms are liberated per the electric spark. N. R. F o w l e r and E. W. J. quantum absorbed, and that in a photographic film M a b d le s (Trans. Faraday Soc., 1927, 23, 301— one silver bromide particle is activated per quantum 306).—The decomposition taking place when an absorbed. In photographic films sensitised with electric discharge between carbon clectrodes is calcium tungstate the density of blackening duo passed through a number of organic liquids from to fluorescent light corresponds with the emission a 25 cm. induction coil and Welnlelt interrupter, of at least thirty fluorescence quanta per X-ray using a primary current of 8 amp., has been studied quantum absorbed. R. W. Lunt. to determine the possible action of these substances Latent image. J. E g g e r t and J. Reitstotter.— in delaying detonation in the internal-combustion Sec B., 1927, 620. engine. Paraffin oil, d 0-82, b. p. 182—300°, benzene, aniline, dimethylaniline, and monomethylaniline System : sodium oxide-barium oxide-silica- all give a deposit of carbon and gases consisting carbon dioxide. I. Reactions in the solid mainly of hydrogen and methane with small quantities state between sodium carbonate, barium carbon of acetylene and other unsaturated hydrocarbons. ate, and silica. H. F. K r a u s e and W . W e y l (Z. The residual liquid from the paraffin oil has a dis anorg. Chem., 1927, 1 6 3 , 355—366).—The evolution tillation range similar to that of the original liquid. of carbon dioxide from a mixture of solid barium In the other cases fractional distillation leaves a carbonate and silica when heated in a current of thick tar. The anilines give hydrogen cyanide carbon dioxide commences at 700—750°. At a which, after a few minutes, causes the liquid to given temperature, the amount of the gas given off become electrically conducting without disruption, is approximately proportional to the logarithm of the so that the discharge ceases. No disruptive dis length of time for which the mixture is maintained charge can be passed through ethyl alcohol, the at that temperature. If the ratio of barium oxide liquid conducting the current, but sparks pass through to silica in the original mixture lies between 1 and the vapour alone. Only a small quantity of carbon 0-2, the amount of silica entering into reaction is deposited, but the gases contain a considerable increases with increase in the relative amount present, quantity of carbon monoxide, and there is a distinct but the amounts of the two components reacting odour of acetaldehyde. When a 1-.25 cm. spark, with do not approach any stoicheiometric ratio. If, on a primary current of 2 amp., is passed between the other hand, the value of the above ratio exceeds copper electrodes through acetylene, the spark gap, about 2, the ratio of the reactants tends to 2BaO: lSi02. after the first flash, is bridged by fine carbon threads Addition of sodium carbonate to the system causes the reaction to start at about 400°. Nevertheless, conducting the current. M . S. B u r r . conductivity measurements show that no fused Chemical method io r the standardisation of eutectic is present at the beginning of the reaction. ultra-violet light. J. E. Moss and A. W. K n a p p . The behaviour of the mixtures Na2C03-BaC03-2Si02 - S e e B., 1927, 635. and Na2C03-BaC03-6Si02 has been examined in Role of water in the photochemical decom detail. “ R. C u t h i l l . position of zinc sulphide. H. B. W e i s e r and A. D. Spontaneous ignition of sodium sulphide. A . G a r r is o n (J. Physical Chcm., 1927, 31, 1237— 1245; M e u r i c e (Ing. Chim., 1925,9, SI—88).—Spontaneous of. Schleede, A., 1923, ii, 813; Maass and Kempf, ignition of crude anhydrous sodium sulphide in ibid., 491).—Mainly a theoretical discussion of the oxygen does not take place unless the material is role of water in the photochemical decomposition of heated locally below red heat, or when it is cooled to zinc sulphide. Zinc sulphide is not photochemically 100° and again exposed to a current of oxygen. decomposed by ultra-violet light in the absence of Powdered, but not molten, sodium sulphide con water, which acts neither as a catalyst nor as a tinues to burn after the withdrawal of an impinging component for the synthesis of formaldehyde which flame. Moist oxygen or air causes the temperature reduces the sulphide (cf. Maass and Kempf, loc. cit.). of sodium sidphide to rise, but ignition does not occur. The water plays the part of an ionising solvent for Fused sodium sidphide containing about 30% of zinc sulphide and adsorbed zinc salts yielding zinc water does not ignite, even with local heating, unless ions which, being adsorbed on the sulphide lattice, it is thereby dehydrated. Chemical Abstracts. render it sensitive to light. Experiments show that Ebullioscopic determination of some com soluble zinc salts containing univalent anions increase plexes. F. B o u r i o n and E . R o u y e r (Compt. rend., the sensitivity of the sulphide. Thus, zinc chloride 1927,1 8 5 , 127-—130).—The existence of the following can render even the unignited zinc-blende sensitive complexes has been demonstrated ebullioscopically, to light. Salts containing ions which are more and in most cases the corresponding affinity-constants readily adsorbed than the cations inhibit the darkening have been determined : in solutions of potassium and of zinc sulphide by light. The mechanism of photo cadmium chlorides, K,[CdCl4] and K[CdCl3], when the chemical sensitisation and stabilisation by adsorbed .former and latter salts, respectively, are in excess ; in ions is discussed. L. S. T h e o b a l d . mercuric chloride and potassium bromide solutions Decomposition of silver brom ide per quantum 2HgCl2,3KBr (in equimolecular solutions) and t>i X :fadiati°n. J. Eggert and W. Noddack (Z. K2[HgCl2], [HgCl2,4KBr], and K2[HgBr4] (for non- nt 222—229).—From measurements equimolecular solutions), the last resulting from he energy absorbed by silver bromide films from double decomposition; for equimolecular solutions ir keam of mean wave-length 0-45 A., a n d of sodium acetate and mercuric chloride om the corresponding amount of silver liberated it 2CH3,C02Na,.3HgCl2 (probably a mixture of two 842 BRITISH CHEMICAL ABSTRACTS.— A. salts), and for non-equimolecular solutions a mixture uniform quality was prepared, and portions were of this salt and one richer in sodium acetate the com oxidised by heating in mixtures of oxygen and position of -which was not determined. J. G r a n t . nitrogen under rigidly controlled conditions of temper Double sulphates of the alkali and rare-earth ature, time of treatment, and the composition and rate metals. IX. Neodymium rubidium sulphates. of passage of the oxidising gas. The bulk density of the charcoal is independent of the degree of oxidation F. Z a m b o n in i and V. C a g l i o t i (Atti R. Accad. Lincei, 1927, [vi], 5, 630—636).—The system when the latter takes place at 500°, but at higher Nd2(S04)3-R b2S04-H 20 has been investigated at temperatures it decreases regularly with increase 25°. The double sulphate, Nd2(S04)3,Rb2S04,8H20, of the degree of oxidation. The adsorption isotherms is in equilibrium with solutions containing up to obtained by determining the quantity of iodine 4-73% of neodymium sulphate and from 1-2 to 45% removed from benzene solutions of iodine of con of rubidium sulphate. The crystals have a : b : c= centrations between 0-2Ar and O-OliV are mostly parabolic, the variations of the two Freundlich 0-3015 :1:0-921; (3=96° 40'. R. W. L u n t . constants being reciprocal; with increasing oxidation Basic beryllium carbonate. F. T a b o u r y the exponent at first decreases, then increases rapidly, (Compt. rend., 1927, 185, 275—277).—The decom and finally decreases slowly. The suggestion is position product at 100° of beryllium ammonium made that the rapid variations correspond with a carbonate prepared by precipitation of pure beryllium change in the number of attracting centres per unit sulphate with ammonia in presence of a stream of surface area of the charcoal, and that the slow change carbon dioxide has not the composition is due to increase of surface area per unit weight. C02,3Bc0,5H20, as is usually supposed, but contains These views are supported by the nature of the bulk ammonia. This is not easily washed out with a density curves. H. F. G ill b e . solution of carbon dioxide in water, and after 20 years the ammonia and water contents are lowered only Azido mixed salts. A. C. V o u r n a z o s (Z. anorg. slightly. The removal of water and of ammonia is Chem., 1927,164, 263—273).—The following white or slightly accelerated by the presence of concentrated colourless compounds have been obtained by the sulphuric acid, and by washing under pressure, reaction in methyl alcohol or acetone solution of respectively. J. G r a n t . sodium azide and a salt: with arsenious chloride, Action of strontium oxide and lead oxide on Na8[AsBr3(N3)8] ; with arsenious iodide, aluminosilicates. B. G a r r e (Z. anorg. Chem., Na8[AsI3,(N3)8]; with zinc chloride, [ZnCJ2,N3]Na; 1927, 164, 202—206; cf. Tammaim and Grevemeyer, with zinc bromide, [ZnBr2,N3]Na; with zinc iodide, A., 1925, ii, 580).—The heating curves for mixtures [ZnI2,N3]Na; with zinc cyanide, [Zn(CN)2,(N3)6]Na6; of barium oxide with nepheline, orthoclase, or leucite with zinc formate, [Zn(HC02)2,N3]Na; with zinc show that an evolution of heat commences at about acetate, [Zn(CH3-C02)2,N3]Na. In general, all the 435°, the effect being more pronounced if hydrated soluble azides form similar compounds with a great mixtures are examined. Alumina is much more variety of zinc salts. The triple compounds readily attacked by barium oxide than is silica, [Zn(N03)2,4ZnCl2,N3]Na4,6H20, 2ZnI2,2NaN3,AgI, although the heat of reaction is smaller, so that it and PbI2,4(ZnL>,NaNo) have been obtained. seems that the extent of interaction in mixtures of R. C u t h ill. solids depends not on the magnitude of the accom Hyposulphurous acid. M. B a z l e n (Ber., 1927, panying heat effects but only on the diffusibility 60, [£], 1470—1479).—The following evidence is of the reactants through the resultants. Mixtures of adduced in favour of the view that the compounds lead oxide with quartz, alumina, or the above silicates of aldehydes with sulphurous and sulphoxylic acids first evolve heat at about 710°, but with the are hydroxysulphonic and hydroxysulphinic acid3 silicates the electrical resistance of the mixtures (cf. Raschig, A., 1926, 598) and that hyposulphurous falls suddenly above 675°, owing to the formation of acid is disulphinic acid, H-S02-S02H. The formation fused eutectics. Lead aluminate may be obtained of the latter compound by reduction of sulphurous by heating an intimate mixture of finely-powdered acid is thus readily explained and the formulation, lead oxide and alumina at 700° for a long time, the as contrasted with that of a mixed anhydride, is in reaction occurring entirely in the solid state. Lead harmony with the stability of the sodium salt only in oxide attacks alumina more readily than it attacks presence of an excess of alkali hydroxide. Powerfu silica. R. C u t h i l l . oxidising agents, such as iodine, cause rupture o the S-S linking with production of sulphate in place Samarium sulphide. W. K l e m m and J. Rocic- of the expected dithionate. Under certain conditions, STROH (Z. anorg. Chem., 1927, 163, 253—256).— manganese dioxide, potassium permanganate, or Heating samarium sulphate in hydrogen sulphide nickel oxide cause the formation of dithiomc aci , at 500—600° does not give a pure sulphide, some which is also obtained from sulphurous acid, ® oxide always being formed. At 800— S60°, however, alkaline solution, however, dithionate is either no the nearly pure sulphide, with df 5-82, is obtained obtained or produced only in subordinate amoun after long heating. There are some signs of the from sulphite. Formaldehyde and sodium existence of a polysulphide. R. Cu t h i l l . sulphite vield sodium hydroxymethane-sulpnona Activation of wood charcoal by progressive and -sulphinate, the salt thus suffering fission wim oxidation in relation to bulk density and iodine addition o f water in the same manner as the ditliiona • adsorption. A. B. P. Page (J.C.S., 1927, 1476— Sodium hydroxymethanesulphinate and so u 1494).—A considerable quantity of wood charcoal of hydrogen sulphite give sodium hyposulphite ai GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 843 formaldehyde. The free hydroxysulphonic acids are sulphoxylic acid and its bearing on the initial stage extremely unstable, whereas the hydroxysulphinic in the Wackenroder reaction are discussed. On acids are stable. decomposition, hyposulphurous acid yields hydrogen Hydroxymethanesulphonic acid is monobasic, sulphide as well as sulphur dioxide. The colour of whereas the corresponding sulphinic acid gives salts this compound, or an isomeride, and of other sulphur of the types, 0H-CH2-S02X and 0X-CH2-S02X. The compounds, is attributed to the presence of a sulphur di-zinc salt is prepared as the trihydrate and mono- atom with a 10-electron sheath. hydrate which when heated at 160— 165°/vacuum The decomposition of thiosulphuric acid may afford the anhydrous compound ; the composition of occur in three ways, expressed by the equations : the latter compound and its stability towards heat H2S20 , ^ H 2S03+S, 2H2S203^ H 2S+ H2S?0 6> and are considered to establish that the secondary salts 2H2S203^=^H20+ H 2S40 5. The decomposition of are formed from the primary compounds by an thiosulphuric acid as expressed by the first of these alkoxide reaction. This conclusion is confirmed equations is probably bimolccular, involving a by the observations that secondary salts do not give diatomic sulphur molecule. The second method of amino-compounds and only primary salts can be decomposition is an essential step in the Wackenroder obtained from the amino-derivatives of mono-salts. reaction, trithionic acid being the primary thionic Attempts to prepare secondary salts by the action acid formed both in the decomposition of thiosulphates of zinc oxide or calcium hydroxide on the zinc or and in the Wackenroder reaction. Thiosulphates calcium salts of the amino-compounds from aldehyde- probably never decompose with the direct formation sulphinic acids were unsuccessful and the preparation of sulphate, which is produced from trithionate. of anhydrous zinc anilinometJuinesidphiiuila shows Decomposition of thiosulphates into the new anhydro- that the sulphoxylic acids cannot be ortho-acids. acid, H2S405, and the oxidation of the latter by The production of a dibarium salt from the condens methylene-blue to tetrathionic acid are described. ation product of sodium hydroxymethanesulphinate The modes of hydrolysis and structural formulae of and monomethylaniline (cf. Forke, Diss., Berlin, the thionic acids are discussed. H. F. G i l l b e . 1923) could not be confirmed. The diformaldehyde- Reaction of sulphur with aluminium and sulphoxylie acid described by Binz (A., 1918, i, 4) magnesium. H. D a n n e e l and K. W. F r o h l i c h must be regarded as dihydroxymethylsulphone ; the (Z. angew. Chem., 1927, 40, 809).—Rapid ignition ready loss of one formaldehyde molecule from this of an aluminium-sulphur mixture by means of a compound is exactly analogous to the instability of mixture of magnesium and barium peroxide resulted phenyl-a-hydroxyethylsulphone, m. p. 52°, prepared in an explosive reaction. A 5 g. mixture of sulphur from benzenesulphinic acid and acetaldehyde in ether. and magnesium, ignited by a little potassium chlorate Methanesulphinic acid is oxidised by iodine to and sulphur, shattered the jaws of a strong iron methanesulphonic acid as final product. Hydroxy stand. A. C o u s e n . methanesulphonic acid is however converted into sulphuric acid and formaldehyde. With permangan Reaction between manganese salts and sodium ate at 0° and in presence of magnesium chloride it hypochlorite in presence of certain other salts. B. E. D i x o n and J. L. W h i t e (J.C.S., 1927, 1469— gives hydroxymethanesulphonic acid. H. W r e n . 1476).—Sodium hypochlorite precipitates manganese Compound intermediate between vanadium almost quantitatively from a solution of a manganous sulphate, V20 5,iiS03 and vanadyl sulphate, salt as hydrated manganese dioxide. The presence V0SO4. V. A u g e r and C. E i c h n e r (Compt. rend., of certain other salts, notably those of copper, cobalt, 1927,185,208—210).—The slow reduction by sulphur nickel, and molybdenum, causes permanganate to be dioxide of a solution of a vanadic salt in sulphuric acid the main product. A study has been made of the by sidphur dioxide gives rise to an indigo-coloured relationships between the time of heating, the volume solution intermediate in composition between the of oxygen evolved, and the quantity of permanganate vanadic and vanadyl states. It is also produced on produced : permanganate formation practically ceases mixing solutions containing equal proportions of the after boiling for about 3 min., by which time about sulphates of the oxides V205 and V204. It has not one third of the total oxygen evolution has taken been possible to isolate this vanadic vanadyl sulphate place. The catalytic influence of cobalt differs w a crystalline state, but the conditions of stability fundamentally from that of copper in that it is of its solution, and its absorption spectrum, have scarcely affected by liydroxyl-ion concentration, that been determined. The colour is readily dispersed the quantity of permanganate formed decreases as by acid, but is regenerated on the addition of water, the proportion of manganous salt is increased, and he formula HSO4-V0(OH)-SO4-V(0H)„-HSO4 is that a different type of precipitate is. formed, the suggested. J G r a n t . cobalt being incompletely precipitated even on pro longed boiling. The necessary condition for the Inter-relationships of the sulphur acids. H. quantitative oxidation of a manganous salt to per « and R - G- Currant (J.C.S., 1927, 1401— manganate hi presence of cupric salts is the neutrality bo).-—When sulphoxylic acid is liberated by ydrolysis from sodium formaldehydesulphoxylate of the solution, which may be maintained by a sodium i readily decomposes into hydrogen sulphide and carbonate-sodium hydrogen carbonate buffer solu u pnurous acid ; from this and other evidence it tion. H. F. G i l l b e . concluded that the hydrolysis of sulphur takes Active iron. A. S i m o n and K. K o t s c h a u [with W. G u t m a n n and G . Buss] (Z. anorg. Chem., * * * £ * * t0 the. reaction S2+2H 2O ^ H 2S+ ■‘■be mechanism of the decomposition of 1927, 164, 101— 126).—Using 5—10 c.c. of a 0-5%. 844 BRITISH CHEMICAL ABSTRACTS.— A. alcoholic solution of guaiacum resin per 250 c.c. of strong acids and moderately strong acids because it water, a blue colour is produced by 5-6 XlO~G g. of involves the greater lieat effect. R. C t jth ill. ferrous iron in presence of hydrogen peroxide in 1 litre of neutral solution, and 6-8 XlO-5 g. in a Weakening of the oxidising properties of ferric slightly acid solution. The best results are obtained chloride on warming. M. J. Gramenitziu (Bio- by adding the hydrogen peroxide to the mixture of chem. Z., 1927, 1 8 5 , 430— ¿32).—1The oxidation of ferrous salt and guaiacum solution. Light should guaiacum, and the liberation of iodine from potassium bo excluded, and appreciable amounts of acetic or iodide, by ferric chloride are much delayed if the hydrochloric acid interfere, whereas alkaline solutions ferric chloride solution has been recently boiled; do not give the test at all. If “ ferrum redactum ” when kept, the cooled solution gradually regains its is ground up in a mortar, it commences to give the original oxidismg activity. The effect may be duo benzidine and guaiacum resin reactions, ferrous to diminution of the dissociated ferric chloride mole hydrogen carbonate being formed by atmospheric cules on boiling; an analogy is drawn between this moisture and carbon dioxide. By filtration of a phenomenon and the behaviour of certain enzymes suspension of the activated preparation through a towards heat. C. R. H a r in g t o n . membrane filter, an active liquid is obtained, but Production of fluorite in the electric furnace. this gradually loses its activity, the activity towards D. C. S t o c k b a r g e r .—See B., 1927, 600. benzidine and guaiacum resin being a function of the ferrous-ion concentration. The activity of the Preparation of boron. L. A n d r i e u x (Compt. liquor hi respect of the catalysed decomposition of rend., 1927, 1 8 5 , 119— 120; cf. this vol., 216).— hydrogen peroxide is scarcely different from that of Boron may be prepared continuously by the electrolysis the liquor obtained from untreated ferrum redactum, at 1100° of the mixture (2B203+Mg0-j-MgF2) in a so that it is uncertain whether the therapeutic charcoal crucible which acts as anode, the cathode efficacy is improved by the grinding. By filtering a being an iron rod. The cathode deposit consists of suspension of ferrum redactum in oxygen-free water boron agglomerated by the solidified electrolyte. It saturated with carbon dioxide through a membrane- is ground and extracted with hydrochloric acid, and filter, a liquid results which is active, and retains its a residue of amorphous boron obtained of 92% purity. activity for weeks, even if light is not excluded, The yield is 95%. J. G r a n t . provided that it is kept out of contact with air. Preparation and properties of pure silicon. The effect of ultra-violet radiation is very slight so R. Ho l b li n g (Z. angcw. Chem., 1927, 40, 655— long as air is carefully excluded. It is concluded 659).—A current of hydrogen, prepared from pure that the activity of natural waters containing iron zinc and pure hydrochloric acid, and exhaustively depends on the presence of ferrous iron, and when freed from all suspended matter and moisture, is this is oxidised the activity disappears. Cobaltous, passed through pure silicon tetrachloride, and the nickelous, manganous, mercurous, and cuprous salts mixture of gas and vapour passed over a glowing or the ground-up metals give, hi presence of hydrogen carbon filament 0-3 mm. thick, maintained at 1000° peroxide, the benzidine and guaiacum resin reactions, by an electric current. The resistance of the fila whilst cadmium and zinc do not do so. ment increases as the temperature falls by deposition R . C u t h i l l . of silicon; it is not possible to prepare rods of thick Precipitation of iridium from its solutions by ness more than 4 mm. in this way, since the current hydrogen under pressure. V. I p a t i e v and J. necessary to give a temperature at the surface of A n d r e e y s e i (Compt. rend., 1927, 1 8 5 , 357—359).— the rod sufficient to ensure decomposition of the The authors’ method (A., 1926, 1219) has been tetrachloride raises the internal temperature to tho extended to chloroiridate solutions at 100° and 103°. point at which the unchanged carbon filament-unites As in the case of platinum the production of metal with the silicon to form the carbide. The product is greatest at low concentrations, and increases with has a metallic appearance, is v e r y stable in the air, pressure, temperature, and time. Under the same and appears to become more brittle as the tem conditions iridium is deposited more completely than perature rises. The coefficient of linear expansion platinum at 100°. In cases of incomplete precipit is 3-55 xlO -6/lS—950°; the electrical conductivity ation a blue, unstable solution of colloidal iridium is increases with rise in temperature. Tables and produced. J . G r a n t . curves are given for the conductivities at different temperatures. S. I. L e v y . [Decomposition of iron carbide by acids.] T. M t l l n e r (Z. anorg. Chem., 1927, 1 6 4 , 186— Purification of cerium. L. I m r e (Z. anorg. 188).—Extrapolation of Eucken and Fried’s data for Chem., 1927, 1 6 4 , 214—218).—If nitric acid solutions the equilibrium C+2H2^ C H 4 (A., 1925, ii, 97) of cerium nitrate are shaken with ethyl ether, part shows that the separation of solid carbon when iron of the cerium passes into the ether, but the accom carbide is treated with acids such as acetic acid is panying impurities or cerous salts do not do so. due to the inertness of the carbon rather than to The distribution ratio varies in a complex manner the hydrogen tension on the carbide being too small ■with the concentrations and with the relative pro for complete reduction of the carbon, as Schenck portions of the phases, but the best results are and Stcnkhoff have suggested (this vol., 532). It is obtained if the acid concentration is about 10'O.A. further probable that of the two reactions Fe.,C4- R . C uthill. ? fg '= 3F?"+CH4+H2 and Fe3C+6H'=3Fe"+C+ Decomposition of phosphate rock by sulphuric 3H2 the latter occurs to the greater extent with both acid. W. S t o l l e n w e r k .—S e e B., 1927, 554. GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. S45 Application of spectrum analysis to the apparatus and technique for the determination of detection of metallic impurities. E. Bayle and gases dissolved in water by evaporating 1—2 c.c. L. Ajiy (Compt. rend., 1927, 185, 268—270).— of it, absorbing the vapour, and measuring the Small quantities of metallic impurities may be pressure of a known volume of the residual gas, are separated from large quantities of salts by electrolytic described. Complete removal of the vapour is deposition from a boiling solution on the tip of an essential and absorption in phosphorus pentoxide electrodc which is subsequently used to obtain the gives more constant pressure values than condensation spectrum of the metal. The deposition may be using carbon dioxide-acetone snow. If tho water performed in presonce of large quantities of alkali, is introduced into a high vacuum, it solidifies at alkaline-earth, or ammoniacal salts, and it has been once, evolving most of the dissolved gas, and then possible to recover 10-4 mg. of copper from 0-5 g. of evaporates slowly. Tho method ensures a more zinc. The sensitiveness of the method varies from complete separation of the gas than that usually 10-6 to 10"10 g. for the metals gold, silver, lead, copper, employed, a value of 34 c.c. of ah1 per litre of distilled iron, cobalt, nickel, chromium, manganese, and zinc. water being obtained. J. G r a n t . J . G r a n t . Evolution of mineral substances and its An absolute method of quantitative analysis analytical applications. A. J o u n i a u x (Bull. Soe. by emission spectra. II. E. S c h w e i t z e r (Z. chini., 1927, [iv], 41, 905—920).—A lecture delivered anorg. Chem., 1927,164, 127— 144).—The “ ultimate- before the Lille section of the Société chimique de ray ” method of determining small amounts of France on May 2, 1927. impurities in a substance is unsatisfactory because the intensities of the ultimate rays are largely de Use of yellow mercuric oxide and of metallic pendent on the experimental conditions. Gerlacli’s mercury as standards in volumetric analysis. method of analysis by comparing the intensity of a I. M . K o l t h o f f and L. H. v a n B e r k (Z. anal. Chem., line in the spectrum of the impurity with that of a 1927, 71, 339—348).—For the standardisation of neighbouring line in the spectrum of the main sub hydrochloric acid with yellow mercuric oxide 1 g. stance both in the substance under examination and of the oxide is dissolved in a warm solution of 20 g. in a series of standards (A., 1925, ii, 711) has there of neutral potassium bromide hi 25 c.c. of water fore been developed. It is hi some cases possible and the liquid is titrated with the acid using dimethyl- to select a number of pahs of lines, one in the spectrum yellow or methyl-orange as indicator. The results of the main substance and the other in that of the are within 0-1% of those obtained with borax. As impurity, the relative intensities of which are com mercury can be prepared in an exceedingly pure paratively insensitive to variations in the conditions condition by distillation in a vacuum it forms a of the discharge producing the spectra. If for eaoh useful standard for thiocyanate solutions instead of pair there is determined the composition of the silver. Provided the temperature of the solution mixture in the spectrum of which both lines are during titration is kept below 15° the error is less equally intense, the test-sample is analysed by than 0-02%, but is increased by working at higher ascertaining for which pair the two lines are of the températures. This may be allowed for by working same intensity. In this way it is possible to determine with solutions saturated with mercuric thiocyanate lead, bismuth, or cadmium in tin, and tin in lead. at the temperature of titration. A. R. P o w e l l . Where a suitable number of pairs of lines cannot bo Precise volumetric analysis. III. Standards found, the spectrum of a second substance is photo for alkaline solutions. K. O. S c h m it t (Z. anal. graphed on top of the spectrum of the substance Chem., 1927, 71, 273—290; cf. this vol., 329).— for analysis. If this auxiliary spectrum is related For the standardisation of alkali hydroxide solutions in a fixed manner to that of the mam sub pure oxalic acid dihydrate or potassium tetroxalate stance by adjusting the time of exposure so that a give equally accurate results. Both compounds selected line in one spectrum has the same intensity should be recrystallised from water hi small crystals as a selected line in the other, both spectra can be and dried at the ordinary temperature. The tetroxal used to find suitable pairs of lines. Bismuth can be ate is made by mixing potassium oxalate (1 mol.) and determined in lead, using as the auxiliary spectrum oxalic acid (3 mol.) solutions at 100° and cooling that of tin. R . C u t h i l l . rapidly. Phenolphthalein must be used as indicator in both cases. Neutral calcium oxalate free from Apparatus for gas analysis. J. N. J. P e r q t j i n . -See B., 1927, 591. acid or basic salts is obtained by treating oxalic acid solution with neutral calcium chloride solution. The Hempel gas analysis apparatus without hydrochloric acid- liberated by the oxalic acid can absorption bulbs. R. C. F r e d e r i c k . —See B., then be used for standardising an alkali hydroxide 1927, 001. solution using methyl-orange or dimethyl-yellow as Modification of the Haldane general air indicator. A. R. P o w e l l . Determination of moisture by the volatile 19^7 GOO a-PPara^US- R- C. F r e d e r i c k .—See B., solvent method. J . M . J o n e s and T. M oL a c h l a n . Gas analysis instrument based on sound- —See B., 1927, 591. measurement. E. G r i f f i t h s .—See B., Detection of chlorides in mercury oxide. *¡»7, 591. C. J. W. F e r r e y .— See B., 1927, 600. Measurement of gases dissolved in water. L. Colorimetric determination of perchlorate in wnoyer (Compt. rend., 1927, 185, 271—273).—An saltpetre. 0. S. F e d o r o v a .—See B., 1927, 600. 846 BBITISH CHEMICAL ABSTRACTS.----A. Volumetric determination of iodides. A. J. was kept in a long sampling tube in a vertical position. J o n e s .—See B., 1927, 554. Samples withdrawn from the same end of the tube Apparatus for the [collection of ammonia in on successive days were of constant composition; the] determination of nitrogen. R. K a t t w i n k e l no stratification had therefore taken place. After (Chera.-Ztg., 1927, 5 1 , 568).—The bulb trap used introduction of carbon dioxide into the bottom of above the distillation flask to catch any spray is sealed such a tube, with avoidance of mechanical disturbance, directly to the condenser so that the vapours pass diffusion was complete within 1-5 hrs. upwards from the distillation flask through the trap, C. R . H a r in g t o n . then downwards through a three-bulb condenser the Quantitative m icroscopic analysis [of rocks]. lower end of which passes through the outer wall H. L . A l l i n g and W. G. V a l e n t i n e (Amer. J. Sei., and downwards to the collecting flask. The top of 1927, 1 4 , 50— 65).—To determine the actual per the condenser tube is provided with a glass stopper centages of the various minerals hi a rock the areas to allow the inside to be rinsed out after the distillation of the fields occupied by them in a microscopic is finished. A. R. P o w e l l . section are traced by means of a camera lucida on a circular area of 50 sq. in. The sum of the areas of Rapid determination of gaseous hydrogen every constituent is then measured by means of a phosphide in a mixture. M . W i l m e t (Corapt. planimeter and from a knowledge of the chemical rend., 1927, 1 8 5 , 206—208).—The colour, weight, composition of the various minerals and of the and composition of the precipitate obtained according complete analysis of the rock the proportion of every to Lemoult’s equation PH3-j-3HgCl2=P(HgCl)3+ mineral present can be calculated. The possible 3HC1, are variable. The ratio of the volume of the sources of error are discussed and various typical gaseous hydrogen chloride, however, to that of the results are given and compared with those obtained reacting phosphine is constant, whatever the nature by other authors on similar rocks. A . R. P o w e ll. of the precipitate. Consequently, an excess of mercuric chloride is shaken with distilled water and Determination of alkalis in ores, clays, and the sample of gas (100 c.c.), and the acid produced is refractory materials. J. C i o c h i n a .—See B., 1927, titrated with 0-lAr-sodium hydroxide solution (n c.c.), 605. with methyl-orange as indicator, after removal of ' Determination of sodium nitrite. F. A. Hoeg. the precipitate by filtration. The corresponding —See B., 1927. 600. volume of phosphine at 15° and 760 mm. pressure is Extension of the use of borax in acidimetry. 0*784» c.c. For less than 0-5% of phosphine by T. M ilobedski and H. K a m in s k a (Bull. Soc. chim., volume the determination is made by comparison 1927, [iv], 4 1 , 957— 960).—The compound with standard solutions, and 1 part in 70,000 parts Na2B40 7,10H20 is obtained in the pure state and may be determined. The standards are stable in protected against efflorescence and carbon dioxide. the dark for 2—3 days. J. G r a n t . It can then be used as a substitute for anhydrous Determination of sulphur [in coal]. H. t e r sodium carbonate when standardising acids, methyl- M e t j l e n .—See B., 1927, 545. red being used as an indicator. F. S. H a w k in s. Determination of sulphate by the palmitate Volumetric determination of calcium and method. J. Z i n k and F. H o l l a n d t (Z . anal. Chem., ferrocyanide ions. T. C a s p a r y A r n a l (Diss., 1927, 71, 386—388; cf. A., 1914, ii, 670, and Bahrdt, Madrid, 1923).—Calcium can be completely and B., 1927, 238).—The palmitate method for the rapidly precipitated in the presence of strontium determination of sulphate hi water gives sufficiently and barium from a dilute solution containing 50 accurate result« for most purposes without previously vol.-% of alcohol by the addition of standard potass removing the lime and magnesia as advocated by ium ferrocyanide solution; a dilute solution of Bahrdt. A combined hardness and sulphate test is ammonium molybdate, acidified with acetic acid, is carried out as follows. Two separate 100 c.c. portions used as an external indicator. of the water are neutralised with 0-liY-hydrochloric C h e m i c a l A b s t r a c t s . acid using methyl-red as indicator, a small excess of Analysis of fluorspar. B r a u e r and R t jth s a tz acid is added to both and 5 c.c. of 0-liV-barium (Chem.-Ztg., 1927, 5 1 , 618—619).—Drawe’s method chloride solution to one portion only, and, after (ibid., 1925, 5 0 , 497, 623) is satisfactory. When the boiling, cooling, and neutralising with sodium hydr mineral contahis barium sulphate, this may he oxide, both are titrated with the palmitate solution. decomposed on boiling with soda, and a c c o u n t must If a c.c. of the latter are consumed by the portion be taken of the barium thus brought into solution. without barium chloride, b c.c. by the portion with S. I. L e v y . barium chloride, and c c.c. by 5 c.c. of barium chloride, Analysis of calcium nitrate. J. M. M c C a n d l e s s . then a -fc—b c.c. of palmitate solution correspond —See B., 1927, 637. with the sulphate content of the water and a c.c. Determination and separation of rare metals with the hardness. A . R . P o w e l l . from other metals. IX. Quantitative separ Thiocarbamide as an impurity in thiocyanates. ation of beryllium and aluminium. L . Alosra T. S. P r ic e a n d J. W , G l a s s e t t .—See B., 1927, 600. and M. Niessbr (Monatsh., 1927, 4 8 , 113-1-1)* Absence of stratification and rapidity of mixing Previous unsatisfactory methods for separating bery of carbon dioxide in air samples. T. M. C a r ium and aluminium are reviewed, and t h e principes p e n t e r and E. L. Fox (J. Biol. C h e m ., 1927, 73, of a possible separation are discussed. The reage ■ 379—381).—A mixture of carbon dioxide and air now employed is an ammonium acetate solutio , GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 847 saturated in the cold and containing 3% of pure cyanide by addition of potassium cyanide and the tannin. This gives with an aluminium sulphate cadmium precipitated from the feebly acid acetate solution a brown precipitate of aluminium hydroxide solution by means of 8-hydroxyquinoline. From the and adsorbed tannin, which, unlike aluminium heavy metals cadmium is separated by double precipit hydroxide alone, is easily soluble in dilute acids; ation in alkaline tartrate solution. A. R. P o w e l l . the reagent may be used for the detection of alumin Salts of the halogen acids of bismuth and ium, having a sensitivity of 1 : 5000. With beryllium cadmium with organic bases and their analytical sulphate solutions the reagent gives no precipitate, application. I. R. B e r g and O. W ü r m (Ber., even on prolonged boiling; since solutions of the 1927, 60, [J3], 1664—1671).—Cadmium may be chloride or the nitrate give slight precipitates, it is determined by treating a solution of the metal in necessary to convert the metals into sulphates before dilute sulphuric acid with sodium tartrate followed separation. As freshly-precipitated and washed by a solution of ß-naphthaquinoline in 0-5A7-sulphuric beryllium hydroxide dissolves rapidly in the reagent, acid, a few drops of ddute sulphurous acid, and finally the beryllium is considered to react chemically to potassium iodide solution, whereby the salt form a soluble complex salt. For the separation of (C13H9N),H2[CdI4] is precipitated. The precipitate beryllium and aluminium, a solution of the sulphates is washed with a solution of ß-naphthaquinoline is diluted with hot water and the ammonium acetate sulphate and potassium iodide in water, and decom and tannin solution, heated at 80°, is added. On posed by ammonia or sodium hydroxide; the solution boiling, the aluminium is quantitatively removed in is acidified with hydrochloric or sulphuric acid and the precipitate, which contains no beryllium. The titrated with 0-liV-potassium iodate solution. The tannin is removed by oxidation with nitric acid; determination of cadmium may be effected in the residual traces of organic substances have no influence same manner in presence of relatively large amounts on the determination of either metal. of zinc; the latter metal is determined by precipit E. W . W i g n a l l . ation from the filtrate with 8-hydroxyquinoline. Its Colorimetric determination of traces of mag separation from cobalt, nickel, manganese, ferrous nesium. I. M. K o l t h o e f (Biochem. Z., 1927, 185, iron, chromium, aluminium, and magnesium is 344—348).—Addition of titan-yellow to an alkaline similarly effected. In the separation of cadmium solution containing small amounts of magnesium from tin and antimony a larger proportion of sodium produces a red colour, the reaction being specific tartrate (or ammonium oxalate) is necessary. for this metal. By this means 0-2 mg. per litre of In the determination of bismuth, the solution, magnesium can be detected, and 0-4—4-0 mg. per slightly acidified with nitric or sulphuric acid, is litre determined colorimetrically. The reaction can treated with an excess of 8-hydroxyquinoline dis not be used in presence of aluminium and zinc salts. solved in 0-2^-sulphuric acid followed by potassium C. R. H a r i n g t o n . iodide until the precipitated salt, (C9H7ÖN),H[BiI4], Colour reaction of magnesium. W. J. P e t r a - collects together. The precipitate is washed with schenj (Z. anal. Chem., 1927, 71, 291—297).— an acid solution containing 8-hydroxyquinoline, When a neutral solution of a magnesium salt is potassium iodide, and a little hydrazine sulphate, treated with a O-ljV-solution of iodine which has dissolved in acid, and titrated with potassium iodate been almost decolorised by addition of a 0-2iV-solution solution. The method is suitable for the separation of sodium hydroxide a deep red adsorption complex of bismuth from the other metals except mercury, of magnesium hydroxide is precipitated. The reaction silver, lead, and thallium. Hydrochloric acid in is perceptible in magnesium salt solutions as dilute considerable concentration is harmful. In the pres as 0'0005iV and the presence of the alkaline earths ence of cupric and ferric salts pyridine must be has no disturbing action. Ammonium, cobalt, and added. A large excess of tartaric acid is required manganese salts interfere. A. R. P o w e l l . if antimony or tin is present. H. W r e n . Determination of small quantities of zinc in Determination of lead and ferrocyanide ions aluminium. W. B o h m .— See B ., 1927, 605. by Fajans’ method. R. B t t r s t e i n (Z. anorg. Chem., Separation and determination of metals by 1927, 164, 219—222; cf. Fajans and Wolff, A., means of 8-hydroxyquinoline. IV. Cadmium. 1924, ii, 776).—Potassium ferrocyanide can be titrated with lead nitrate, using a 0-4% solution of R. Berg (Z. anal. Chem., 1927, 71, 321—331; cf. following abstract).—The cadmium compound with sodium alizarinsulphonate as indicator, the colour o-hydroxyquinolme is precipitated in solutions con change at the end-point being from yellow to red. taining sodium acetate or tartrate under conditions The most suitable concentration of the nitrate solu similar to those described already for the zinc com tion is 0-03—0-015JV. Lead may be determined by pound. The precipitate contains 2HaO, but, after adding excess of ferrocyanide and titrating back the excess. Fajans’ adsorption method of titration can ^ 8 at 100°, it consists of Cd(C9H60N)2,l'5H20 ic*1 becomes anhydrous at 130°. As the cadmium be used successfully only if the anion of the salt to compound is readily soluble in hot 10% acetic acid, be determined forms a sparingly soluble salt with the heavy metal cation, which is less soluble than '' ie.rcas copper compound is insoluble in this the salt of the heavy metal cation and the dye anion, ]Oo/’ C0P?er may bo separated from cadmium in this also being sparingly soluble and different in tb cn°etic ac^ anfl the cadmium recovered from colour from the original solution. R. C u t h i l l . i v ky neutralising with sodium carbonate of e more of the reagent. For the separation Quantitative analysis of a mixture of rare aamium from mercury the latter is converted into earths. E. D e l a u n e y (Compt. rend., 1927, 185, 848 BRITISH CHEMICAL ABSTRACTS.----A. 354—357).—The variation in size of tho absorption- thiocyanatc reaction for iron is most sensitive and bands of solutions of neodymium, praseodymium, at the same time specific if the material to be examined and a mixture of these elements, in neutral and in is first incinerated or evaporated, then calcined in a nitric acid solutions, has been plotted against the porcelain crucible, the residue cooled, moistened thickness of liquid used. Since Beer’s law is obeyed, with 1 drop of a 50% solution of ammonium thio- tho strength of an unknown solution (X ) may be cyanate, and 1 drop of 10% sulphuric acid added. determined from the thickness (e) of a solution of The liquid becomes rose-coloured, but the reaction known concentration (C) required to produce an is specific for iron only if the ash particles them effect equivalent to the thickness E of the former. selves are coloured. In such a delicate reaction it Thus, X —CEje. The error is less than 0-05%.. may be necessary to take precautions against dust. By means of the X-ray examination of dysprosium 0-01 jig. of iron was thus detected. D. G. H e w e r . rare-earth fractions (A., 1925, 822) the high magnetic Determination of ferrous iron in silicates. susceptibility of this element has been confirmed. L. A. S a r v e r . —S ee B., 1927, 557. J. G r a n t . Separation and determination of metals by Determination of tin by “ cupferron.” Separ means of 8-hydroxyquinoline. V. Aluminium. ation from antimony, arsenic, lead, and zinc. R. B e r g (Z. anal. Chem., 1927, 71, 361—380).— A. P i n k u s and ( M l l e . ) J. C l a e s s e n s (Bull. Soc. The slightly acid solution of aluminium salt is treated chim. Belg., 1927, 36, 413—433).—An improved with 3—5 g. of sodium acetate and a slight excess of method of determining stannous and stannic tin by a 2% alcoholic solution of 8-hydroxyquinoline. precipitation with cupferron is outlined (cf. Pinkus After heating at 60—70° the greenish-yellow, crystalline and Belcho, this vol., 639). The method enables precipitate of Al(C9H6ON)3 is collected on a porous this metal to be quantitatively precipitated in glass filter crucible, washed with hot water, and presence of quinquevalent antimony, arsenic, lead, either dried at 110° and weighed (5-87% Al) or dis and zhic, which may be determined in the filtrate solved hi dilute hydrochloric acid and the S-hydroxy- by tho usual methods. The method may also be quinoline content determined bromometrically. This applied in presence of certain other metals. procedure serves to separate aluminium from magnes S. Iv. T w e e d y . ium and the alkaline earths. Aluminium is also pre Liquid amalgams in volumetric analysis. cipitated by the reagent from ammoniacal (but not VIII. Oxidimetric determination of tin and from caustic alkaline) tartrate solutions as follows : copper by bismuth amalgam. Ii. Sqmeya (Sci. Sufficient tartaric acid to keep the aluminium in Rep. Tohoku Imp. Univ., 1927, 16, 515—520).— solution is added followed by 5—10 g. of ammonium Quadrivalent tin salts can be determined accurately chloride, ammonia until neutral, and a 2% alcoholic by reducing to the bivalent salt with bismuth amalgam solution of the reagent until the supernatant liquid and hydrochloric acid, and titrating with permangan is coloured orange. Copper, cadmium, and zinc are ate. The acidity must be between 5N and 12N and separated from aluminium by precipitation with the the mixture must be shaken for ten minutes at 45°. same reagent hi tartrate solutions containing sodium Phosphates, some sulphates, and chlorides with the hydroxide the filtrate is acidified and the aluminium exception of sodium or ammonium chlorides have precipitated as above after addition of ammonia. no influence on the accuracy of the method. Cupric A. R. P o w e l l . salts can be determined hi the same way, provided Potassium permanganate as an acidimetric the acidity is between 7N and 10A7. p . H a w k in s . standard. T. H e c z k o (Z. anal. Chem., 1927, 71, S. 332—33S; ef. Tananaev, A., 1925, ii, 440).—Tana- Reduction of stannic chloride by metals. naev’s method is subject to error due to the large J. W. Appling and J. H. R e e d y (J. Chem. Education, amount of ammonium salt used and to the danger 1927, 4, 527—531).—The solution is concentrated of a small quantity of the liberated ammonia being to 10 c.c., 5 c.c. of 6ili-hydrochlorie acid arc added, oxidised to nitric acid. The following procedure is and the solution is heated just below the b. p. for 3—4 recommended : A measured amount of permanganate min. with 10 mg. of aluminium wire; any metallic solution previously standardised against oxalic acid tin is dissolved hi concentrated hydrochloric acid is treated with a slight excess of sulphuric acid and and filtered into mercuric chloride solution, winch with 3-^4 times as much hydrogen peroxide as is d e t e c t s 0'01 m g . in 10 c.c. Chemical A b s t r a c t s . demanded by the equation : 2KMn04+ 3 H„S0., Determination of titanic acid in refractory 5H202=lY2S04-|-2MnS04-[-SH20-}-502. After com earths. L . L e m a l . —See B., 1927, 602. plete decolorisation has occurred, 0-5 g. of ammonium Determination of vanadium in iron minerals sulphate is added and the solution titrated with and rocks. V. A. Silberjutz and L. V. R o z h k o v a . potassium hydroxide slightly beyond the end-point with methyl-red; the titration is then finished with —See B., 1927, 559. a few drops of tho sulphuric acid solution and a Liquid amalgams in volumetric analysis. IX* correction applied for the acidity of the peroxide New determinations of vanadium and tungsten. used. The results are within 0-2% of those obtained K. S o m e y a (Sci. Rep. Tohoku Imp. Univ., 1 with sodium carbonate. A. R. P o w e l l . 521—529).—Vanadium, present as yanadic acid,. determined by reducing it to the bivalent state ^ J Detection of traces of iron in combustible zinc amalgam and mineral acid of concentration 0 j— volatile substances. E. K a h a n e (Ann. Chim. 4N, adding excesses of iodine, sodium h y o r o g c anal., 1927, [ii], 9, 198— 198).—The ammonium carbonate, and sodium arsenite, and titra g GENERAL, PHYSICAL, AND INORGANIC CHEMISTRY. 849 back with standard iodine solution. Another method 163, 297—301).—Heating certain quartz bulbs in of determination is by reducing the vanadate to the which the pressure had been reduced to a few bivalent state with lead amalgam and hydrochloric thousandths of a mm. at temperatures above about acid stronger than 9-5N, oxidising to the quadrivalent 600° caused an appreciable and continuous increase state with copper sulphate, and titrating with di- in the internal pressure, in spite of the fact that chromate. Sexavalent tungsten is determined by the vessels had previously been heated in a vacuum reducing to the tervalent state with lead amalgam and in the usual way, and that steps were taken to titrating with copper sulphate. F. S. H a w k j n s . prevent diffusion. The magnitude of the effect depended to some extent on the nature of the gas Determination of tantalum by X-ray spectro used for heating in the blow'ing of the bulbs. Where scop y . G. v o n H e v e s y and J. B ö h m (Z. anorg. a mixture of hydrogen and acetylene had been used Ckem., 1927, 164, 69—80).—The tantalum oxide for this purpose, a dark sublimate appeared on the content of various minerals has been determined by iimer wall of the bulb, probably originating in some adding erbium oxide until a certain line in the X-ray dissolved carbon-containing gas. By keeping such spectrum of one element is of the same intensity as a bulb for a long time at 1000° alternately evacuated another line in the spectrum of the other element, and filled with oxygen, it could temporarily be and then finding the ratio in which the pure oxides improved. It therefore seems that quartz is able to must be mixed to give the same result. In general, take up gases and retain them very tenaciously. the minerals need not be opened up. The most suitable comparison lines for most of the elements R . C u t h i l l . Simple automatic mercury still. H. L . B r o n between sodium and uranium are given. s o n (J. Opt. Soc. Amer., 1927, 14, 517—518).—A R. C u t h i l l . simple still is described that will distil at the rate Determination of the precious metals in ores. of 110 g. of mercury per hr. for three days without 6. L t jn d e .—See B., 1927, 605. attention. The power consumption is 25 watts. Thermostat and observation tubes for polari- R. W. L u n t . metric work. T. S. P a t t e r s o n (J.C.S., 1927, Apparatus for the semi-micro-determination 1717—1720).—A polarimeter tube having a vertical of mol. wts. by the ebullioscopic method. E. side tube is placed in position in a thermostat, in S u c h a r d a and B . B o b b a n s k i (Chem.-Ztg., 1927, the sides of which two pieces of brass tubing are 51, 568).—The apparatus consists of a small bulb fixed in such a maimer that their ends may be to which is sealed at its upper end a horizontal cemented to the ends of the polarimeter tube, with undulating tube connected with a funnel in which glass discs in between. In order to prevent the is sealed a small test-tube of mercury into which the condensation of moisture on the end plates when the thermometer dips. The vapour from the liquid heats apparatus is used at a low temperature, a current of the mercury to a constant temperature and then dry air is allowed to flow through the brass tubes. passes back along another tube, connected with a H. F. G i l l b e . reflux condenser, into the boiling bulb again. To Thermoregulator. S. C . C o l l in s (J. Physical carry out a determination the solvent (4—5 c.c.) is Chem., 1927, 31, 1097— 1098).—The tliermoregulator boiled gently in the bulb and the mercury tube is is operated directly by an alternating current of 110 heated gently until the vapours just cease to con volts, the heating effect being produced by the dense on the outside; in a further 5—7 min. the passage of the current through the dilute salt solution whole apparatus is at equilibrium and the tem of the bath itself. The differential expansion of ether perature of the mercury is read. Heating of the vapour and air forms the basis of the sensitive boiling bulb is continued and a weighed quantity of member, and the maximum temperature variation the substance the mol. wt. of which is required is at low temperatures is not greater than 0-02°. The dropped down the reflux tube into the liquid. After regulator can be used up to 68°. a further 5 min. the rise in temperature of the mercury L . S . T h e o b a l d . is read to 0-001° and the mol. wt. calculated as usual. Simple colorimeter. R. C. F r e d e r i c k (Analyst, A. R. P o w e l l . 1927, 52, 469).—Two colourless glass tubes, 3 mm. Apparatus for physical or chemical experi apart, to which glass discs have been attached, are ments at various temperatures under liquid connected by side tubes at their lower ends to two pressures of 15,000 kg./cm.2 J. B a s s e t (Compt. adjustable glass reservoirs which can be moved up rend., 1927, 185, 343—345).—The apparatus consists and down by sliding cradles on metal rods, with fine essentially of a high-power piston-pump connected adjustments by screws. An adjustable mirror reflects by a narrow' tube -with a reaction chamber furnished hght through the cylinders and the colour images with a support for a crucible, and also with insulated are thrown on an upper mirror. The standard and electrodes for the measurement of conductivity, or sample solutions are poured into the respective for heating or electrolysis of the reaction mixture, reservoirs which are moved up and down until an under pressure. An air-tight system of jointing is exact match is obtained, and the ratio is determined employed, and the apparatus has been used safely y reading the scale on the back of the instrument, over a range of pressures up to 15,000 kg./cm.2, the e capacity of each cylinder being such that 100 c.c. pressure being variable to within a few hundred kg. 0 so*ution reaches the 100 mark on the scale. J. G r a n t . p D. G. H e w e r . Sonic interferometer for liquids. JVC. Hub b a r d and A. L . L o o m is (Nature, 1927, 120, 189).— \\ t T ° 10n gases from hot quartz vessels. »• tfiLTZ and H . M ü l l e r (Z. anorg. Chem., 1927, An interferometer, which is in many respects the o K 850 BRITISH CHEMICAL ABSTRACTS.----A. sonic analogue of the Perot-Fabry interferometer, is plate in the upper part of this mantle so that the described. The instrument is capable of measuring hot liquid passes upwards through it and overflows the velocity of compressional waves hi small quantities at the top back into the distilling flask. For extrac of liquids with an accuracy of 1 in 103; corrections tions with heavy liquids the tube through which the for the elasticity of the vessel are eliminated. Values vapour enters the extraction column is bent at right of the velocity of sound waves at various temperatures angles at the top, so that tho condensed vapours fall in water, sodium chloride solutions, mercury, carbon down the sides of the outer mantle and percolate disulphide, and chloroform arc tabulated. The downwards through the mass to be extracted, which results lead to a method for calculating the number is placed on a perforated plate halfway down the of degrees of freedom, and consequently the association column. The liquid below the plate overflows back of molecules in the liquid state. A. A. E l d r t d g e . into the flask through a tube leading from the bottom of the mantle up through the centre tube to a point Apparatus for determining high m. p. R. just below the level of the solid on the plate; A n s c h u t z (J. pr. Chem., 1927, [ii], 116, 291—292).— A. R. P o w e l l . A tall cylindrical copper air-bath with mica windows All-glass gas circulating apparatus. W. S. is figured. The bottom is protected by a copper F u n n e l l and G. I . H o o v e r (J. Physical Chem., 1927, flame spreader. The thermometer and a stout 31, 1099— 1100).-—A pump capable of circulating asbestos inner jacket depend from the cover, which is dry gases in a closed system over a wide range of removable. H. E. F. N o t t o n . pressures is described. Tho essential feature is a Perforated extraction apparatus for heavy and glass piston filled with soft iron wire actuated in a light liquids. M. W a g e n a a r (Chem.-Ztg., 1927, length of glass tubing by means of two solenoids. 51, 528).—For the extraction of a solid with a light L. S. T h e o b a l d . liquid such as ether or benzene the vapours pass up Relationship between Chinese and Arabic tho central tube of the extraction column and con alchemy. J. R. P a r t i n g t o n (Nature, 1927, 120, dense at its upper end, tho drops of liquid falling into 158).—Although Stapleton, Azo, and Husain (Mem. a funnel at the top of. a narrow tube which enters the Asiatic Soc. Bengal, 1927, 8, 405) regard Chinese outer mantle of the apparatus at the lower end. alchemy of 200 B.C. as well established, the author The solid to be extracted is placed on a perforated considers this unproved. A. A. E l d e id o e. Mineralogical Chemistry. Atmospheric ozone and solar variability. Quantitative microscopic analysis [of rocksj. H. H. C l a y t o n (Nature, 1927, 120, 153— 154).— H. L . A l l i n g and W. G . V a l e n t i n e .—See this vol., The monthly means of the values obtained by Dobson, 846. Harrison, and Lawrence (this vol., 439) for the Composition and structure of meteoric iron amount of ozone hi the earth’s atmosphere at Oxford from Tamentit. Oxidation of meteoric iron at show an inverse relation to the monthly means of a high temperature. A. L a c r o ix (Compt. rend., solar radiation, as measured by the Smithsonian 1927, 185, 313—317).—The structure of the meteoric Institution, and to Wolfer’s sunspot numbers. The iron previously described (ibid., 1927, 184, 1217) correlation coefficient are, respectively, r = —0-54^ has been determined. In particular, regions of 0-11 and r=—0-62±0-09. A. A. E l d r i d g e . colour due to parallel bands of thin taenite, in bands Helium in Canada. R. T. E l w o r t h y .—See B., of camacite, or formed from grains of camacite sur 1927, 554. rounding small round grains of taenite, have been Occurrence of helium in oil-well gases. D. noted. Grains of schreibersite surrounded by large B u t e s c u and V . A t a n a s i u .—See B ., 1927, 580. grains of pyrrhotite were also observed in the cam acite. Analysis showed tho presence of iron (91%)> Seasonal variation in inorganic nitrogen nickel (8-4%), and traces of cobalt, manganese, compounds in the water of Lake Castelgandolfo. phosphorus, sulphur, carbon, and silicon. Oxidation S. C a m p a n i l e (Atti R. Accad. Lincei, 1927, [vi], 5, in the oxygen-aeetylene flame at 1580°, and examin 705—711).—The inorganic nitrogen content (almost ation of the nickel content of the magnetic oxide, entirely nitrates) hi the water of Lake Castelgandolfo supports the author’s theory that the chondrites are reaches a maximum in January and a minimum in, derived from the same magma hi which the pro August. This variation can be accounted for by the portion of the metals is fairly constant, the element* use made of the nitrates by the plankton population being partly or totally oxidised. Tho nickel con (the growth of which is very abundant during the centrates hi the last portions of iron remaining in the early summer months), which gradually consumes the intrates produced by animal and vegetable decay metallic state. J- G r a n t . during the winter. In tho deep central waters of the Amphibole grunerite of the Lake Superioi lake the plankton growth is smaller and hence the region. S. R i c h a r z (Amer. J. Sci., 1927, |yj> amplitude of the variation hi the inorganic nitrogen 14, 150— 154).—Analysis of fresh grunerite, from content is smaller than the corresponding amplitude Mt. Humboldt, Michigan, after separation of small of the variation for the shore water. E . A. L u n t . amounts of calcite and magnetite, gave : Si02 4s-oo, ORGANIC CHEMISTRY. 851 A1203 1-02, Fe203 1-14, FeO 39-20, MnO 0-66, CaO 6-33, MnO 1-04, A1203 17-96, CaO 15-93, MgO 0-42, 1-31, MgO 4-06, K20 0-19, Na20 1-06, H20 (over Ce203 3-47, (La, Nd, Pr, Sm, Y, Eu)a0 3 5-73, combined 110°) 1*71, total 98-88; ¿3-44. The material is water 2-22, moisture 0-08, total 100-80%. The light-grey with a yellowish tingo and forms small general formula appears to be H2M"4(M""2)3Si6028. laths. Extinction-angle 14—15°, 2V large, negative, Details of the analytical method and a possiblo a 1-666, p 1-684, y 1-700. Compared with the original structural formula are given. J. S. C a r t e r . griinerite from France, this shows less FeO and more Palladium mineral from Potgietersrust MgO, with correspondingly lower values for the platinum fields. H. R. A dam (J. Chem. Met. Soc. refractive indices. L. J. S p e n c e r . S. Afr., 1927, 27, 249—250).—A silvery-white mineral Orthite from Arendal (Norway). II . L l o r d y obtained from pannings in the Potgietersrust district Gamboa (Anal. FIs. Quim., 1927, 25, 216—229).— of the Transvaal contained 70-4% Pd, 26-0% Sb, and The composition of orthite, especially as regards the 3-3% “ gangue.” The palladium and antimony cor occurrence of rare elements, appears to vary con respond with the formula Pd3Sb. The mineral has siderably with the locality. Analysis of a dark d 9-5 and is insoluble hi hydrochloric acid, slowly brown mineral (d 3-22) from Arendal (Norway)- gave attacked by nitric or by sulphuric acid, and readily the following results : Si02 36-92, Fe203 10-70, FeO soluble in dilute aqua regia. A. R. P o w e l l . Organic Chemistry. Anomalies in the properties of long-chain general, tautomerism is regarded as a consequenco compounds. W. B. L e e (Nature, 1927, 120, 48).— of the existence of an ion common to two isomeric Cumulative evidence can now be adduced indicating forms. Such ion must be multipolar and of equal that anomalies or turning points exist in many global charge and contrary sign to that of mobile of the properties of certain long-chain compounds substitution. This phenomenon, termed synionism, at or near the fifth, tenth, and fifteenth carbon atoms, is always realised when a mobile group is attached the abnormality being most pronounced at C15. to an atom linked to another doubly-linked atom. A. A. E l d r i d g e . Thus the compound A!B-CX ionises in the form Low-temperature oxidation of hydrocarbons. A^B^'C^X*, which is also the activated form of J. S. L e w is (J.C.S., 1927, 1555— 1572).—When par XA-BIC. The consequences of synionism are as affins are slowly heated in a bulb at constant volume follows : (1) X is only slightly mobile : AX-BIC and a sudden rise in the pressure occurs at the “ critical A:B-CX may exist separately and are isomeridcs. inflexion temperature ” (C.Ï.T.), indicating rapid All reactions not involving the common ion are normal chemical action at this point involving an increase for both forms, but when this ion comes into play one in the number of molecules. An oxidising catalyst at least of the isomeridcs exhibits an abnormal such as platinum promotes pressures higher than reaction. (2) X is highly mobile, but of the two normal below the C.I.T., whereas lead tetraethyl positions it can occupy one confers on it greatly usually inhibits the initial oxidation; the activity increased mobility. X will then be fixed solely of this negative catalyst, however, decreases slowly. or almost so at the other position, and the compounds It is suggested that oxygen combines with loosely- are pseudo-isomeric. If X is replaced by the less attached hydrogen atoms of the paraffins, the products mobile X ' by a reaction involving the common ion, being water and unsaturated hydrocarbons, this two isomeric reaction products may often be separ explaining the increase in the number of molecules, ated. (3) When X is highly mobile and the positions the high percentage of water, and the presence of A and C are similarly influenced, AX-BiC and unsaturated hydrocarbons immediately above the A:B-CX arc desmotropic. Examples of these different Secondai7 reactions, with formation of cases are citcd. . T. H. P o p e . aldehydes, peroxides, etc., occur later, causing a Preparation and physical properties of iso- slight fall in the temperature—pressure curves just butylene. C . C. C o f f i n and O. M a a s s (Trans. Roy. above the C.I.T. The exothermic nature of the Soc. Canada, 1927, [iii], 21, III, 33—40).—iso- initial reaction, together with the increase in pressure Butylene, m. p. 146-8°, b. p. -6-6°, was prepared <1110 to the larger number of molecules present, by the dehydration of wobutyl alcohol by alumina promotes detonation, and the action of anti-knocks at 250—300°, dried by a freezing method, and fraction 15 u® to their prevention of this primary dehydro ated in a vacuum. Values are tabulated of the genation. 33 A n d e r s o n . vapour pressure [e.g., 1044 mm. at 1-8°, 2017 mm. Catalytic reactions of ethylene. H. W . W a l k e r at 22-1°), density (d01 0-6190, d22'5 0-6444), surface —feee this vol., 837. tension (14-84 at 0°) and molecular surface energy (299-3 at 0°) over a considerable range of temperatures. New class of tautomeric compounds. Ionic The physical properties of ethylene, propylene, and e°ry of tautomerism. C. P r é v o s t (Compt. isobutylene are summarised. A. A. E l d r i d g e . tiT ’h i — 134).—The ionised forms of c°Trapounds are represented by the scheme Reactions of nitrosyl chloride. IV. Action CTrirpi n S ^ “-CH+ -R2), this being common to cf nitrosyl chloride on ketoximes. II. R h f.i n - CHXR-CH:CHR2 and GHR^CH-CHXR2; and, in b o l d t and M . D e w a l d (Annalen, 1927, 455, 300— 852 BRITISH CHEMICAL ABSTRACTS.— A. 314).—Tlie chloronitroso-derivatives formed by the hi rates of isomérisation with temperature, are action of nitrosyl chloride on ketoximes are blue, respectively, 8450^600, 22,000±2000, and 4250+ unimolecular liquids or crystalline solids which do 800 g.-cal./mol. P . G. W il l s o n . not polymerise at the temperature of liquid air. They are more stable than the aa-chloronitroso- Polyvinyl alcohol. W. 0. H e r r m a n n and W. compounds (this vol., 229) and do not pass into iso- H a e h n e l (Ber., 1927, 6 0 , [B], 1658—1663).—Poly-' nitroso-compounds. They are oxidised by air and vinyl alcohol is prepared by the hydrolysis of polyvinyl light or, better, by warm nitric acid to chloronitro- esters by alkali or acid. Since the substance has derivatives. In this way are prepared p(3-dWoro- marked adsorptive power for inorganic salts, it has miraso-dei'ivatives of propane, b. p. 70° (cf. Ponzio, a high ash content when prepared by means of alkali, A., 1906, i, 482) ; butane, b. p. 24— 25°/22 mm. ; whereas acid hydrolysis gives a purer product from pentano, b. p. 32°/23 mm. ; y-methylbutane, b. p. which acid can bo removed by dialysis. The pro 31°/26 mm. ; hexane, b. p. 47— 48°/21 mm. ; 8-methyl- perties vary greatly with the mode of preparation pentane, b. p. 41— 42°/18 mm.; yy-dimethylbutane, both in respect of colour and density. Most of the m. p. 121—122°; ?i-octane, b. p. 41°/4 mm.; n- forms are soluble in water but a black, insoluble undecane, b. p. 84— S5°/3 mm. ; a-phenylpropane, modification may be prepared by heating an aqueous b. p. 65°/4 mm., and ay-diphenylpropane, m. p. solution of polyvinyl alcohol with hydrochloric acid 90— 91°, decomp. 105° ; the (ifi-cJiloronilro-dcrivativcs followed by dialysis of the product. As judged by of butane, b. p. 51—52°/16 mm. ; pentane, b. p. determinations of mol. wt. by osmotic methods it 72— 13°¡22 mm. ; hexane, b. p. 83—84°/18 mm. ; has the composition (CII2;CH-OH)20. When heated S-methylpentane, b. p. 79°/17 mm. ; yy-dimethyl- at 250°/1000 atm. it forms a hard, elastic material, butane, m. p. 169— 170° ; ?i-octane, b. p. 115°/19 mm. ; d 1-5810. It behaves generally as a reversible colloid n-undecane, b. p. 119—120°/4 mm.; a-phenyl- similar to gum arabic or albumin. It is well adapted propane, b. p. 88°/2 mm. ; ay-diphenylpropane, m. p. as a protective colloid for metals, hydroxides, oxides, 127° ; also yy-chloronitrosopentana, b. p. 32°/20 mm. ; sulphides, etc. When heated at 200—220°/30 atm. yy-chloronitropenlane, b. p. 73°/24 mm. ; ethyl propyl polyvinyl alcohol appears to undergo transformation. ketoxime, b. p. 86°/17 mm. ; yy-chloronitrosohexane, It adds chlorine or bromine, forming compounds b. p. 46— 47°/17 mm. ; yy-chloronitrohexane, b. p. which have not been investigated fully; they are 79—80°/17 mm. ; §§-chloro7iitrosoheptane, b. p. 49°/ transformed by boiling water into black polyvinyl 12 mm. ; S8-chloronitroheptane, b. p. 94— 95°/17 mm. ; alcohol. Iodine and potassium carbonate convert 00-chloronitrosohentriacontane, m . p . 49— 50° ; ca- it into iodoform. The action of oxidising agents is chloronitrosopentatriacontane, m . p . 51— 52° ; aa- described. With sodium hydroxide it gives sodium chloronitropentatriacontune, m . p. 52°; l:\-chloro- polyvinyl oxide trihydrate. Acids or their anhydr nitrosoayclohexane, b . p . 52°/12 m m . ; a n d 1 : 1- ides convert it mto polyvinyl esters. Its relation chloronilrocydohexane, b . p . 93— 94°/13 m m . Benzo- ship to the carbohydrates is shown by the production phenoneoxime,butane-J3y-dione- mono- and-di-oxim es, of substances resembling amyloform with formalde benzilmonoxhne, fluorenoneoxime, and phenanthra- hyde. Like crude rubber, it can be vulcanised with quinonemonoxime do not give chloronitroso-deriv sulphur in the presence or absence of accelerators. atives with nitrosyl chloride. H. E. P. Notton. H. W een. Stereochemistry of the tetrahedral carbon Mechanism of the change of isonitro- to nitro atom. VI. Configuration of the glycols compounds. G. E. K. B r a n c h and J. Jaxon- obtained by reduction of aldehydes by zinc- D e e l m a n (J. Amer. Chem. Soc., 1927, 49, 1765— copper couple. R. K u h n and O. R e b e l (Ber., 1779).—When the sodium salts of isonitromethane, 1927, 6 0 , [5], 1565— 1572).—The reduction of gly- phenyKsonitromethane, and jo-isonitrophenol in oxylic acid, benzaldehyde, acraldehyde, croton- 0'01Ar-aqueous solution are added to 0 01A7-aqueous aldehyde, and cinnamaldehyde has been examined, hydrochloric acid at temperatures between —23-8° The configuration of the glycols formed from the and +5-2°, the rate of decrease in conductivity falls first two substances is established by their known very rapidly at first, and then becomes and remains resolvability. In the cases of the unsaturated glycols proportional to the conductivity of the solutions obtained from the last three aldehydes the structure due to the isonitro-eompounds. It is concluded is established by ozonisation hi glacial acetic aeia that the first rapid change in conductivity is due solution (gelatinous, highly polymerised ozonides to the establishment of an equilibrium according are produced in chloroform or c a r b o n tetrachloride) to the scheme B -C H :N < 2 + H + R-CH-N-OH, followed by decomposition of the ozonides and osi • x 0 / ation of the products by bromine to r- or meso- whilst the subsequent slower change is due to an tartaric acid. In all cases either the r- or the glycol appears to be produced exclusively, it is isomérisation according to the scheme R-CH'N<^q _ not possible to establish a simple relationship between the electrochemical nature or valency demand o — >R-GH-N 126-5, iodine value 171-1, ReicherWVIeissl value 1-09. Na2[Cu(C2H203)2],2-5Me0H, and cuprisalicylale, The unsaponifiablo portion (30% of tho oil) has a Na2[Cu(C7H403)2], may be obtained. As shown by setting point below 0°, »JJ 1-5198, iodine value 136-0, hydrogen-ion concentration measurements in solution and possesses in marked degree the characteristic cupric salicylate is more acidic than the glycollat-e odour of parsley. On fractional distillation myristicin or lactatc, and, as expected, the complex salicylates was identified in the fraction of b. p. 70—100°'/18 mm. and mandelates are found to be more stable than the whilst that of b. p. 163°/18 mm. contained a substance corresponding glycollates and lactates. The following C10Hi8O2 of very agreeable odour. Tho fatty acids salts have been isolated from aqueous solutions: from the oil (65%) were dark green in colour and sodium hydrogen cuprimandelate, NaH[Cu(C8H603)2]; had m. p. 26° (indef.), nf, 1-4597, iodine value 96-6, silver cuprimandelate, Ag2[Cu(C8HG03)2]; mercurom acid value 188-3, and were separated into solid (45%) cuprimandelate, Hg2[Cu(C8H603)2],5H20 ; ferric and liquid acids by fractional recrystallisation of cuprimandelate, Fe2[Cu(C8H603)2]3,14H20 ; cupric the lead salts from alcohol. The solid acids consist cuprimandelate, Cu[Cu(C8HG03)2]. mainly of “ petrosclic acid,” C18H3402 (cf. Vongcrich- B. W. A n d e r so n . ten and Köhler, A., 1909, i, 454; Hilditch and Jones, Oxalato-derivatives of the alkaline-earth this vol., 540), m. p. 29-4°, 1-4534, iodine value metals and lead. R. S c h o l d e r , E. G a d e n n e , and 89-9, and acid value 198-7 (cf. Palazzo and Tamburello, H. N ie m a n n (Ber., 1927, 60, [5], 1488—1498).— A., 1915, i, 862). On ozonisation it yields lauric The complex oxalates of the alkaline-earth metals acid (m. p. 43-6°) and adipic acid, and the liquid and lead exist in three types exemplified by the methyl ester on hydrogenation affords methyl stearate, following compounds : m. p. 39-2°. These facts are hi agreement with the r9 o-o-Ba o i T.- formula CII3-[CH2]10-CH :CH-[CH2]4-C02H ascribed Lco-o- -o ,h 2o , by Vongerichten and Köhler to petroselic acid. JO-O- The solid fatty acids also contain a small quantity of palmitic and stearic acids. The liquid fatty acids, 30« the lead salts of which were soluble in alcohol, were and [Sr5(C204)G]K2,12H20. The salts are prepared distilled in a vacuum and yielded, on treatment with from their components under highly individual con bromine in ethereal solution, linoleic tetrabromide, ditions. They are colourless, microcrystalline pow m. p. 114-2°, but no linolenic hexabromide, and there ders, insoluble in water, by which those belonging fore contained 33% of linoleic acid, tho remaining to the first two types are immediately decomposed. acids being of the oleic series. A5-Oleic acid was Salts of the following formulae are described : proved to be present by the formation of As-elaidic K2C,04,BaC20il,2H20 ; Rb2C204,BaC204,2H20; acid, m. p. 43°, on treatment of the liquid fatty acid Tl2C;04,BaC204,2H20 ; (NH4)2C204,2BaC204; with nitrogen peroxide, and confirmed by the pro Cs2C204,2BaC204; KoC,04,5BaG204,4H20; duction of ii-nonoic and azelaic acids on ozonisation. K2C,04,2PbC204,4H„0; Rb2C204,2PbC204>4H20 W. J. P o w e l l . (o r " 2 fl20); “ Cs2C„04,PbCo04,2H20; Preparation of myristic acid from nutmeg H2C204,2SrC204)2H20 ; “ H2C204,2SrC204; butter and ucuhuba fat. P. E. V e r k a d e and J. H2C204,2SrC204,2• 5H20 ; (NH4)2C204,2SrC204; C o o p s (Rec. trav. chim., 1927, 46, 52S—533).—Nut K2C204)2SrC!04; 2 Rb2d o 4,2SrC204; meg butter is the most convenient source of myristic Cs2Co04,2SrC204; K2C204,5SrC204,12H20; acid since it contains hi appreciable quantities only Na2C204,5SrG>04,12ELO; K 2C204,CaC204,H20; triolein and trimyristin, and the latter, the chief Rb,G,04,Caa04,H20 ; CsoC,04,CaC204,H20. constituent, is readily obtained in a pure state by H . W re n . recrystallisation from a mixture of 4 vols. of 96% Partial replacement of the oxalate residue hi alcohol and 1 vol. of ether. Myristic acid, setting oxalato-anions of bivalent metals. R. S choldeb point 53-6°, is obtained in nearly theoretical yield [with E. G a d e n n e and H. N ie m a n n ] (Ber., 1927, 60, by saponification and recrystallisation of the product [jB], 1499—1509; cf. preceding abstract).—The from 80% acetic acid. The fatty acids from a sample behaviour of strontium oxalate towards concentrated of ucuhuba fat contained myristic acid (58%), solutions of a number of alkali salts is described. w-decoic acid, and lauric acid (8%), which were separ Typical results are obtained with sodium thiosulphate ated by fractional distillation of the methyl esters. solution, which deposits crystals of strontium Smce many previous investigators (cf. Reimer and oxalate or the more stable sodium strontium Will, A., 1885, 1197; Nördlinger, A., 1886, 139; oxalate, Na2C204,5SrC204,12H20. Sodium nitrite and Valenta, B., 1889, 202) have found ucuhuba fat to potassium acetate are exceptional shice they yield, contahi no higher saturated acids other than myristic the compounds Na2C2O4,SrC2O4,NaNO2,H20 and acid, it is concluded that the ucuhuba fat of commerce K2C204,3SrC204,2CH3-C02KJ4-5H20. The oxalates may be of varied botanical origin. W. J. P o w e l l . of the alkaline earths exhibit enhanced solubility in solutions of alkali formates and hypophosphites but Metallic hydroxy-acid derivatives. IV. Com in the majority of cases either double decomposition plexes formed by copper with the monobasic ensues or the corresponding double oxalate crystall monohydroxy-acids. I. W. W ark (J.C.S., 1927, ises; the salts SrC204,H-C02K,2H20, 1753— 1758; cf. ibid., 1923, 123, 1816).—Sodium SrCo04,H-C02Rb,2H20, SrC204,KH2P02,2H20, and cuprimandelate, Na2[Cu(C8Hc>03)2], is best prepared CaC“204,2H-C02K,H20, have been isolated. Oxalates by dissolving cupric mandelate in alcoholic sodium of bivalent heavy metals are more freely soluble ethoxide; in a similar manner sodium cupriglycollate, than those of the alkaline earths hi alkali formate ORGANIC CHEMISTRY. 855 and hypophosphito solutions and yield double two phenomena are superimposed. With increasing oxalates or mixed compounds, of which the follow dilution, the complex dissociates more completely ing individuals are described : ZnC204,2H>C02K ; into the ions of the simple oxalate and, simultaneously, CdCA,2H-C02K,(H ,0 and 3H20 ) ; CoC204,2H‘C02K ; tho degree of dissociation of the complex and the CoC204>3H*C02Na; “ CoC204,H-C02NH4; simple oxalate increases. With the zinc, cadmium, 2CdC,04,KoC204,2H-C0oK,2H20 ; and cobalt compounds the decomposition of the com 2ZnC204,3KH2P02,2H20 ; 5NiC204,xl6H-C02Na,5H20 ; plex is so pronounced that, in comparison, the increase 3(MC204,(NH4)2C204,7fi20. On the supposition that of a with increasing dilution is almost without moment. the oxalates of the alkaline-earth metals are them With the more stable ferrous oxalate complex, the selves complex compounds, e.g., [Ba(C204)2]Ba, the hicrease hi the actual degree of dissociation is more behaviour of these compounds in solutions of the important. The very individual behaviour of the alkaline-earth formates has been investigated. oxalates of the heavy metals, which are otherwise very When the same basic ion is present in each salt tho similar in their properties, is a further argument in oxalate is insoluble. With dissimilar cations en favour of auto-complex formation. It is probable hanced solubility is observed. The systems thus that the constitution of the auto-complex oxalates produced are exceedingly labile and the extent to cannot be expressed by the simple formula, which double decomposition occurs depends greatly [X"(C204)2]X ". H. Wren. on the temperature; the compound, Oxalochlorides of cerium. L. D e d e and W . [BaC204,(H;C02)2]Ba,6H20, is the only member of F a b e r (Ber., 1927, 60, [5], 1654— 1658).—Addition the class which could be isolated. H. W r e n , of concentrated oxalic acid solution to a boiling, well- stirred solution of cerium chloride in water as long as Auto-complex formation with oxalates of the initial precipitate immediately dissolves causes the bivalent metals. II. Determinations of con compound, CeCl(C204),3H20, to crystallise from the ductivity and solubility. R. S c h o l d e r [with E. cold solution. The salt is stable to cold but not to G a d e n n e and Ii. N ie m a n n ] (Ber., 1927, 60, [2?], boiling water; it may be crystallised from fuming 1510—1525; cf. preceding abstracts).—The con hydrochloric acid. Evaporation of the mother- ductivities of saturated aqueous solutions of the liquors in a vacuum leads to the isolation of the salt, oxalates of barium ,(-}-0-5, 2, and 3-5H20), strontium Ce2Cl4(C204),8H20, which is more readily prepared (+1H20), calcium (+ IH 20), magnesium (+2H 20), from cerium chloride, and the compound CeCl(C204); zinc (+2H20), cadmium (+3H 20), ferrous iron it is decomposed by excess of cold w'ater. H. W r e n . (+2^0), cobalt (+2H 20), nickel (-¡-2H20), and silver have been determined and their solubility lias Therapeutic action of some bismuthyl deriv been found by direct measurement (treatment of the atives of organic hydroxy-acids. C . H. B r o w n solution with sulphuric acid followed by concen in g , J. B. C o h e n , R. Gulbransen, E. P h i l l i s , and tration and titration with 0-01IV-permanganate). W . R. S n o d g r a s s (Proc. Roy. Soc., 1927, B, 102, The production of an auto-complex is regarded as 1—9).—Bismuthyl compounds of saccharic acid, established if the ratio, eonductivity/solubdity is disodium saccharate, potassium mucate, gluconic acid, considerably less than the conductivity at infinite disodium gluconate, mannonic acid, galactonic acid, dilution as deduced from the sum of the mobilities of lactobionic acid, maltobionic acid, tartaric acid the ions. This is not the case with the oxalates of (C8H10O12,BiO,2H2O), disodium tartrate, ethyl hydrogen barium, strontium, calcium, and silver, whereas with tartrate, ethyl tartrate, glyceric acid, ethyl glycerate, those of magnesium, zinc, cadmium, non, cobalt, and sodium gallate, malic acid, citric acid, glycollic acid, nickel complex compounds appear to exist in solution. dihydroxymalonic acid, ethyl dihiydroxymalonate, tar- Unless, therefore, the possibility of auto-complex tronic acid, and thiobenzoic acid, are prepared by formation is excluded, the applicability of Kohlrausch’s treatment of the acid, ester, or salt with bismuth method for the determination of the solubility of nitrate in acetic acid. Excepting the citric acid and sparingly soluble substances appears doubtful. citric ester compounds, all are soluble in aqueous ■H. W r e n . alkali, the saccharic acid compound being stable even Auto-complex formation with oxalates of in boiling concentrated alkali. In the case of tartaric hivalent metals. II. Dilution curves. R. acid several bismuthyl compounds are obtained: Sch o ld er (Ber., 1927, 60, [5], 1525— 1532; cf. C4H40 6N03-Bi0, from a warm solution of bismuth preceding abstract).—Since it is possible that the nitrate in dilute acetic acid and aqueous tartaric acid; abnormally low values of the equivalent conductivity C4H406-Bi0, from cquimolecular amounts of bismuth of the oxalates of zinc, cadmium, ferrous iron, nickel, nitrate and tartaric acid in hot acetic acid; and and cobalt may be due to the slight dissociation of C4H406Bi*N03,5H20, from excess of tartaric acid in these salts, the effect of dilution on the value of A and boiling acetic acid. Glycollic acid readily gives a also on the degree of dissociation a definite antisyphilitic action in man, but are not which could not be completely purified; hydrolysis curative and present no advantage over the known with potassium ethoxide converts it into the bismuth preparations. C. H o l l i n s . potassium salt, C23H30O14K2, from which the corre Polarimetric and electrometric study of the sponding copper salt, m. p. 169—170° (decomp.) after alkali aluminotartrates. A double mutarot- softening at 160°, is obtained. H. W r e n . ationphenomenon. P a r i s e l l e (Compt. rend., 1927, Sulphosuccinic acid. H. J. B a c k e r and J. M. 185, 130—132).—The curves obtained from deter van der Zanden (Rec. trav. chim., 1927, 46, 473-. minations of the specific rotatory powers of mixtures 491).—The neutralisation of the sulphonic group in containing one aluminium ion to one molecule of ¿-sulphosuccinic acid, obtained by recrystallisation of tartaric acid with increasing proportions of sodium the neutral strychnine salt, has little effect on the hydroxide indicate the existence of a neutral sodium rotatory power, but there is a marked reduction if hi aluminotartrate, C02Na-CH(A10)-CII(0H)-C02Na, addition one or both carboxyl groups are neutralised; which is decomposed by an excess of alkali into thus the free acid, the mono-, di-, tri-sodium, and the sodium tartrate and meta-aluminate. Mutarotation tri-ammonium salts have [il/]D=53, 52, 39, 33, and 34, phenomena varying in sign and rate of change, and respectively. This behaviour is analogous to that depending on the pH value, were observed for solutions of a-sulphopropionic, a- and (3-sulphobutyric, and other than those containing less than 1 mol. or more a-sulphovaleric acids. ¿-Sulphosuccinic acid, which, than 5 mols. of sodium hydroxide to 1 mol. of aluminium. like its salts, is readily racemised at 100°, is moderately They indicate molecular transformations. Analogous stable at ordinary temperatures and may be prepared results were obtained for potassium and ammonium by the action of sodium sulphite on ¡¡-bromosucciiiic hydroxides. J. G r a n t . acid in wealdy alkaline solution. Sulphosuccinic acid Allenetetracarboxylic ester. F . F a l t i s and J. is best prepared by the action of sodium hydrogen P i r s c h (Ber., 1927, 60, [B], 1621— 1632; cf. A., sulphite on maleic or fumaric acid. The reaction 1922, i, 624).—Ethyl sodiodicarbethoxyglutaconate is takes place in the cold, and the sulphonated acid is obtained in good yield from ethyl malonate, chloroform, isolated as the barium salt (yield 90%). The free and sodium ethoxide in ethyl alcohol if undue rise of acid is obtained by decomposing the silver salt with temperature is avoided, thus excluding the production hydrogen sulphide and evaporating the filtered of the sodium derivative of ¿sobutanehexacarboxylic solution; it forms hygroscopic crystals of the mono ester. It is converted by bromine in chloroform or hydrate, which, when heated in a closed tube, decom ether into ethyl y-bromo-ay-dicarbethoxyglutaconate, pose at 60°, and become coloured at 80° but do not which when treated with moist silver oxide in boiling melt. A colorimetric determination of the tertiary alcohol affords ethyl allenetetracarboxylate, dissociation constant gave k3— lxl0~5, whilst by an C(C02Et)2:C:C(C02Et)2, m. p. 84°, in 30% yield. The electrometric method Mook has obtained /;2=l-6 X10"4 ester immediately decolorises cold, neutral perman and ¿3=0-5 x 10~5 (private communication). The ganate solution but does not add bromine or hydrogen silver, barium, lead (+4H 20), potassium (anhydrous, in the presence of palladised barium sulphate. decomp. 227°), and thallium (anhydrous, decomp. The action of potassium ethoxide (1 mol.) on ethyl 116— 120°) salts arc described. The primary strych y-bromo-ay-dicarbethoxyglutaconate leads unex nine salt was not obtained in a crystalline form, but pectedly to the conversion of one half of the ester the neutral tristrychnine, salt and an acid salt, into ethyl potassio-ay- dicarbethoxyglutaconate (the 3C4H60?S,8C21H2202N2, decomp. 245°, were isolated. corresponding copper and calcium salts are described), Sulphosuccinic acid may also be prepared by the action whereas the other half appears to be transformed into of sodium sulphite on bromosuccinic acid, but ethyl y-bromo-ap-diethoxy-ay-dicarbethoxyglutarate; secondary reactions cause the yield to be low (40%). the latter compound could not be isolated and its form The method involving the direct sulphonation of ation is deduced from its conversion when distilled succinic acid described by Fehling is unsatisfactory into ethyl carbonate, polymerised ethyl a-bromo- since the interaction of sulphur trioxide and succinic acrylate, ethyl mesoxalate, and (?) ethylene. If the acid in equimolecular quantities results in the form proportion of potassium ethoxide is increased to 2 ation of succinic anhydride, whilst with excess of the mols., the potassio-derivative is obtained in 63-4% former at 50° the product contains unchanged succinic yield. acid, sulphosuccinic acid, and disulphosuccinic acid, of Conversion of the bromo-ester into the y-lactone, which the lead and thallium (decomp. 145°) salts are C13H160 8 (cf. Faltis, loc. cit,), is conveniently effected described. W. J. P o w e l l . by distillation under 14 mm. pressure. By treatment Exchange of functional groups between two with concentrated potassium ethoxide solution it is molecules. A. V e r l e y (Bull. Soc. chim., 19^> transformed into the potassium salt, [iv], 41, 788—S04).—The carbonyl group in ketones, aldehydes, or esters possesses the general property of c(C02Et):cH> c :c < 0Et,in s3% yield; the corre- combining with 1 mol. of metallic alkoxides, wita sponding copper salt has 2EtOH instead of 5H20 as evolution of heat, affording compounds of the type, described. Attempts to open the lactone ring by CRR'(OM)-OR", for which the name metallic “ hemi- using an excess of potassium ethoxide were not acetal ” is proposed. Both the metallic and the free successful. The corresponding sodium salt is hemiacetal are largely dissociated in solution an described. Treatment of the potassium salt with have not been obtained pure. Benzaldehyde an aqueous ethyl alcohol and concentrated sulphuric aluminium ethoxide in absolute alcohol afford b7/o acid leads to the production of an ester, C^H^O^, of a crystalline powder, apparently a mixture o ORGANIC CHEMISTRY. 857 CHPh[OAl(OEt)2]-OEt, CH2Ph-0-Al(0Et)2, and Diacetylglyceraldehyde is converted by glacial acetic CPh(0-CH2Ph)[O-Al(OEt)2]-OEt, since on treatment and hydrobromic acids into dimeric acetobromoglycer- ■svith dilute sulphuric acid it yields benzyl alcohol, aldehyde, m. p. 168—169° benzaldehyde, and ethyl and benzyl benzoates. lL b ? ch'ch*'oa°L With aluminium ethoxide and acetone the yield of (decomp.), which is converted by methyl alcohol hemiacetal varies from 40% to 80%. The sodium and silver carbonate into acetylglyceraldehyde methyl- hemiacetal obtained from sodium ethoxide and methyl cycloacetal, m. p. 101-5—102-5°, and thence by methyl- nonyl ketone on treatment with ethyl bromide affords alcoholic ammonia into glyceraldehyde methyloyclo- a small amount of the methyl acetal of methyl nonyl ketone, a reaction supporting the structure advanced acetal, >CH-CH2-0H ,m.p. 158-5— 159-5° _CH(OMe) above. With esters, aluminium ethoxide affords the Crude acetobromoglyceraldehyde is hydrolysed by hemiacetal in 30—80% yield. The formation from silver carbonate and aqueous acetone to dimeric acetyl these hemiacetals of products in which the functional glyceraldehyde, m. p. 118-5°, the m. p. of which is groups of the original compounds have been inter depressed by crystallisation probably by reason of changed is attributed to intramolecular change in the migration of the acyl groups. The successive action hemiacetal, e.g., CH2R-0-CHR'-0H— -> CH2R'*0,CHR,0M (combination of aldehyde with of hydrogen chloride and methyl alcohol and silver carbonate on dihydroxyacetone affords the primary alkoxide) or CHRR',0*CR"R"',0M— > corre- CHR"R"'*OCRR'-OM (ketone and secondary alk- sponding methylq/c/oacetal, -9 >C(OMe)-CH2-OH, oxide). In the cases where the hemiacetal has the CELj structure CHRR'-0-GHR"-0M (aldehyde and second m. p. (anhydrous) 131—132°, m. (+ H 20) 91° ary alkoxide) or CH2R-0-CR'R''-0M (ketone and (corresponding acetate, m. p. 138°). primary alkoxide) such exchange does not occur. In Glycollaldehyde is conveniently prepared by heating the third stage the new hemiacetal dissociates in dihydroxymaleic acid in pyridine at 50—55°, removal solution into alkoxide and carbonyl compound, the of the latter under diminished pressure, and sub metal being finally distributed between the two sequent distillation of the residue. It may also be alcohols in proportion to their mol. wt. The above prepared by ozonisation of allyl or cinnamyl alcohol theory of exchanges is developed to explain the and treatment of the ozonides with zinc dust and Claisen-Titschenko reaction, the formation of a glacial acetic acid. The refractive index of the hemiacetal, CHR(OAlk)-OM, being regarded as the freshly-distilled substance undergoes rapid increase first stage, from which 1 mol. of metallic alkoxide is to a constant value, possibly indicating intramolecular eliminated, giving CHR(0M)-0-CHR-0Alk, from transformation. The aldehyde is converted by acetic which, by migration of the OM group, the product anhydride and pyridine into dimeric acetylglycoUalde- CH2R-0-CR(0M)-0Alk is formed. Cannizzaro’s hyde, [ 9 ^>CH-OAc m.p. 157—158°, which is trans- reaction is given a similar interpretation, R-CHO + LCH2 J2 NaOH=CHR(ONa)-OH — y CHR(OH)-OCHR-ONa formed by hydrogen bromide in glacial aceticJacid —> CR(OH)(ONa)-OCH2R — > R-COONa + into dimeric bromoglycollaldehyde (bromoethylene oxide), CH2R-0H. Aldolisation is similarly explained, m. p. about 136° (decomp.), and thence into glycollalde only those aldehydes aldolising which are capable of hyde methykycloacetal, m. p. 72°; glycollaldehyde yielding an enolic form. ethylcwcZoacetal, m. p. 59-5°, is similarly prepared. The reaction between alkoxides and ketones, H. W r e n . aldehydes, and esters affords a means of preparing Isolation of ketones by means of their oxonium otherwise inaccessible esters of secondary or tertiary compounds. W. Tschelincev and ( M l l e . ) L. alcohols. Thus 1 mol. of methyl anthranilate and 1 mol. N a s a r o v (Bull. Soc. chim., 1927, [iv], 41, 805—808).— of geraniol, when heated at 100—120° in presence of Addition of an ethereal solution of magnesium bromide 0-051/ of sodium, aluminium, or magnesium ethoxide, to a solution of a ketone or ether oxide in benzene or after distillation of the methyl alcohol and removal light petroleum affords a crystalline precipitate con of unchanged methyl anthranilate, affords geranyl sisting of magnesium bromide combined with 2 or 3 anthranilate, b. p. 188°/4 mm. Esters of tertiary mols. of ketone (cf. A., 1924, i, 929), which can be alcohols are readily obtained by leaving the alcohol for utilised for the separation of ketones. Compounds of several days in contact with excess of acetic-formic magnesium bromide with the following are described : anhydride. The formate thus obtained is mixed with acetone -(3 mols.); methyl ethyl ketone (3 mols.); 1 mol. of the methyl ester of the desired acid and y-methylpentane-ß8-dione (3 mols.); and camphor treated with 0-025 M of the sodium derivative of the (2 mols.). The dietherate, 2Et20,MgBr2, is also tertiary alcohol at 100— 120°, affording methyl described. R- B r ig h t m a n . iormate and the required ester. Electrolytic reduction of acetone. E. M ü l l e r . These exchanges suggest that organic compounds —See this vol., 840. containing metals are capable of ionising, affording ions containing the metal which give reactions strictly Reduction of oximes of unsymmetrical ketones parallel to those between metallic salts and bases but and of ß-ketonic esters. P. B i l l o n . —See this c enng in order of velocity. R. B r i g h t m a n . vol. 879. Hydroxymethylenemesityl oxide. H. Pauly Glyceraldehyde and glycollaldehyde. H. O. L. and L. Strassberger (Ber., 1927, 60, [.B], 1679— ’ isch er and C. T atjbe [in part with L. Feldmann] 1680).—Hydroxymethylenemesityl oxide [y-Jceto- z- (Ber., 1927,60, [B], 170^1709; cf. this vol., 3 4 0 ).- methyl-AaB-hexadien-a-oZ], b. p. 55—56°/4-5 mm., 858 BRITISH CHEMICAL ABSTRACTS.----A. 3870 mm., df* 1-0034, w f5 1-50765, «£* 1-51574, Acyl wandering. B. H e l f e r i c h and W. K l e in 1-53790, is prepared by the addition of a mixture of (Annalen, 1927, 455, 173— 180).—The isomerisation ethyl formate and mesityl oxide to sodium wire covered of (3-cZ-glucose 1:2:3: 4-tetra-acetate (this vol., 135) by ether. The corresponding copper salt, m. p. 130°, also proceeds in the fused substance at 140° in ordinary anil, C13H16ON, m. p. 60°, semicarbazone, m. p. 178°, glass or platinum vessels, but not in Jena glass or and isooxazole, b. p. 193—194°, are described. quartz, and is conveniently effected by 0-00LY- H. Wren, sodium hydroxide at the ordinary temperature. Structural relationships in the carbohydrate Since the same equilibrium product is obtained from group. W. N. H a w o r t h (J.S.C.I., 1927, 46, 295— either isomeride the change closely resembles the 3 0 0 t ). mutarotation of a sugar; the latter is therefore no /-Arabinal. J. M eisenheimer and H. J t t n g longer a certain proof of the presence of a 1-hydroxyl (Ber., 1927, 60, [5], 1462—1465; ef. Gehrke and group. p-cZ-Glucose 1 : 2 :3 : 6( ?)-tetra-acetate gives Aichner, this vol., 544).—Z(+)-Aeetobromoarabinose with methyl iodide and silver oxide a small yield of (cf. Hudson and Dale, A., 1918, i, 335), conveniently P-methylglucoside tetra-acetate; this must be due to prepared by the action of hydrogen bromide and further acyl wandering since the starting product is not acetic anhydride on Z-arabinose at 0°, is reduced by identical with cZ-glucose 2 : 3 : 4 : 6-tetra-acetate. zinc dust and acetic acid to Z-diacetylarabinal which Pure p-eZ-glucose 1 : 2 : 3 : 6( ?)-tetra-acetate 4( ?)- could not be caused to crystallise. It is converted by toluenesulphonate, m. p. 117—118°, sintering from cold barium hydroxide solution into Z-arabinal, m. p. 112°, [a]$ —19-3° or —10-1°, is converted by careful 81—83°, [a]n —202-S° in water, which is not hygro hydrolysis (Zempl6n, A., 1926, 822) into d-glucose scopic and can be preserved unchanged in presence of 4( ?)-toluenesulphonate, m. p. 165—167° (decomp.), air. Cautious treatment of Z-arabinal with ¿Y-sulphuric [<*]d +23° to [a]f, -f-41°. On reacetylation the latter acid affords 1 -deoxyarabinose, C5H10O4, m. p. about 90° gives the initial tetra-acetate, which is not identical after softening at 80° (phenylbenzylhydrazone, m. p. with glucose tetra-acetate 3-toluenesulphonate (Freu- 127— 129°). H. W r e n . denberg, A., 1922, i, 523). H . E. F. N o t t o n Dynamic isomerism. XXIII. Mutarotation Influence of solvent and of concentration on in aqueous alcohols. E. M. R i c h a r d s , I. J. optical rotation of penta-acetylglucose and F a u l k n e r , and T. M. L o w r y (J.C.S., 1927, 1733— penta-acetylmannose. P. A. L e v e n e and I. 1739).—In the mutarotation of dextrose and tetra- B e n c o w i t z (J. B io l. Chem., 1927, 73, 679—694).— methylglucose in aqueous alcohols, abrupt breaks Curves and tables are given shoving, for the penta- occur in the velocity coefBcient-water concentration acetyl derivatives of a- and p-glucose and a- and curves at 50% and 70% of water in the case of methyl (3-mannose, the relationship between the actual and and ethyl alcohols respectively. Curves showing the specific rotations and the concentration in various variation of dielectric constant or the partial vapour solvents. Most of the curves relating actual rotation pressure of the water in the water-alcohol solutions to concentration show a break at a certain concentra give no indication of this change. A connexion tion, and the curves for the different solvents diverge between thehydrogen-ion concentration of the medium more widely as the concentration increases. Specific and velocity of mutarotation is highly probable, rotation changes rapidly with concentration in the B. strong solutions, W. A andn d every r s o nlittle. in the ddute solutions. Acetone sugars. XII. Transformation of The numerical order in which the solvents arrange rf-galactose into d-fucose [rhodeose]. K. F r e u - themselves as regards their effect on rotation is the d e n b e r g and K. R a s c h ig (Ber., 1927,60, [I?], 1633— same for the two dextrose derivatives but different for 1636).—The jp-toluenesulphonyl derivative of diiso- each of the mannose derivatives, except that all forms show the lowest rotation in pyridine. The possible bear ing of these observations on the structure of the penta- acetyl derivatives is discussed. C. R. H a k in g t o n . h ? o>CMc* (I.) (II.) Two new pentabenzoylglucoses. H. H. S chlu- CMe2< ° 'Y '5 b a c h and W. H u n t e n b u r g (Ber., 1927, 60, [¿>], 2 O-C-H 1487— 1488).—a-Pentabenzoyl-h-glucose, m. p. U S- H 1200, [a];? +58-6° in chloroform, is prepared by the CH2I action of benzoyl chloride and pyridine in the presence propylidenegalactose is converted by sodium iodide of chloroform on the additive compound of carbon in acetone at 125° into the corresponding iodohydrin, tetrachloride and tribenzoylglucose derived from wo- (I)> m. p. 72°, [a]g -50-4° in s-tetrachloroethane, propylideneglucose (cf. Fischer and Rund, A., 1910, winch is reduced by sodium and moist ether to crude i, 363). If the tribenzoylglucose is treated with diisopropylidene-rf-fucose from which tZ-fucose, m. p.; benzoyl chloride and 20% sodium hydroxide, . 140—145°, [a]o +75-7° in water (final value), is benzoyl-h-glucose, m. p. 149—151°, [a]i> —52-b ^ in derived, thus confirming the structure (II) for the chloroform, is produced. H. Wb e n . methylpentose. Homogeneous diisopropylidene-d- Action of benzylamine on dextrose in a c e tic fucose, prepared from d-fucose, acetone, and sulphuric acid. III. C. N. C a m e r o n (J. Amer. Chem. boc., acid, has m. p. 37°, [a]1* -52-4°, [a]& -61-7° in 1927, 49, 1759— 1765; cf. A., 1926, 1228).—Glucose- substance. Diisopropylidene-l-fucose, m. p. 37°, [et]g benzylamide, m. p. 81-5°, [a]f —22-66° in met ^ +52-2°, [a]« +62-1°, and diisopropylidene-dl-fucose, alcohol, is obtained by boiling dextrose in JO /o m. p. 41°, are described. H. W r e n . alcohol with 3 mols. of benzylamine. The optica ORGANIC CHEMISTRY. 859 rotation of a solution of dextrose and benzylamine in Treatment of the product with phenylhydrazine alcohol at the ordinary temperature first becomes affords small amount of the phenylosazones of gluco slightly more positive, then less positive, and finally arabinose and maltose, whereas the cZ-gluco-d- negative (cf. Irvine, J.C.S., 1908, 93, 1429; 1910, 97, erythrose (I) is incapable of yielding an osazone. 1449). If acetic acid (2 mols. per mol. of benzylamine) The structure (II) for maltose is thus confirmed. is also present, the first change to positive rotation is ß-Octa-acetylmaltose dissolved in chloroform is con eliminated. The reaction between dextrose and verted by hydrogen iodide and subsequent treatment benzylamine in alcohol is also catalysed by acetic acid with silver oxide into hepta-acetylmaltose, m. p. 176°. in amount only sufficient to keep the solution The product does not yield furfuraldehyde when sub approximately neutral. These acetic acid solutions jected to Tollens’ reaction and hence has not suffered become coloured, due to reaction between the acetic degradation (cf. Irvine and Dick, J.C.S., 1919, 115, acid and the glucosebenzylamide, and contain 593). H. W r e n . methylglyoxal, identified as the ^-nitrophcnyl- Constitution of the disaccharides. XIII. The osazone. In aqueous solution, glucosebenzylamide is y-fructose residue in sucrose. W. N. Haworth, hydrolysed to dextrose and benzylamine. In presence E. L. H i r s t , and V. S. N i c h o l s o n (J.C.S., 1927, of a trace of acetic acid, glucosebenzylamide is formed 1513—1526).—In presence of dilute hydrochloric acid from its constituents, and a small proportion of brown tetramethyl-y-fructose is converted into (¿-methozy- oil is precipitated. If the acetic acid is present in the 5-?n(dhylfurfuraIdeJiyde, b. p. about 54°/0-07 nun. proportion of 1 mol. per mol. of benzylamine, no (oxime, m. p. 103— 104°; semicarbazone, in. p. 166— reaction takes place. F. G. W i l l s o n . 167°). On oxidation this gives u>-melhoxy-5-niethyl- Sugar syntheses. VII. Synthesis of prime- furan-2-carboxylic acid, m. p. 72—73°, which is also verose. B. H e l f e r i c h and H . R a u c h (Annalen, formed by methylation of o-hydroxy-5-methylfuran- 1927, 455, 168— 172).— ¡3-d-Glucose 1:2:3: 4-tetra 2-carboxylic acid, m. p. 165‘5—167°, obtainable either acetate (this vol., 135) condenses with acetobromo- by hydrolysis and oxidation of u-hromo-5-methyl- xylose in chloroform in presence of silver oxide to furfuraldehyde or by acetylation and subsequent give 6-$-d-xylosido-d-glucose hepta-acetate, m. p. 216° hydrolysis of chitonic acid. The above inter-relation (corr.), [a]j? —23-5° in chloroform. This is hydro ships confirm the substituted hydrofuran formula lysed by the method of Zemplen (A., 1926, 822) to previously suggested (cf. A ., 1926, 1126) for tetra- Q-$-d-xylosido-d-glucose, m. p. 208°, sintering from methyl-y-fructose. The action of dilute nitric acid 192°, [aj'fj -)-23-80 to —3-4° in water, which has been converts tetramethyl-y-fructose into a trimethoxy- identified with primeverose (Goris, Mascre, and Visch- lactol ethyl ester, C11H20O7, which it is difficult to niae, A., 1913,i ,576; 1920,i,14; Bridei,A., 1925,i,760) obtain in a pure condition. The corresponding methyl by conversion into its osazone, m. p. 220°, [a]1,] —109-7° ester on methylation gives a product from which a or —108° in pyridine. H . E. F. N o t t o n . crystalline amide, m. p. 100— 101°, is obtainable. B. W. A n d e r s o n . Degradation of reducing bioses. VII. Con Constitution of the disaccharides. XIV. stitution of maltose. G. Z e m p l ć n (Ber., 1927, Melibiose and its relationship to raffinose. W. 60, [B], 1555— 1564).—Maltose, purified by con C h a r l t o n , W. N. H a w o r t h , and W. J. H i c k i n - version into the p-octa-acetate followed by hydrolysis BOTTOM (J.C.S., 1927, 1527— 1536).—Hydrofysis of of the latter compound with barium hydroxide or, heptamethyl-methylmelibioside (after repeated re- preferably, sodium methoxide, is converted into the crystallisation, m. 13. 106— 107°, [a]D 4-97-8°) which non-crystalline oxime, [a]}? +85-6° in water, which had been encountered formerly during the isolation is transformed by acetic of hendecamethylraffinose (J.C.S., 1923, 123, 3125) anhydride and sodium was found to yield 2:3:4: 6-tetramethylgalactose acetate into oda-acetyl- and a liquid trimethylglucose which on methylation maltobiononitrile mixed formed 2:3: 4-trimethyl-a- and -ß-methylglucosides. with acetylated maltose- This confirms the modified formula for melibiose oxime. The product is advanced by Charlton, Haworth, and Peat (A ., 1926, nu dissolved in chloroform 273). B. W. A n d e r s o n . (I.) OJ-VU-n and treated with methyl- Lactose solubility and lactose crystal form alcoholic sodium methoxide ; the material thusobtained ation. II. O. F. H u n z i k e r and B. H . N i s s e n (J. is re-acetylated and, since further quantities of oeta- Dairy Sei., 1927, 10, 139—154).—Saturated lactose acetyhnaltobiononitrile are thereby produced from solutions containing milk colloids yield normal the acetylated maltoseoxime, a repetition of the crystals; sucrose prevents their full development. degradation is necessary whereby ultimately a pro- Crystals in ordinary sweetened condensed milk are of -----OH-OII____CH____• duct containing 49-7% of hepta-acetylgluco lactose. * Chemical Abstracts. H-O-OH i H-C-OH arabinose is isolated. Melezitose a compound of sucrose with HO-C-H I HO-O-H dextrose ? 31. B r i d e l and C. A a g a a r d (Compt. 0 The free glucoarabinose ■OH obtained by hydro rend., 1927, 185, 147— 148).—The results obtained lysing the hepta- with enzyme preparations made from Aspergillus acetate with barium niger show that a preparation which acts slowly on .ih2-o h OH sucrose may hydrolyse melezitose rapidly, and vice L. hydroxide is trans (II.) formed into the oxime versa. The non-identity of the enzymes which attack which is acetylated and degraded in the usual manner. sucrose and melezitose, thus demonstrated, disproves 860 BRITISH CHEMICAL ABSTRACTS.----A. Kuhn and von Grundherr’s view that melezitose is a the pure gum, (CGH10O5)„, [a]ft +88-8°. The crude compound of sucrose with dextrose (A., 1926, 1127), and pure materials differ little in chemical composition and the nature of the non-reducing ¿-fructose united and in general properties except towards Fehlhig’s with the dextrose remains to be determined. solution. Towards chlorine dioxide their behaviour T. H. P o p e . is almost identical. H. W r e n . Lichenin. III. Lichenin, Pringsheim’s lich- Preparation of yeast gum by enzymic degrad osan, and Bergmann's lichohexosan. K. H e s s ation and the detection of an enzyme in yeast and H . F r i e s e (Annalen, 1927, 4 5 5 , 180—205).— which hydrolyses yeast gum. H. K r a u t , F. Attempts to purify lichenin by dissolution in hot water E i c h h o r n , and H. Rubenbauer (Ber., 1 92 7, 60, [2?], were unsuccessful, but by reprecipitation from alkaline 1644— 1648; cf. preceding abstract).— The isolation solution by means of carbon dioxide or concentrated of yeast gum by Salkowski’s method involves the sodium hydroxide, and finally from a cuprammonium use of 3 % sodium hydroxide solution and hence the solution as a copper-alkali compound, a non-reducing possibility that the gum is to some extent denatured. product, [ajg +8-33° in 22V-sodium hydroxide, is Tho product has therefore been isolated by successive obtained. In cuprammonium solution this shows a treatments of yeast with ethyl acetate, pepsin, and similar optical behaviour to that of cellulose, the either papain with or without hydrocyanic acid as rotation being first increased and then lowered by activator or diastase; it is remarkable that papain addition of sodium hydroxide. The formation of a is most active in absence of the activator. Products single copper complex containing 9Cu : 10C6Hi00 5 is of low mol. wt. are removed by precipitation with indicated, but it is probable that the lichenin still alcohol and dialysis and final purification is achieved contains inactive impurities and that the actual ratio by adsorption with kaolin and aluminium hydroxide. is 1:1. Lichenin triacetate, purified by repeated The substance appears identical with Salkowski’s reprecipitation, has [a]^ —3S° to —39° in chloroform. yeast gum, but comparison of the adsorption isotherms Previous work (A., 1926, 715) which has been over of the products suggests that their degree of dis- looked by Pringshcim (A., 1925, i, 1385; this vol., persivity differs. Since the sum of the amounts of 136) and by Bergmann and Knehe (A., 1926, 714; yeast gum obtained by the fermentation process and cf. this vol., 341) has shown that heating at 235° in remaining in the unfermentable residue is consider naphthalene is not necessary to depolymerise this ably less than that obtained by Salkowski’s method, substance, since this is effected in glacial acetic acid it must be assumed that an enzyme is present in yeast at the ordinary temperature. It is suggested that which hydrolyses yeast gum and retains its activity the changes produced by the former treatment are after treatment of the yeast with ethyl acetate at due to the partial decomposition of the acetate. 3 7 °. The enzyme appears present in the yeast in an Lichosan (lichohexosan), [a]g ± 0 ° in water, +30-4° unusual manner and separated from the yeast gum. in 2Ar-sodium hydroxide, prepared by the glycerol It is liberated by definite processes during autolysis method contains 6% of reducing matter (as dextrose; or plasmolysis. Yeast gum is not hydrolysed by Allihn’s method). In accordance with the results of taka-diastase, emulsin, or the extracts from Aspergillus Pringsheim and of Bergmann it gives a triacetate, niger or malt. H. W r e n . [a]” —20° in chloroform. Neither of these substances is, however, pure. The former is separated by one Saccharification of dextrins. P. P e t i t and precipitation from aqueous alcohol into fractions of R i c h a r d (Compt. rend., 1927, 1 8 5 , 224—225).-— widely-differing rotation, whilst repeated fractional Dextrins prepared by the action of amylase on starch precipitation of the acetate affords a product, [a]p paste at 50° (I) and 70° (II) were s u b m itte d to the —35-9° in chloroform, identical with lichenin tri further action of amylase, and the percentages of acetate and yielding on hydrolysis a non-reducing maltose formed at different temperatures were tabu lichosan (lichenin), [ajg +8-42° in 2AT-sodium hydr lated. The optimum temperature in each case was oxide, which is sparingly soluble in cold water. about 52°, when 13% and 47% of (I) and (II), re- Lichosan is therefore lichenin which contains sufficient spectively, were converted into maltose. Equations impurity to render it water-soluble. The bearing are suggested for giving the proportion of maltose of these facts on the theoretical considerations of formed at any given temperature. The residua Pringsheim and of Bergmann is fully discussed and it is dextrins in all cases contained almost the same suggested that further work on lichenin must be percentage of dextrose. B. W. A n d e r s o n . preceded by its isolation in a pure state. Recent advances in our knowledge of starch. H. E. F. N o t t o n . A. R. L i n g (J.S.C.I., 1 9 2 7, 46, 2 79 — 2 8 1 t ). Yeast gum and the purification of compounds with high mol. wt. by adsorption. H. K r a u t and Starch. XX. Disaggregation of the poly- F. E i c h h o r n (Ber., 1927, 6 0 , [£], 1639— 1643).— amyloses. H. Pringsheim and P . M e y e r s o h n Purification of yeast gum is effected by treating a (Ber., 1927, 60, [£], 1709— 1716).—From calculations definite quantity of the product in a constant volume of the mol. rotations it is deduced that the con of solution with varying amounts of adsorbent and figuration of the amylobiose union occurs once ui determination of the optical activity of the residual diamylose and twice in triamylose. The mol. w solution; purification is regarded as complete when the of tetra(triacetyl)amylose is normal in benzene, adsorption isotherm follows a normal course. Yeast whereas in phenol or glacial acetic acid the simp es gum, prepared according to Salkowski’s method consists possible value (that of diamylose acetate) is observe- of 14% of reducing sugars readily adsorbed by kaolin Similarly, a-hexa(triacetyl)amylose has the mo . w • (but not by aluminium orthohydroxide) and 86% of of diamylose acetate in phenol. It has not ORGANIC CHEMISTRY. 861 found possible to obtain solvents in which the acetates and preceding abstract).—The conversion of cellulose of fi-tri- and B-hexa-amylose show differing behaviour. into cellobiose, determined as octa-acetate, during Both acetates give the value for the triacetate in acetolysis with acetic anhydride and sulphuric acid glacial acetic acid or phenol and of the hexa-acetate is independent of the origin, pre-treatment, or physical in benzene. Tetra(triacetyl)amylose and a-hexa- condition of the cellulose. The yield in all cases is (triacetyl)amylose pass hi boiling naphthalene into about 50% of the theoretical. The polarimetric the acetate of diamylose, from which diamylose is changes during acetolysis show a similar parallelism for obtained by hydrolysis. H. W r e n . the different celluloses examined (Kaldbaum cotton, Conditions under which the iodine-starch linters, ramie, wood cellulose, mercerised cotton; reaction does not occur normally. M. J. these have already been shown by Hess, Messmer, and Lubitsch, A., 1925, i, 1246, to be chemically Gk a m e n it z k i (Biochem. Z., 1927, 185, 427—428).— In presence of excess of potassium iodide, hydrogen identical). Experiments with cellulose triacetate, peroxide, and an acid, the blue colour given by iodine which in dilute solution in glacial acetic acid has the and starch is intensified, instead of being abolished, low mol. wt. of acetylglucosan, show that the form ation of cellobiose is also independent of the state by heat. C. R. H a r i n g t o n . of association of the cellulose derivative, a yield of Inulin. III. L. S c h m i d and G. B i l o w i t z k i 39-5% being obtained. C. H o l l in s . (Monatsh., 1927, 48, 163— 165).—Inulin dissolved in Cellulose. XXIX. Preparative separation of dry piperidine does not elevate the b. p. of the latter, cellulose crystals from bast fibres. I. From and is thus not depolymerised (cf. A., 1925, i, 1386; ramie fibres. K. H e s s and G. S c h u l t z e (Annalen, this vol., 342). E. W . W i g n a l l . 1927, 456, 55—68).—Selected ramie fibre, repeatedly Cellulose. XXVI. Crystalline triethylcellul- purified with alkali, chlorine dioxide, and sodium ose. K. H e s s and A. M ü l l e r (Annalen, 1927, 455, sulphite until ash-free (alM-3+3-410 in cuprammonium 205—214).—Ethylation of alkali-cellulose with ethyl hydroxide solution), is acetylated for 8 hrs. at 70— chloride gives only the diethyl ether (cf. A., 1921, 75° with sulphuric acid, acetic anhydride, and benzene, i, 710), but by using ethyl sulphate and alkali as and the triacetate dissolved out in glacial acetic acid described for cellobiose (A., 1925, i, 1383) triethyl- or chloroform. The unacetylated cellulose appears cellulose, m. p. 255°, sintering from 240°, [a]î5 +26-1° in the form of spindle-shaped crystals, 0-05—0-1 mm. in chloroform, +49-1° in pyridine, is obtained. The long, suspended in the solution, and may be separated products from cellulose-^ (73%), viscose-cellulose by sedimentation from the detritus with which it (64%). and cuprammonium-eellulose (84% of theor is mixed. The crystals are identical chemically with etical yield) are chemically identical and, unlike tri- pure cellulose prepared from ciystallised diacetate. methylcellulose (this vol., 44), insoluble in water. The “ intercrystal substance ” which is removed as The pure substance crystallises readily^ from benzene, triacetate, when regenerated from the latter by but if separation is too rapid an amorphous powder hydrolysis with2Ar-methyl-alcoholic sodium hydroxide, or elastic film is obtained. H. E. F. N o t t o n . shows in cuprammonium solution a slightly smaller optical rotation than the crystals. C. H o l l in s . Cellulose. XXVII. Oxycellulose. K . H e s s Lignin. III. Tautomeric forms in soluble and G. K a t o n a (Annalen, 1927, 455, 214—226).— Further evidence is adduced in favour of the view lignin. A. F r i e d r i c h (Z. physiol. Chem., 1927, that oxycellulose is a mixture of cellulose with pro 168, 50—67).—The preparation of the soluble lignin ducts of its oxidative degradation (cf. A., 1925, i, of pine wood, free from impurities which have similar 519). Cellulose has been oxidised by means of properties, is described, and it is found that the bromine water and calcium carbonate (Faber and products can be separated by boiling chloroform into lollens, A , 1899, i, 854), permanganate (Nastjukoff, two substances differing only in solubility and colour. A, 1901, i, 315), nitric acicl (Cross and Bevan, J.C.S., These two products are readdy interconvertible, and from the colour reactions with ferric chloride and anc* cliroin^° a°id (Vignon, A., 1898, i, behaviour towards bromine they are regarded as Pr°ducts cannot be purified by boiling with water, owing to hydrolysis, but complete puri enolic and ketonic forms. The enolic form (chloro fication is effected by prolonged extraction with 5% form-soluble) has a mol. wt. of about 650, whilst sodium hydrogen carbonate (5— 15% loss), and that of the ketonic form is about double this value. A . W o r m a l l . nnally with 0-5AT-sodium hydroxide. No cellulose- Ultra-violet absorption spectra of lignin and e, matter is extracted by the sodium hydrogen carbonate, but only simple compounds similar to substances with the coniferyl residue. R . O . H e r z o g and A. H i l l m e r (Z. physiol. Chem., 1927, ose which pass into solution during the initial oxid- 168, 117—123; cf. this vol., 342).—The absorption a ion of the cellulose. The purified oxycelluloso shows a diminished solubility in 2AT-sodium hydr- curves of coniferin, coniferyl alcohol, and poly merised coniferyl alcohol have similar shapes but oxi e from which it is almost quantitatively repre- show some differences, especially in the region of the ipi ated by acetic acid. Its specific rotation-con- shorter waves. The curve for the polymeride is most en ration curve in cuprammonium solution is entical with that of pure cellulose. like that of ligninsulphonic acid, but the results sug gest that the molecule of the latter consists in part . H. E. F. N o t t o n . only of coniferyl complexes. A. W o r m a l l . a ? 1 °.se- XXVIII. Formation of cellobiose. & of cellulose. III. H . F r i e s e and K. Humus substances. E. S c h m i d t and M. (Annalen, 1927, 456, 38— 54; cf. this vol., 44, A t t e r e r (Ber., 1927, 60, [5], 1671 1679). Furfur- 862 BRITISH CHEMICAL ABSTRACTS.— A. aldehyde or humus substances of differing origin are to isolate hexarnethylencimine, b. p. 134— 135°/759 allowed to remain in the dark during ;9 days in mm., df 0-8643, nf; 1-4570 (hydrochloride, m. p. 222°). contact with 3% chlorine dioxide solution in the In addition, a-amino-£-&.*'-hexenylamino-n-hea:ane, presence of precipitated calcium carbonate and a CH2:CH-[CH2l4-lSrH-[CH2]G-NH2, b. p. 137—140°/12 trace of vanadium chloride. After removal of excess mm., df 0-8990, is produced; the hydrochloride, m. p. of chlorine dioxide, the calcium oxalate produced is 188°, chloroplatinate, decomp. 215?, methiodide, isolated and weighed as calcium oxide or the oxalic C17H3SN2I2, m. p. 223°, and the non-crystalline acid is isolated from it if the salt is very impure; p¡crate and benzoyl derivative are described. maleic acid is isolated as such from the filtrate and H. W r e n . weighed or converted into calcium maleate and Decomposition of quaternary ammonium weighed as calcium oxide. In addition to the acids, hydroxides. Methylalkoxymethyldiethyl- an ill-defined degradation product of the humus is ammonium hydroxides. T. D. S t e w a r t and J. G. formed which contains calcium hr varying amount. A s t o n (J. Amer. Chem. Soc., 1927, 49, 1718—172S). Since the amounts of oxalic acid formed from the —When an aqueous solution of methylethoxymethyl- same initial material under apparently identical con diethylammonium hydroxide is evaporated at the ditions fluctuate considerably it is impossible to attach ordinary temperature in a vacuum over phosphoric any well-defined theoretical significance to them. oxide, it commences to decompose when the com The mean quantities in g. of maleic acid derived position of the solution approximates to that of a from 10 g. of the various products are indicated by tetrahydratc of the base, yielding methyldiethylamme figures placed after the names : furfur aldehyde, S-2; (18-5 mols.%) and mcthylcthylamino (ST5 mols. %), humin from furfuraldehyde, 4-32; humic acid from the latter being accompanied by an equivalent of f urfur aldehyde, 2-55; humic acid from sucrose, 1-00; ethylene. Above 100°, at atmospheric pressure, de humic acid from dextrose, 1-10; humic acid from composition takes place with formation of metliyl- sphagnum moss, 0-94; humic acid (Merck), 0-85; diethylaminc almost exclusively. Treatment of di- humic acid from quinol, 1-00; humic acid from methylaminomethyl isobutyl ether (Robinson, J.C.S., pyrogallol, 0-75. The production of maleic acid 1923, 123, 536) with ethereal methyl iodide affords appears to depend on the presence of the group trimethylisobiitozymethylammonium iodide, m. p. 103— OCHiCH’C or CiCH-CHIC, which may occur hi either 110°, from which the corresponding hydroxide {chloro- the benzene or furan ring. Since, however, it may be platinate, decomp. 231—233°):was prepared in aqueous assumed that maleic acid is formed with equal solution. On evaporation of the latter at the ordinary readiness and therefore in equal amount from sub temperature as above, decomposition takes place stances containing a similar arrangement of the with the production of triinethylamine as the only C4 chain it appears that a structural difference in amine. Dimethyldiethylammonium hydroxide de respect to this group exists between the products composes similarly hi aqueous solution with formation derived from furfuraldehyde and the humic acids of ethylene and dimethylethylamine. The carbonate from the carbohydrates, phenols, and moss. decomposes hi aqueous solution, a solid hydrogen The relative quantities of maleic acid derived from carbonate behig precipitated. The latter decomposes furfuraldehyde humus and the corresponding humic when heated, yielding ethylene, dimethylethylamine, acid support the view that the action of potassium carbon dioxide, and water. Fused methylethoxy- hydroxide on the former is accompanied by a profound methyldiethylammonium iodide has dm l-361o, change and does not consist merely in hydration. A 2-56 at 110°. F. G. W illso n . H. W r e n . Infra-red absorption spectra of organic deriv So-called carbohydrate group of protein. atives of ammonia. V. Primary, secondary, Preparation of glucosaminomannose. S. and tertiary alkylamines. F. K. B e l l (J. Amer. k e l and C. J e l l i n e k (Biocliem. Z., 1927,185, 3J*— Chem. Soc., 1927, 49, 1837—1845; cf. A., 1926, 399).—Egg-white was hydrolysed with barium hydr 453).—The infra-red absorption spcctra of mono-, oxide ; the barium was removed as carbonate an di-, and tri-n-propyl-, - «-butyl-, and -¿soainyl-amines the filtrate treated with lead acetate and ammonia, have been examined. All show the band at 3-45 ¡x, the precipitate was dissolved in dilute acetic act , characteristic of the methyl group, a less intense re-precipitated, collected, and decomposed^ 1 band at 6-85 ¡x probably related harmonically to carbon dioxide; the filtrate from the lead carbona c the former, and bands of uniform intensity, throughout was treated with mercuric chloride and, after some the series at 7-2—7-3 |x and about 9-3 ¡x. The primary days, was filtered, concentrated, and treated vi amines show a marked band at 3-05 ;x. This persists alcohol. The aqueous solution of the_ resulting Pr® at lower intensity with the secondary amines, but cipitate was treated with cupric chloride and a a i, is practically absent with the tertiary derivatives, the precipitated copper compound was dissolve j thereby confirming earlier results on the differentiation methyl alcohol and treated with hydrochloric aciu between the three classes of amines. The primary and excess of ether; the resulting precipitate amines are differentiated further from the secondary the formula C12H23O10N; similar preparations vcro and tertiary amines by a band at about 6-2 ¡j.. obtained from egg-white and from egg-yolk al u F. G. W i l l s o n . by tryptic digestion followed by purification Hexamethyleneimine. Ill, J. v o n B r a u n a n d described above. In both cases the prod uc < O. G o l l (B e r ., 1927, 60, [2?] 1533— 1534; c f . A., optically inactive. On hydrolysis with , 1910, i, 821).—By the action of alkali on £-bromo-n- acid, the substance yields glucosamine hydroc i hexylamine in quantity it has been found possible and mannose; the absence of free anono-m g ORGANIC CHEMISTRY. 863 indicates that, in this compound, glucosamine must ductivity and f. p. of aqueous solutions of hexamethyl be combined with mannose through the amino-group. guanidinium picrate indicates that it is ionised to C. R. Harington. about the same extent as sodium picrate, so that the Degradation of amino-acids and amino- internal complex salt formula previously suggested purines by methylglyoxal and related sub for this substance (loc. cit.) applies, if at all, oidy to stances. 0. N e u b k r g and M. K o b e l (Biochem. Z., the solid. According to the dynamic formula for 1927,185, 477—479).—When heated in aqueous solu guanidhiium salts the two forms of guanidinium tion, methylglyoxal and alanine react to form carbon picrate (von Cordier, A., 1906, i, 486) and of methyl- dioxide, ammonia, and acetaldehyde. Reactions of guanidinium picrate (Gulewitsch, ibid., 637) cannot similar type occur, in general, between glyoxal deriv be stereoisomerides, but it is suggested that dimor atives or dihydroxyacetone, and amino-acids or phism may occur according as the ions in the crystal aminopurines. C. R. H a r i n g t o n . lattice are separate or united by auxiliary valencies. On repeating Gulewitsclfs work, methylguanidinium Synthesis of taurine. C. S. M arvel, C. F. picrate is found to crystallise from alcohol hi an B a ile y , and M. S. Spare erg (J. Amer. Chem. Soc., orange-yellow monotropic [3-form, which is stable at 1927, 49, 1833— 1837).—Treatment of ethylene di the ordinary temperature but passes when heated bromide (615 g.) in boiling 95% alcohol (1250 c.c.) at 150° or shaken with a solvent into the stable egg- and water (450' c.c.) with anhydrous sodium sulphite yellow y-form. On recrystallising either form from (125 g.) in water (450 c.c.) affords sodium S-bromo- aqueous picric acid, a stable a-form, m. p. 200-5— ethylsulphonate- in 78— 90%. yield. Treatment of 201-5° after shrinking at 190°, is obtained. Con the latter with an equal weight of phosphorus penta- version of the a- or y- into the (3-form can be effected chloride yields S-bromoethylsul'phonyl chloride, b. p. only by reerystallisation. The a- and (3-forms differ 119—121°, d™. 1-921, ?if, 1-5242 (yield 64—71%). in crystalline form and optical properties: Tho When the latter is treated with water until solution y-form is identical witli the a- in chemical properties is complete, the solution evaporated under reduced and is probably a pseudomorph of the latter after pressure, and the residue treated with concentrated the ¡3-form. aqueous ammonia, taurine is obtained in 16% yield, When NNN'- trimetliyl- N"N" - diethylguanidine, ■whilst a 44—51% yield of taurine is obtained by b. p. 75-2°/14-5 mm., purified through the picrate, keeping sodium ¡3-bromoethylsulphonate in aqueous m. p. 126—127°, is converted as previously described ammonia for 5—7 days, and subsequently evaporating into A7ATAT'-trimethyl-iY'.Ar"iV"-tricthylguanidinium to dryness and extracting the residue with alcohol. picrate or chloroplathiate, only one product is obtained F. G. W i l l s o n . in each case, the supposed isomerides being actually Diacylamides. II. Preparation of dipropion- impurities introduced by using impure trimethyldi- amide and diisobutyramide. K. B r u n n e r , R. ethylguanidine. Attempts to obtain isomerides by G ru n er, and Z. B e n e s (Monatsh., 1927, 48, 123— recrystallising the pure salts were unsuccessful. 124; cf. A., 1924, i, 1310).—Dipropionamide is ob When pentainethylguanidinc is heated with dicthyl- tained by heating potassium cyanate with propionic amine, or pentaethylguanidine (picrate, m. p. 92-5— anhydride at 100°, adding benzene, and re-heating; 94°) with dimethylamine at 100°, both are recovered diisobutyramide by using isobutyric anhydride and unchanged. Tho preparation of penta-alkylguanidincs heating at 138—140°. E. W. W ignall. by Lecher and Graf’s method (A., 1923, i, 761) is Peralkylated guanidines. IV. H. L e c h e r therefore not accompanied by the displacement of [with F. G r a f , F. G n a d i n g e r , K. B o l z , and K. one amino-residue by another, and the source of the Ch b d o b a ] (Annalen, 1927, 455, 139— 168).—N m '- impurity in the trimethyldicthylguanidine remains Tridhyl-S-methyl-ifi-lhiocarbamide, b. p. 85°/12 mm. unknown. H. E. F. N o t t o n . (corr.), is obtained by boiling together diethylamine and ethylthiocarbimide hi benzene and niethylating Carbamide series. Transformations of nitro- the product (cf. A., 1925, i, 1392). With diethyl- guanidine. T. L. D a v is and A. J. J. A b r a m s (Proc. amme and mercuric chloride it gives pentaethyl- Amer. Acad. Arts Sci., 1926, 61, 437—457).—Mtro- gvanidine, b. p. 93—94°/13 mm., from which liexa- guanidine “ dearranges ” to form nitroamide and wiylguanidinium iodide is obtained. Hexaclhylgvan- cyanamide, or ammonia and nitrocyanamide. In mnium, jncmte, m. p. 90-5—92°, forms an additive concentrated sulphuric acid, nitrous oxide and later product, m. p. 164— 166°, with sodium picrate (1 mol.), carbon dioxide, with nitrogen, are evolved, as anticip out it does not separate in combination with hexa- ated if nitroamide were present, and the solution, methylguanidinium picrate from solution or from a although containing no nitric acid, serves for the used mixture. Pentamethylthiuronium picrate gives nitration of aniline, phenol, and acct-p-toluidide. Gquim°lecUla,r additive product, m. p. 175-5— In aqueous solution, dearrangement in both ways is n , ? '^thsodium picrate. Hexamethylguanidinium indicated. When digested with ammonia, nitro- • 4: Q-trinitro-m-tolyloxide, m. p. 100— 102°, from guanidine yields guanidine (from the cyanamide) and e corresponding iodide and ihallous trinitro-m-tolyl- carbamide (originating from the nitrocyanamide). nnt6 > ^th sodium trinitro-m-tolyloxide but Guanidine carbonate is readily prepared in 90% of with sodium picrate, whilst lioxatne thy Ig u anid in - tho theoretical yield by digesting nitroguanidine with picrate does not combine with sodium trinitro- excess of aqueous ammonium carbonate for 10— 12 nmK l i , factor influencing combination is lirs. With aniline and water, nitroguanidine yields In nt ability of both components to unite diphenylcarbamide with some phenylguanidine and e crystal lattice. Determination of the con phenylcarbamide. With aqueous methylamme at 864 BRITISH CHEMICAL ABSTRACTS.— A. 60—70° methylnitroguanidine, m. p. 160-5— 161°, is is obtained, which on concentration turns blue and obtained from either a- or [3-nitroguanidine. Ethyl- deposits a dark blue substance which develops an nitroguanidine, m. p. 147— 148°, butylnitroguanidine, odour of carbylamine on treatment with alkali; this m. p. 84—85°, and benzylnitroguamdine, m. p. 183-5°, is probably identical with the substance described by were also obtained. Nitrosoamide is probably present Hofmann (Annalen, 1904, 337, 33). Similarly when in an aqueous solution of nitrosoguanidine. A cold, methyl sulphate reacts with potassium ferrocyanide acidified solution converts dimethylaniline and di- in presence of absolute methyl alcohol, a colourless phenylamine into nitroso-derivatives. substance,(?) [Fe(CN)]GH5Me3,Me2S04, is obtained; C h e m i c a l A b s t r a c t s . this turns blue when preserved, gives with alkali the Acetoguanaminesulphonic acid and related carbylamine Odour, and forms silver and zinc salts substances. R. A n d r e a s c h (Monatsh., 1927, 48, which also turn blue rapidly. 145— 154).—Diguanide acetate, m. p. 175°, is prepared The product of methylation by methyl sulphate in from diguanide sulphate; the action of copper acetate the absence of alcohol, hexamethyl ferrocyanide on dicyanodiamide (cyanoguanidine) yields copper methyl sulphate (cf. Hartley, J.C.S., 1910, 97, 1066, diguanide. By-products of the preparation of copper 1725), is converted directly into the chloride by heat diguanide sulphate from cyanoguanidine are melamine ing with hydrochloric acid and barium chloride. (2:4: 6-triamino-1 : 3 : 5-triazine), from a solution of Reactions of this type, together with the develop which nitric acid precipitates a nitrate, and guanyl- ment of the carbylamine odour, suggest the exist carbamide (nitrate prepared). Diguanide hydro ence of a stable hexa(methylcarbylamine)ferrous ion, chloride, C2H7N5,2HC1, sinters from 200°, and has [Fe(CNMe)e]", of which the above is the chloride. completely melted at 350°; copper diguanide nitrate, On heating this chloride and extracting with chloro (C2H6N5)2Cu,2HN03,H20, and hydrochloride, form, a solution of a-tetramethyl ferrocyanide (Hartley, 2(C2H6Ns)2Cu,4HCl,5H20, are described. J.C.S., 1913,103,1196) is obtained, which on evapor Diguanide acetate when heated with acetic an ation gives the (3-form, insoluble hi chloroform. It is hydride yields acetoguanamine ( 2 :4-diamino-6- now found that the a-form, rapidly separated, dis methyl-1 : 3 : 5-triazine) which with chlorosulphonic solves hi water much more slowly than the ¡3-form; acid gives the to-sulphonic acid (barium salt). whereas the latter gives an immediate precipitate Cyanoguanidine when heated with acetic anhydride with silver nitrate, the former reacts very slowly; reacts vigorously to give acetoguanide (4-amino-2- the conductivity in solution is much greater for the hydroxy-6-methylhexahydro-l : 3 : 5-triazine) (pierale, P-form than for the a-form. The j3-form yields a m. p. 240—260°), of which the o -sulphonic acid proportion of cyanide ion indicating the formula (barium salt) is prepared. [Fe(CNMe)4](CN)2; it gives no coloration with ferric Acetoguanide, when heated with concentrated chloride. When, however, the crude chloride is sulphuric acid, yields acetoguanamide [2:4-dihydroxy- treated with methyl alcohol and heated, the above G-methyl-1 : 3 : 5-triazine] (picrate, m. p. 270—280°, a-form remains in the chloroform extra ct, but the decomp.), of which the o>-sulpho?iic acid (barium salt) is substance which crystallises, and is thereafter insoluble prepared. The a-sulphonic acids of the 6-propyl and hi chloroform, has the electrolytic conductivity of a 6-zsopropyl homologues (cf. Nencki, A., 1876, ii, 187) uni-bivalent salt, and composition and behaviour are also prepared. E. W. W ignall. consistent with the formula Catalytic synthesis of hydrocyanic acid from [(MeNC)2Fe(Me0H)2](CN)2(H20)4; the co-ordination nitric oxide and hydrocarbons. E. E lod and H. number is again 6. On evaporating the chloroform containing the N e d e l m a n n . —See this vol., 838. a-tetramethyl ferrocyanide, a product is obtain™ Action of molecular and combined oxygen on which rapidly turns red; treatment with water gi'fe potassium cyanide at 300—500°. E . B i e s a l s k i a red solution from which chloroform extracts the and H . v o n L e p p (Ber., 1927, 60, [5], 1459— 1462; a-form. This gives yellow crystals, which no longer cf. Hofmann and others, A., 1926, 370).—Potassium turn red, but dissolve in water slowly to a colourless cyanide mixed with soda-lime and porous clay gives solution. The properties agree with the non-ionic 23-2% of its nitrogen as nitrate and 2-6% as nitrite formula [(MeNC)4Fe(CN)2] : the substance gives a Avhen heated hi air at 270°. Addition of silver powder violet colour with ferric chloride. The red, aqueous or nickel carbonate increases the yield of nitrate to solution yields on evaporation a red reshious substance, 65-2% and 71-5%, respectively. Oxidising agents Fe(Me),(CNUH20)2, which at 100° loses 1 mol. o such as copper, manganese, or arsenic oxides, potass water to give [(MeNC)3Fe(H20)(CN)2]. This behaves ium dichromate, or the oxides of tungsten or molyb towards sdver nitrate similarly to the above a'*or. ’ denum do not effect the conversion of potassium with potassium ferricyanide it gives slowly a ue cyanide into nitrate but, in the absence of air, give coloration, and ultimately ferric ferrocy«11}* free nitrogen. H. W r e n . separates; with potassium ferrocyanide a 11L Alkylation of hydroferrocyanic acid. F. H o l z l green coloration is obtained. On h e a t i n g alone [with^W. H a u s e r and M. E c k m a n n ] (Monatsh., 1927, with sodium hydroxide solution, a carbylamine o 48. 71—86).—When silver ferroevanide is treated is observed. . , Hnrt. with methyl iodide (Hartley, J.C.S“, 1912, 101, 705), It is thus established that the isomerism o _ the substance MeGFe(CI\T)6I2,4AgI is obtained, and ley’s a- and p-tetramethyl ferrocyranides is no ■ o thence Me6Fe(CN)6(N03)2 and Me4Fe(CN)6. In ab cis- and ¿rans-nature, but is due to a change solute methyl alcohol, methyl ferrocyanide is pro co-ordination number. The crude a-form, how . duced directly. As a by-product, a yellow liquid may be a cis—trans isomeric mixture. ORGANIC CHEMISTRY. 865 Ethylation of silver ferrocyanide by ethyl iodide or an inhibiting effect, and although a higher yield is gives tetraethyl ferrocyanide of which no (3-form or obtained by adding the alkyl halide dissolved in a aquo-derivative exists. There is no reaction with hydrocarbon to a given amount of ether and mag potassium ferro- or ferri-cyanide; the reaction with nesium than by adding the halide in a mixture of silver nitrate is very slow; the conductivity in solu ether and hydrocarbon, neither procedure is as satis tion is very small, indicating that the non-electrolyte factory as the use of ether alone. Thus, using 0-2 complex is only slightly dissociated. The substance g.-mol. of ether to 1 g.-mol. of halide and 100 c.c. is therefore regarded as [(EtNC)4Fe(CN)2]. of benzene, the yields of magnesium w-butyl bromide Propylation by propyl iodide yields similarly the and of magnesium phenyl bromide, after refluxing compound, [(Pr“NC)4Fe(CN)2], m. p. 107— 111°, which for 4 hrs., are reduced by 10% and that of magnesium is apparently a mixture of isomerides, since addition benzyl bromide by 30% (cf. Gilman and McCracken, of water causes partial decomposition, with the separ A., 1924, i, 23), but even these yields can be obtained ation of a white substance; evaporation of the aqueous only by adding a portion of the alkyl halide in solution gives a substance of the same m. p. and com ether alone in order to start the reaction. Toluene, position, which gives no white substance with water. xylene, and light petroleum have a similar retarding A by-product of the propylation is a substance, effect. Experiments carried out with ether alone at C20H32O4N8Fe3, obtained by extracting the original 20° show that the minimum amounts of ether (in product with slightly aqueous alcohol. On account g.-mol. per g.-mol. of halide) required for maximum of its colourless nature, development of a carbylamine yields are, with magnesium n-butyl bromide, 1-3— odour under the action of alkali, partial transform 1-5 (yield 94%); with magnesium phenyl bromide, ation into potassium ferrocyanide by heating with 4—5 (93%); with magnesium benzyl bromide, 6—7 potassium cyanide, and gradual dissolution in pyridine, (93%). Grignard reagents were prepared from the the formula following halides, the figures quoted being the pro portion of solvent (ether unless otherwise stated) and ? 2°C N CN ? N (PraN'C)2---Fe Oxidation of cacodyl oxide. A. V a l e u r and P. ide induces reaction. Thus in presence of about M /30 Gaillio t (Compt. rend., 1927, 185, 70—71).— chromic chloride, magnesium phenyl bromide rapidly Cacodyl oxide is converted by a slow stream of absorbs 1 mol. of carbon monoxide, the reaction oxygen under water at the ordinary temperature into product affording on fractional distillation traces of cacodylic acid, trimethylarsine, monomethylarsine chromium carbonyl, phenol, and benzaldehyde and oxide, and arsenious acid with small amounts of in addition about 10% of diphenyl, 15% of benzo- trimethylarsine oxide and methylarsinic acid. The phenone, 15% of benzhydrol, 10% of triphenylvinyl- cacodylic acid is formed by direct oxidation, the tri carbinol, and 2% of triphenylcarbinol. The benz methylarsine, monomethylarsine oxide, and arsenious hydrol and benzophenone arise from decomposition acid are formed by simultaneous self-oxidation and of benzpinacone, fractional crystallisation of the reduction. E. A. L u n t . reaction mixture affording about 33% of this product. Benzil is probably the primary product, the benz f ^ Grignard starter. R. W . H u f f e r d (J. Amer. pinacone arising by the action of 2 mols. of mag , e™-.S°c., 1927, 49, 1845— 1846).—The preparation nesium phenyl bromide, 2PhMgBr + COPh-COPh of Grignard reagents is often facilitated by the — ^ CPh2(OMgBr)-CPh2-OMgBr — > addition of a small quantity of anhydrous aluminium CPh2(OH)*CPh2-OH. Traces of benzil were detected romide, freshly prepared by heating aluminium with from the reaction product below 0°, and a little tri- bromme- F. G. W i l l s o n . phenylmethane was isolated. Triphenylvinyl alcohol Effect of some solvents on the yields of Grig- is probably formed by dehydration of triphenyl- ^ ^agents. H . G i l m a n and R. M c C r a c k e n ethylene glycol (from phenylbenzoin) and the tri- ft • u Chim-’ 1927) 461 463— 472).—A study of phenylmethane from ¡3-benzpinacolin, from benz oarf? -0* some Grignard reagents in ether-hydro- pinacone. It is suggested that a complex is primarily eth 0n u 1XturCS an<^ *n varying concentrations of formed in which the chromium has the co-ordination er. Hydrocarbons have in general a retarding number 6. The reducing action observed on decom o L 866 BRITISH CHEMICAL ABSTRACTS.— A. position with water may be attributed to either acid being positively catalysed according to the reduced chromium or reduced magnesium. conditions employed, although in a few instances, R . B r i g h t m a n . such as the nitration of salicylic acid, and the nitration Action of magnesium organo-derivatives on of hydrocarbons in presence of small concentrations of JV-diethylformamide. N. M a x im (Bull. Soc. chim., mercury salts, the effect is a negative one. Increase 1927, [iv], 4 1 , 809— 813).— Magnesium ethyl bromide of oxidation does not take place at the expense of or iodide and JV-diethylformamide in ethereal solution nitration, since a larger proportion of the organic afford exclusively y-diethylaminopentane, b. p. 143°/ compound undergoes reaction, but if the temperature 760 mm. (picrate, m. p. 84°) (cf. Viguier, A., 1912, i, 7). be carefully controlled direct oxidation is in every With magnesium tsobutyl bromide, however, the case little more than occurs in absence of mercury. reaction affords in addition to about 22% of 8-diethyl- As with ethylene and acetylene, there is a tend amino-$r\-dimethylheptane, b. p. 95°/19 mm., 206°/ ency, particularly with hydrocarbons, to form nitro- 760 mm. (picrate, m. p. 89—90°), about 29% of iso- hydroxy-compounds (cf. this vol., 643) and the valeraldehyde, the reaction thus partlv pursuing the evidence supports the view that nitration proceeds by' course, H-CONEt2+RMgX — ^ R-CHO+NHEt2, preliminary addition of nitric acid to the aromatic observed by Bouveault (A., 1905, i, 116) and by nucleus (cf. Meisenheimer, A., 1901, i, 135; Straus and Houben and Doescher (A., 1908, i, 27). Ekhard, A., 1925, i, 1138). The increase (per cent.) of R. B r ig h t m a n . total nitration obtained by the addition of 0-1—0-5% Course of the Leuckart xanthate reaction of mercuric nitrate is, with xylene 0-8, naphthalene [ethyl- and methyl-sulphonylbenzene-2 : 4-di- —2-7 to —6-8, phenanthrene 13-1, hromobenzene sulphonyl chlorides]. J. Pollak, K. Deutscher, 2-56—3-99, phenol 21-7—25-0, chlorophenol 3-1— and ( F r l . ) M. K r a u s s (Monatsh., 1927, 48, 103—111; 6-25, o-cresol 18-6— 19-1, naphthol 10-7—11-4, benz- cf. Hurtley and Smiles, A., 1926, 948).—In attempting aldeliyde 8-3—9-6, jp-hydroxybenzaldehyde 18-1— the preparation of benzene as-trisulphonic acid by 22-2. With anthracene, oxidation and mononitration treating diazotised anilinedisulphonic acid with are decreased, dinitration being increased. potassium xanthate, it was found that whilst oxid W. J. P o w e l l . ation of the product by nitric acid gives apparently Optical identification of the naphthalene- the desired acid, oxidation by potassium perman sulphonic acids by means of their benzyl-ii- ganate gives rise to a sulphone, owing to decomposition thiocarbamide salts. R. M. H a n n and G. L. of the xanthate derivative to give an alkylthiol K e e n a n (J. Physical Chem., 1927, 31,1082—1090).— derivative. When nitric acid is used and the product Optical data on the benzyl-t/r-thiocarbamide salts of is treated with phosphorus pentachloride, there is a-, fi-, 1 : 5-, 2 : 6-, 2 : 7-, and 1 : 6-naphthalene-mono- obtained, not benzenetrisulphonyl chloride, but and -di-sulphonic acids are given in a form suitable for l-chlorobenzene-2 : 4-disulphonyl chloride, sulphur rapid identification by microscopical observation. dioxide being lost. L. S. T h e o b a l d . When potassium permanganate is used, the product [Mechanism of the formation of diphenyl from of chlorination is ethylsidphonylbenzene-2 :4 -disul- benzene.] O. F u c h s (Ber., 1927, 60, [5], 1663).— plionyl chloride, m. p. 162-5— 163°. This is identical The arrangement of Pyl’s main a n d control experi with a specimen prepared by sulphonating thio- ments are not sufficiently similar to justify the con phenetole to a mixture of thiophenelole mono- and di- clusion which he has reached (cf. this vol., 654). sulphonic acids (thiophenelole-2 : 4-disulphonyl chloride, H. W r e n . m. p. 72—73-5°, prepared), and treating the mixed Hydrogenation under pressure of tetraphenyl- potassium salts with potassium permanganate, where methane and p-hydroxytetraphenylmethane. by ethylsulphonylbenzene-mono- and -di-sulphonic acids V. N. Ipatiev and B. N. D olgov (Compt. rend-, (potassium salts) are obtained, and finally chlorinating 1 9 2 7, 185, 2 1 0 — 2 1 2 ).— Tetraphenylmethane, when the latter. hydrogenated at 275— 285°/80— 100 atm. using a By similarly treating thioanisole, methylsulphonyl- nickel oxide catalyst, yields tricycZohexylmethane an benzene-2 : 4-disulphonyl chloride, m. p. 154— 156°, is dicT/ctohexylmethane. _p-Hydroxytetraphcnylmetnaiie, obtained. The hydrolysis of these two acid chlorides similarly treated, yields cycfohexanol, dicj/ciohexj requires 5 mols. of potassium hydroxide : the sulphone methane, and phenyldicycZohexylmethane. group is thus apparently hydrolysed. B. W. A ndebson. E. W. W ignall. Dehydrogenations and hydrogenations cata Action of aqua regia on fluorene. E. B l u m e n - lysed by metallic oxides. P. S a b a t i e r and - • stock-Halward (Monatsh., 1927, 48, 99— 101).— Fernandez (Compt. rend., 1927, 185, 241—- )• From the product of the prolonged action of aqua It has been found (cf. Sabatier, this vol., 73/) regia on fluorene (cf. Datta, A., 1916, i, 715) some metallic oxides dehydrogenate primary alcoho s p-dichlorofluorenone (Goldschmiedt, A., 1896, i, 174) aldehydes, as well as dehydrating them to uVsa,urf. is isolated. E. W. W ignall. hydrocarbons. • Manganous oxide has no dehyclra i g, but a slight dehydrogenating action, which is a i ESect of mercury salts in the nitration of greater with zinc oxide; alumina has scarce y j aromatic systems. P. V. McKie (J.S.C.I., 1 9 27, dehydrogenating action. Piperidine, stable in a g 46, 2 61—2 6 2 t ).—In the nitration of aromatic com tube at 600°, is converted by manganous oxi pounds by various methods the effect of small this temperature into pyridine and dipvriay , quantities of mercuric nitrate may be considerable, hydrogen being evolved. either the nitrating or the oxidising function of the Nitrobenzene vapour passed with hydrogen ORGANIC CHEMISTRY. 867 heated manganous oxide is reduced slowly at 300°, A., 1920, i, 303). Aniline-2 : 4 : Q-trisulphonamide, rapidly at 600°, to aniline, with diphenylamine, tri- m. p. 291°, and -trisulphonanilide, m. p. 240—241°, were phenylamine, water, ammonia, and some benzene and prepared. The acid chloride is obtained in only small carbon dioxide Zinc oxide gives similar results (cf. its yield if sodium chloride is absent (the free acid then catalysis of the reduction of carbon dioxide at high being formed). It is also obtained when acetanilide, pressures to methyl alcohol); without a catalyst the or aniline-mono- or -di-sulphonic acid is employed : reaction is slight. these substances do not give the blue impurity obtained Zinc oxide is more active than manganous oxide in when aniline is used. catalysing the reduction of ¿sovaleronitrile to di- and p-Toluidine gives similarly its 3 : 5-disulphonyl tri-isoamylamines, and that of isobutyronitrile to the chloride, yellow, m. p. 156°, disulphotiamide, m. p. corresponding primary and secondary amines. Hexo- 257°, disulphonanilide, m. p. 192°; m-phenylene- nitrile is reduced by either oxide at 500° to dihexyl- diamine gives its 4 : 6-disulphonyl chloride, m. p. 274— amine, with mono- and tri-hexylamines. 275° (after sintering), which turns reddish-violet in Manganous oxide does not reduce satisfactorily sunlight, disulphonamide, m. p. 187°, disulphon ethylene or acetone derivatives. E. W . W i g n a l l . anilide, m. p. 236°; ^-phenylenediamine, however, Diacylamides. III. Formation of amidines. gives its tetrachloro-derivative. K. Brunner, (Frl.) M. M atzler, and V. M o s s m e r Sodium acetylanthranilate heated with sodium (Monatsh., 1927, 48, 125— 131; cf. A., 1924, i, 1310). chlorosulphonate for 3 hrs. at 200° gives 4-keto- —Diacetamide, when heated at 150— 160° with aniline 3-o-carboxyphenyl-2-methyldihydroquinazoline, hydrochloride, gives mainly acetanilide, but also some NN' - dipli&nylacetamidine, NPhlCMe-NHPh, m. p. G^ Carbylamines. XVI. Reactions with hydr- ment of diphenylmethylamine hydrochloride in oxylamine hydrochloride. M. P a s s e r i n i (Gaz- absolute alcohol with sodium ethoxide (3 mols.) and zetta, 1927, 57, 452— 456).—The reaction of carbyl- bromine (1 mol.), with subsequent acidification, amines with hydroxylamine hydrochloride varies with affords benzophenone in 66% yield, presumably the solvent. In alcohol, phenylearbylamine gives through the corresponding imine, formed by elimin anilinoformaldoxime (Nef, A., 1895, i, 11); it is ation of hydrogen bromide from the iV-bromoamine. suggested that diphenylformamidine is first produced, Treatment of diphenylmethylamine hydrochloride since this substance is the product in acetone solution, with aqueous sodium hypochlorite yields i\-chloro- which removes excess of hydroxylamine. Alcoholic diphenylmethylamine, which is converted by absolute- potassium hydroxide converts anilinoformaldoxime alcoholic sodium ethoxide into benzophenoneimine. into phenylcyanamide. y-Carbylaminoazobenzene in E. G. W i l l s o n . acetone solution yields largely di-p-benzeneazodipfienyl- Arylamine salts of naphthalenesulphonic formamidifte, NPh:N-C6H4-N:CH*NH-C6H4-N:NPh, acids. IV. Arylamine salts of a-naphthol-4- in. p. 196—197°; if the crude product is hydrolysed by sulphonic acid, acetylation of naphthionic acid, alcoholic potassium hydroxide, p-aminoazobenzene is and arylamine salts of acetylnaphthionic acid. obtained, with a substance probably p-cyanamidoazo- R. B. F o r s t e r and R. W a t s o n (J.S.C.I., 1927, 46, benzene, m. p. 163° (cf. Pierron, A., 1906, i, 772), since 224—226t).—The following salts of a-naphthol-4- when boiled with hydrochloric acid it is converted into sulphonic acid have been prepared, and their 2>-carbamidoazobenzene; jj-formamidoazobenzene is solubilities in 100 parts of 1% acetic acid (S) deter also produced. E. W. W i g n a l l . mined : (a) from 1 mol. each of acid and base, aniline, m. p. 186— 187°, S at 15° 5-38; o-toluidine, m. p. Positive halogens attached to carbon in the 203—204°, S at 20° 1-66; p-toluidine, m. p. 196°, S at aromatic series. IV. Selectivity of halogen 15° 0-6S; m-xylidine, m. p. 228—229°, S at 12° 0-23; removal. B. H. N i c o l e t and R. B. S a n d i n (J. ¡¡/-cumidine, m. p. 227—228°, S at 17° 0-216; a-mph- Amer. Chem. Soc., 1927, 49, 1806— 1810; cf. this vol., thylamine, m. p. 216—217°, S at 19° 0-18; $-naphthyl- 869).—In support of the theory which predicts that amine, begins to decompose at 270°, S at 18° 0-053; halogen atoms ortho or para to an amino-group should p-chloroaniline, m. p. 184— 185°, S at 15° 0-53j exhibit “ positive ” properties, it has been found that p-nitro-o-toluidine, m. p. 249° (decomp.), S at 18° o-iodo-p-toluidine remains unaffected under conditions 0-28; o-anisidine, m. p. 202—203°, S at 17° 1-37; which result in the ready replacement of iodine by p-anisidine, m. p. 224°, S at 16° 0-45; (b) from 2 hydrogen in the hydrolysis of »i-iodo-^-toluidine. mols. of acid and 1 mol. of diamine, benzidine, begins Treatment of o-iodo-jp-toluidine in ether with iodine, to decompose at 310°, S at 14° 0-17; tolidine, m. p. calcium carbonate, and water affords 2 : 5-di-iodo-p- 214—215°, S at 16° 0-12; dianisidine, m. p. 207— toluidine, m. p. 110° (acetyl derivative, m. p. 193°), 209°, S at 18° 0-25. Naphthionic acid does not yield which is reconverted into o-iodo-p-toluidine by arylamine salts, owing possibly to inner salt formation aqueous 10% hydrochloric acid. Bromination of between the ammo- and sulphonic groups of the acia. o-iodo-p-acetotoluidide with bromine in glacial acetic On acetylation, however, this inhibiting influence is acid yields 5-bromo-2-iodoacet--p-toluidide, m. p. 165— removed and acetylnaphthionic acid (cf. Schroeter, 166°, from which 5-bromo-2-iodo-p-loluidine, m. p. A., 1906, i, 415), which is prepared in 95% yield by 86— 87°, is obtained on hydrolysis with aqueous 20% boiling the acid with acetic anhydride in presence oi hydrochloric acid. Bromination of o-iodo-^-tolu- pyridine, yields the following salts: aniline, m. p. idine in glacial acetic acid affords 3 : 5-dibromo-2- 231—232°, S at 14° 3-0; o-toluidine, m. p. 260—261, iodo-p-toluidine, m. p. 109° (acetyl derivative, m. p. S at 16° 0-28; p-toluidine, m. p. 232—233°, 1927, 49, 1796— 1801; cf. A., 1922, i, 121).—Treat and negative halogens. B. H. N i c o l e t (J. Amer. ment of resorcinol in aqueous 20% hydrochloric acid Chem. Soc., 1927, 49, 1810— 1814; cf. this vol., 868, with iodine monochloride (2 mols.) affords 4 : 6-di- and preceding abstract).—The theory of alternating iodoresorcinol, m. p. 145° (dibenzoyl derivative, m. p. polarities predicts correctly'the respective negative and 195—200°). A-Iodo-3-hydroxyphenyl benzoate, decomp. positive natures of the halogen atoms in 1-chloro- 153—155°, is obtained from monobenzoylresorcinol 2 : 4-dinitrobenzene and l-iodo-3 : 5-diaminobenzene. and iodine chloride in glacial acetic acid, whilst Accordingly, the halogen atom of l-chloro-3 : 5-di 5-iodo-2 : i-dihydroxy benzoic acid, m. p. 172°, is aminobenzene and l-iodo-3 : 5-dinitrobenzene should obtained similarly from resorcylic acid in ether. also exhibit negative and positive characteristics, 3:5 -Di- iodo - 2 : 4 - dihydroxybenzoic acid, decomp. respectively. It has now been found, however, that 193—196°, is obtained by treatment of resorcylic neither of these compounds can be dehalogenated, acid in ether with iodine and litharge, whilst i-chloro- i.e., that their halogen atoms show no indications of Q-iodo-m-plienylenediamine is obtained similarly from polar characteristics. It is therefore concluded that 4 - chloro - m - phenylenediamine in methyl alcohol. the possibility of reactionis conditioned by factors other A-Iododiacetyl-m-phenylenediamine, decomp. 175— than polar structure, and it is suggested that the 180°, is obtained by treating ??i-aminoacetanilide in removal of halogen from the o- or p-derivatives takes aqueous 20% hydrochloric acid with iodine, with place through the intermediate formation of a subsequent acetylation. 4 : 6-Di-iodo-m-aminoacet- quinonoid derivative, e.g., according to the scheme anilide, m. p. 172— 174°, is obtained by treating :c (Nh 2)-c i: — ^ :c (Nh 3ci)-c i: — ^ -c (:n h 2ci)-c h i- m-aminoacetanilide with iodine chloride in warm — >- •C(NH2):CH-+C1I. l-Iodo-'i : 5-dinitrobenzene, aqueous 10% hydrochloric acid. All the above yellow, m. p. 99°, was prepared from 3 : 5-dinitro- derivatives, as well as 4-iodoresorcinol, 4-iodo-m- aniline. On reduction and subsequent acetydation it phenylenediamine, 4 : 6-di-iodo-m-phenylenediamine, yields l-iodo-3 : 5-diacetamidobenzene, m. p. 291°. 2-iodo-^-phenylenediamine, and 3-iodo-p-toluidine, F . G. W i l l s o n . are hydrolysed with replacement of iodine by hydrogen Benzidine monohydrate. M. p. of benzidine. ■when treated with aqueous 10% hydrochloric acid R. J. W. L e F e v r e and E. E. T u r n e r (J.S.C.I., and stannous chloride in glacial acetic acid at 100°. 1 9 27, 46, 209 — 2 1 0 t ).—Benzidine forms a mono The results obtained are in accordance with pre hydrate, m. p. 104— 1 0 5 ° (with effervescence) when dictions based on the theory of induced alternate taken very rapidly. The transition temperature polarities (cf. Lapworth and Shoesmith, J.C.S., 1922, benzidine hydrate zzZ water+benzidine is at about 121,1391). F. G. W i l l s o n . 7 1 °. Benzidine separates anhydrous from aqueous solutions at temperatures above 8 0 ° and hydrated at Positive halogens attached to carbon in the temperatures below 6 0 °. The commonly accepted aromatic series. III. Derivatives of p-phenyl- m. p. of 122° for benzidine is shown to be traceable to enediamine, ^-nitroanilinę, and mesitylene. the use, hi error, of partly hydrated specimens. B. H. N i c o l e t and W. L. R a y (J. Amer. Chem. Soc„ 1927, 49, 1801— 1806; cf. this vol., 868).— Stereochemistry of aromatic compounds. III. Iodomesitylcne is converted into mesitylene, indic Condensation of aromatic diamines with dicarb- ating the positive nature of the halogen atom, when oxylic anhydrides. R. K u h n , P. J a c o b , and M. heated with hydrogen chloride in glacial acetic acid at F u r t e r (Annalen, 1927, 455, 254—271).—In agree 135—150°, or with acetic acid, hydrochloric acid, and ment with the results of Le Fevre and Turner (A., stannous chloride at the same temperature. Iodo- 1926, 1131), monophthalylbenzidine [hydrochloride, benzene is unaffected by hydrogen chloride in glacial decomp. 310°; acetyl derivative, m. p. 332° (all m. p. acetic acid at 150°. 2-Iodo-'p-phenylenediamine, m. p. corr.); benzylidene derivative, m. p. 339°], mono- 110-5° (diacetyl derivative, m. p. 211-5°; dibenzoyl phthalyldi-o-anisidine, m. p. 221° (Kaufler and BoreJ, derivative, m. p. 254°), obtained by reduction of A., 1907, i, 794, 795) [hydrochloride, m. p. 278° 2-iodo-4-nitroaniline with stannous chloride, is con (deoomp.); benzylidene derivative, m. p. 200°; acetyl verted into p-phenylenediamine when boiled with derivative, m. p. 298°], and monophthalyl-2:7- aqueous 10% hydrochloric acid, or with glacial iicetic naphthylenediamine, m. p. 249° (acetyl derivative, acid and hydrochloric acid, or when heated with m. p. 306°; benzylidene derivative, m. p. 150°), are concentrated hydrochloric acid at 105°. In the last shown to possess free amino-groups. They cannot, wo cases, 2 : 6-di-iodo-4 -nitroanilinę is formed. therefore, have a cyclic structure. 2 : 7-Diphthal- 2-Iodo-p-phenylencdiamine is deiodinated similarly imidonaphthalene, m. p. 314°, exists in yellow and by hydrochloric acid in presence of stannous chloride, colourless forms. Attempts to prepare a cyclic but much less rapidly than o-iodoaniline. 2-Bromo- compound from AriST'-dim ethylbenzidine (Willstatter y-phe,nyk)wliamine, m. p. 76° (diacetyl derivative, and Kalb, A., 1904, i, 1050) (dihydrochloride, m. p. p. 200°), obtained by reduction of 2-bromo- 249°; diacetyl derivative, m. p. 242°) and phthalic 4-mtroaniline, is debrominated more slowly than the anhydride at 160° gave a monophthalyl derivative, corresponding iodo-derivative. Reduction of 2-bromo- m. p. 276°. Since, however, this contains a free -nitroacetanilide affords ‘i-bromo-A-aminoacetanilide, imino-group and gives an acetyl derivative, m. p. 216°, m . P- 123°. Bromination of 3-bromo-4-aminoacet- which is hydrolysed by alcoholic potassium hydroxide anmde in glacial acetic acid yields 2:3: 5-tribromo- to aphthalamic acid, CMU22iN204,m.p. 253°,it has prob 4-anmmcetanilide, m. p. 207°. F. G. W i l l s o n . ably the structure, NHMe-CjH4-C6H4-N surprising. The above phthalyl derivatives give solutions, the reaction being pseudo-unimolecular characteristic colour reactions with sulphuric and and very sensitive to the hydroxyl-ion concentration. chromic acids. Monosuccinyl-NN'-dimethylbenzidine, The value of k in this case is 6-13 X103. 2 : 6-Dibromo- m. p. 269°, gives an acetyl derivative, m. p. 292°. benzoquinoneoxime is probably the primary product NN'-Dimethylphthaldianilide has m. p. 186-5°. NN’- of the reaction. This substance has a solubility in Dimethylbenzidme and carbonyl chloride in tolueno water 8-5 X 10~^M at 20°, and its absorption spectrum, give an amorphous 'product, ( ?)(C15H14ON2)4. A together with that of the chloroimide, is given. monophthalyl derivative of pp'-diaminodiphenyl- L. S. T h e o b a l d . methane could not be prepared. The latter gives - [Nuclear condensation of phenols with with p-toluenesulphonyl chloride in hot aqueous nitriles.] J. H o u b e n (Ber., 1927, 60, [B], 1554).— suspension, pp' -di- p - toluenesulplionamidodiphenyl - A reply to Hoesch (this vol., 353). H . W r e n . methane, m. p. 164°, which is converted by methyl Nature of the alternating effect in carbon sulphate and alkali followed by hydrolysis into oily chains. XX. Conditions underlying vicinal W'-dimethyldiaminodiphenylmethane (dinitroso-deriv- substitution in o-substituted benzenes con ative, m. p. 99°). This condenses with phthalic taining op-orienting groups. C. K. I n g o l d and anhydride at 190° to a diphthalyl derivative, m. p. E. W. S m it h (J.C.S., 1927, 1690— 1695; cf A., 1926, 221° (indef.). Thus, even under favourable conditions 831, 833, 947).—Nitration of o-chloro-, o-bromo-, and formation of cyclic derivatives of the Kaufler type o-iodo-anisolc shows that the proportion of vicinal does not take place; this is, however, not regarded as substitution of an o-disubstituted benzene containing evidence against a similar formula for benzidine op-orienting substituents increases with increasing derivatives since o-phenylenediamine also fails to disparity between the directive powers of the groups. give a cyclic phthalyl derivative. The proportion of 6-isomeride formed in the nitration H. E. F . N o t t o n . of different o-derivatives of anisole is : o-fluoro-, 66%; Caoutchouc and guttapercha. II. Disazo- o-chloro-, 56%; o-bromo-, 52%; o-iodo-, <38%; compounds from dihydroxy- and tetrahydroxy- o-methoxy-, 0%. M. C la rk . diphenyldihydrocaoutchouc. E. G e i g e r (Helv. Chim. Acta, 1927, 10, 539—543; see below). Caoutchouc and guttapercha. I. Condens — 4 : 4' - Dihydroxydiphenyldihydrocaoutchouc is ation of caoutchouc and guttapercha dihromides coupled with diazobenzene to give a dye, m. p. 205— with phenols and phenol ethers. E. G e ig e r 210° (decomp.); with p-nitrodiazobenzene giving a (Helv. Chim. Acta, 1927,10, 530—538; cf. Weber, A., dye, m. p. 260—270°; with diazotised naphthionic 1900, i, 353; Fisher, Gray, and McColm, A., 1926, acid and sulphanilic acid, and with tetrazotised 730).—Caoutchouc dibromide when heated at 90—120° benzidine. The analogue of diamine-green-B, p- with ferric chloride and excess of phenol gives 4:4'- dihydroxydiphenyldihydrocaoutchouc (dibenzoate, nitroaniline— >- H-acid -<— benzidine— -> dihydroxy- diphenyldihydrocaoutchouc, is bluer than the phenol m. p. 195— 200°). Similar compounds are obtained (para) coupling. p-Nitrodiazobenzene (2 mols.) from o-cresol (m. p. 165— 178°; dibenzoate, m. p. couples with 2 : 2 ': 4 : 4'-tetrahydroxydiphenyldi- 190—195°), to- and p-cresols, resorcinol (not melted hydrocaoutchouc to give a dye, m. p. 210—215° at 300°; tetrabenzoate, m. p. 240—245°), pyrogallol (decomp.). The products áre truly colloidal dyes, and (hexabenzoate prepared), anisole (m. p. 150 160 , coupling is about as rapid as with p-cresol. cf. Fisher, Gray, and McColm, loc. cit.), and phenetole (m. p. 210—215°). Guttapercha dibromide also C. H o l l i n s . Phenol tests. Velocity of indophenol form condenses with phenol, m-cresol, and resorcinol, giving hydroxylated didryldihydroguttaperchas, melt ation. H. D. G i b b s (J. Physical Chem., 1927, 31, 1053—1081).—The reaction between 2 : 6-dibromo- ing, respectively, at 170— 175° (dibenzoate, m. p. benzoqumone-4-chloroiinide and phenol, producing 190— 195°), 150— 160° (dibenzoate, m. p. 175—18»), 2 : 6-dibromobenzenoneindophenol, has been studied and above 300° [tetrabenzoate, m. p. 195—-W (decomp.)]. C. H o llin s . quantitatively at various pn values in the alkaline region, the velocity of reaction being measured by a Monothioethylene glycol. III. Nitrophenyl spectrophotometric method. In buffered solutions thioethers. G. M. Bennett and W. A. Berk\ containing an excess of phenol, the reaction is pseudo- (J.C.S., 1927, 1666— 1676).—The following were unimolecular and can be expressed by an equation prepared by reaction of ethylenechlorohvdrin wi of the type k = 2-3026 log [a¡(a—x)]/tbcc, where a, t h e potassium salts of 0 -, m-, and p-nitrothiopheno , b, and a are the molar concentrations of 2 : 6-dibromo- respectively : o-nitrophenyl $-hydroxyethyl siUp}\ e> benzoquinonechloroimide, phenol, and phenoxide, m. p. 100°; m-nitrophenyl $-hydroxyethyl sulp 1 respectively. When the concentrations of phenol m. p. 42-5° (-p-nitrobenzoyl derivative, ni. p. and imide are nearly equal, the same value of k and p-nitrophenyl fi-hydroxyethyl sulphide, m. p- is obtained from an equation for a reaction of the (lit. 59°). p-Nitrobenzyl ^-hydroxyethyl sutpnm, second order. At 20°, k is 1-63 X104. The production m. p. 37-5°, and p-nitrophenyl y-hydroxypropij su of the blue colour given by the indophenol in alkaline phide, m. p. 41-5°, were prepared by «nal°g°” _ solution is a very delicate test for phenol, and the methods. The following are also described. velocity of reaction has been measured at concentra nitrophenyl $-chloroetliyl sulphoxide, in . p - 84 , J tions below the limits of many usual tests, fair results nitrophenyl $-chloroethyl sulphide, m . p . 62° (sulpnox 1 , being obtained at a dilution of 1 part in two million. m . p . 80° ) ; m-nitrophenyl p-chloroethyl sulphide, m -p - The temperature coefficient of the reaction is con 31°; p-nitrobenzyl fi-chloroethyl sulphide, m. p- siderable. The chloroimide decomposes in alkaline 47°; p-nitrophenyl y-chloropropyl sulphide, m. P- ORGAN 10 CHEMISTRY. 871 50°; o-nitraphenyl $-bromoethyl sulphide, m. p. 63° 1912, 101, 958; Sachs and Mosebaeh, A., 1910, i, (sulphozide, m. p. 112°); p-nitrophenyl $-bromoethyl 726), with sulphuric acid (d 1-84) at 70° affords a sulphoxide, m. p. 100°; m-nitrophenyl fi-bromoethyl sulphonic acid (chloride, m. p. 140—141°; amide, sulphide, ra. p. 32°; o-nitrophenyl {i-iodoethyl sulphide, m. p. 235—236°). Nitration with nitric acid (d 1-47— m. p. 64°; p-nitrophenyl fi-iodoethyl sulphide, m. p. 1-48) at 15—20° affords 3-chloro-4-nitroacenaphthene, 67°; di-m-nitrodiphenylthiolcyc\obutane (?), m. p. m. p. 136—138° (Farnell, J.C.S., 1923, 123, 60), 136°. Crystallographic data are given for the o- from which 3-chloroA-hydroxyacenaphthene, m. p. nitro-hydroxy-, -chloro-, -bromo-, and -iodo-sulphides 123°, is obtained through the amino-compound. and the 2>nitrochloro-, p-nitrobromo-, and p-nitro- 3-Chloro-i-hydroxy-5-benzencazoacenaphthene, red, has iodo-sulphides. M. C l a r k . m. p. 175—176°. Oxidation of 3-chloroacenaphthene with sodium dichromate in acetic acid at 40—50° Influence of the sulphur atom on the reactivity affords 3 : 3'-dichlorobisacenaphthenedione (I), m. p. of adjacent atoms or groups. II. Comparative 324—325° ; at 105— 120°, Z-chloroace?mphthenequinone reactivities of chlorine in some ¡3- and y-chloro- sulphides. G. M. B e n n e t t and W. A. B e r r y (J.C.S., 1927, 1676—1684).—Certain chlorosulphides, including o-, m-, and p-nitrophcnyl p-chloroethyl sulphides, p-nitrobenzyl (3-chloroethyl sulphide, p- nitrophenyl y-chloropropyl sulphide and the unsub stituted phenyl (3-chloroethyl and phenyl y-chloro propyl sulphides, have been compared as to their velocities of reaction with water in alcoholic solution at 75° and with potassium iodide hi acetone solution at 55°. The order in which the substances are arranged with respect to the hydrolysis is the opposite of that m. p. 212—213°, is obtained, whilst excess of indicated by the reaction with potassium iodide. sodium dichromate affords 4-chloronaphthalic This contrast, and the results of Conant, Kirner, anhydride, m. p. 216—217°. With nitric acid (d 1-52) and Hussey (A., 1925, i, 494) and of Olivier (A., 1923, in sulphuric acid this affords a ¿imiro-derivative, i, 197), are all accounted for in accordance with the in. p. 192— 193° ; and with resorcinol 5-chloronaphthal- electronic theory of valency on the assumption that jluorescein (II), orange-red, giving a strong green a positive charge on the chlorine atom facilitates the fluorescence in alkaline solution. reaction with potassium iodide, the first and character 4-Chloronaphthimide, m. p. 301—302°, and methyl istic stage of the reaction being the formation of a 4-chloronaphthalate, m. p. 91—93°, are also described. complex between the chloro-compound and the iodide On fusion with sodium hydroxide at 220—230°, ion. The hydrolytic reaction, on the other hand, is 4-chloronaphthalic anhydride affords 3-hydroxy- accelerated by a negative charge on the chlorine naphthalic anhydride, m. p. 280°. 4-HydroxyA- atom (Oxford and Robinson, A., 1926, 397). More benzeneazonaphthalic anhydride, bronze-yellow, has over, on this assumption, the results of this comparison m. p. 261°. R. B r ig h t m a n . are in agreement with one of the authors’ previous Isomeric transformations of cyclic compounds conclusions (this vol., 355). The following are under the influence of catalysts. II. Dehydr described: phenyl y-chloropropyl sulphide, b. p. ation of the alcohols CfH10O ; decomposition of 137°/13 mm.; o-nitrophenyl (i-piperidinoclhyl sulphide, the alcohols C4H80 with aluminium oxide as m- p. 45°; p-nitrophenyl $-piperidinoethyl sulphide, catalyst. M. D o j a r e n k o (Ber., 1927, 60, [.B], m- P- 52°. M. C l a r k . 1536—1553).—Methylcp/cZobutanol is converted by Synthesis of safrole and o-safrole. W. H. passage over heated aluminium oxide mainly into isoprene accompanied by small amounts of ¡3-methyl- Pe r k in , jun., and V. M. T r i k o j c s (J.C.S., 1927, 1663—1666).—When, the monoallyl ether of pyro- A^-butene, cymene, and caoutchouc-like polymerides ; catechol is heated at 170— 180°, it undergoes the gaseous hydrocarbons are also evolved. At 370— Claisen rearrangement, yielding a mixture of 1:2- 375° the amount of volatile hydrocarbons is consider dihjdroxy-Z-allylbenzene, m. p. 28°, b. p. 143-5— able, but diminishes at 400° owing to production of 145 /15 mm. (dibenzoyl derivative, m. p. 60—61°), larger quantities of polymerides. o/c/oButylcarbinol is similarly isomerised, cj/cZopentene being formed in uwr *' 2‘^ y <^roxy'4-allylbenzene (cf. Kawai, A., J-G, 609). These substances are converted respect- more than 75% yield. Methylci/ciopropylcarbinol yields mainly piperylene accompanied by small 1 ,y by treatment with methylene iodide and amounts of divinylmethane. ' Enlargement of the ring anhydrous potassium carbonate in dry acetone solution with production of methylcycZobutene is a very mto o-safMe, b. p. 102-5— 103°/13 mm. and 226— subsidiary process. Propylene is formed in about -w /762^mm., 1-5359 (pentabromo-derivative, 2-5% yield at 350—360°. The alcohols C4HsO (cyclo- ,P- 1^4°), and safrole, n)l 1-5381 (pcniabromo- propylcarbinol, ci/eZobutanol, and allylcarbinol) behave denvative, m. p. 169°). " M. C l a r k . very similarly towards aluminium oxide, the reaction an^C-tna^ ^ ? ne‘ TV- 3 - Chloroacenaphthene being complex. The initial stage consists in decom 7 * tactions. K. Dziewonski and (Mme.) M. position according to the scheme, C4H80 = i q.>7 ze'vsk a-Barano wska (Bull. Acad. Polonaise, CH3'CH:CH2-fH 20+ C , in which formaldehyde is ’ "■*■> A, 65—79).—3 - Chloroacenaphthene, not a primary product. Isomérisation, C4H80 = P- 69-/0° (cf. Crompton and Walker, J.C.S., H20+C H 2:CH-CH:CH2, takes place to a very limited 872 BRITISH CHEMICAL ABSTRACTS.— A. extent (3% in the case of allylcarbinol and not more steryl benzoate; the anisate, m. p. 147— 148°, giving than 7-5% with cÿcfobutanol and cyc/opropylcarbinol). an orange-coloured, cloudy liquid with a violet fluores The change, C4Hs0 = C 4H60+ H 2, leads to normal cence, clearing at 210—215°, indicated a molecular products with cycZobutanol and allylcarbinol, whereas formula C27H460. ci/ctopropylcarbmol becomes isomerised to cyclo- No explanation is suggested for the change in m. p. butanone and Av-butenaldehyde. The reaction, of phytosterol when purified through the digitonide. C4H80=C H 3-CH:CH2+C 0 + H 2, is of little import E . W . W i g n a l l . ance and the induced hydrogenation (butylene Action of organo-magnesium compounds on formation) is a secondary process, as also is the poly oximino-ketones. Synthesis of some oximino- merisation observed at higher temperatures. alcohols. A. Orekhov and M. Tiffeneau (Bull. The influence of temperature on the course of the Soc. chim., 1927, [iv], 41, 839—S43).—The action of reaction has been most fully investigated with cyclo- Grignard reagents on oximino-ketones of the types propylcarbinol and methylcj/cZopropylcarbinol ; in Ar-CO-CHiNOH, Ar-CO-CAr'(NOH), and other cases the temperature limits were comparatively Ar-C(NOH)-CO-R, affords the corresponding oximino- narrow. In all- instances the relationships are alcohols, from which the amino-alcohols are obtained similar. Rise of temperature causes more complete on reduction. Magnesium phenyl bromide and dehydration, the optimum being 350—400°, when oximinoacetophenone afford, in 75% yield, $-oximino- formation of water is nearly quantitative. Under aoL-diphenylethyl alcohol, m. p. 121°. Similarly, these conditions the maximum yields of volatde magnesium phenyl bromide and fl-benzilmonoxime hydrocarbons are obtained. Further rise of temper afford (3-oximino-aa[3-triphenylethyl alcohol, m. p. ature favours the production of polymerides. The 153— 154°, identical with the oxime of phenylbenzoin formation of gaseous hydrocarbons increases uniformly prepared by Delacre (A., 1S95, i, 485), a reaction with rise in temperature. This reaction is very which indicates that the latter oxime possesses the subsidiary with the alcohols C6H100, but is more same spatial configuration as B-benzilmonoxime. important with the compounds C4H80, from which Magnesium methyl iodide and [3-benzilmonoxime propylene is mainly produced. H. W r e n . afford a-oximino-xfi-diphenylisopropyl alcohol, m. p. 120— 121°. Since this is identical with the reaction Derivatives of cholesterol. S. F r a n k e l and P. product from magnesium phenyl bromide and D o m b a c h e r (Ber., 1927, 60, [B], 1484— 1487).— phenyl oximinobenzyl ketone, it is concluded that During unsuccessful attempts the latter has a spatial configuration corresponding to prepare cholesteryl phos with that of [3-benzilmonoxime (Meisenheimer, A., phates by the action of 1922, i, 152). R. B k ig h tm an . di-CH2Pi'£ cholesterol on phosphoryl chloride,phosphoric anhydride, Dehydration in the trisubstituted secondary- or hydrogen phosphates, or tertiary glycol series (migration of the benzyl by fermentation, hypochol- radical). (M l l e .) J. L e v y and R. L a g r a v e (Bull. esterol, C22H360, m. p. 83°, Soc. chim., 1927, [iv], 41, S33—839).—By dehydr hypocholesteryl etlier, C44H70O, ation with 50% oxalic acid, aay-triphenyl-afi-pro- H H m. p. 178°, and hypocholestene pydene glycol affords 30% of ccap-triphenylpropalde- (I), m. p. 330°, have been isolated. H. W r e n . hyde (oxime, m. p. 91°) and 70% of benzyl diphenyi- methyl ketone (cf. A., 1924, i, 283). The formation Rape oil phytosterol. L. S c h m id and A. of the former product by migration of the benzyl W a s c h k a t j (Monatsh., 1 9 2 7 , 48, 1 3 9 — 1 4 4 ).—Rape group is interpreted as indicating that the migratory oil phytosterol is most probably identical with sito tendency of the benzyl group is equal or superior to sterol. Isolated from rich fractions of rape oil (cf. that of hydrogen. The ketone probably results Windaus, A., 1 90 9, i, 2 2 S ) by extraction with light from the semihydrobenzoin transformation and only petroleum, hydrolysis, and recrystallisation from to a slight extent from isomerisation of the triphenyl- acetone, petroleum, and alcohol, it was acetylated by propaldehyde, the latter change being effected under acetic anhydride and then brominated. Tetrabromo- the influence of concentrated sulphuric «acid. Vinyl brassicasteryl acetate first separated, and was found dehydration without transposition is improbable. to have the same crystalline form and optical pro The fact that triphenydpropaldehyde is not formed perties as tetrabromostigmasteryl acetate. The fil in the dehydration of benzylhydrobenzoin (which trate from bromination when reduced by sodium also yields aay-triphenylpropan-P-onc) supports the amalgam and by zinc dust gave a phytosteryl acetate, view of Orekhov that in this dehydration the second softening 120— 1 2 7 °, m; p. 132— 13 3 ° (corr.), hydro ary hydroxyl and not the tertiary is eliminate!, lysed to phytosterol, softening at 1 36 — 1 3 7 °, m. p. CH2PlrCPh(OH)-CHPh-OH — > CH2Ph-C0-CBPh, 139— 1 4 0 °. This was suspected to be impure, and (cf. A., 1919, i, 205). R- B r ig h tm a n . therefore a digitonide was prepared, from which the liberated sterol had m. p. 13CC— 1 3 7 ° after softening Action of hydrobrom ic acid on diphenyldi- at 1 32 — 1 3 3 ° ; this preparation gave no depression methylbutinenediol. J. S. S a l k i n d and 0 - O ^ t - of m. p. on mixing with sitosterol from wheat-germ, Kina (J. Russ. Phys. Chem. Soc., 1927,59,283—-S i )■ with which it was crystallographically identical. This reaction was investigated to determine why tetra- The acetate thence obtained, m. p. 127— 128° after methydbutinenediol on treatment with hydrobromic softening at 124-5°, was identical with sitosteryl or hydriodic acid gives chiefly CMe^.CX’CA.U e2 acetate from the phytosterol of the calabar bean; (X=halogen), whilst diphenylbutinenediol with ny the benzoate had m. p. 143°, the same as that of sito- bromic acid gives chiefly 3-bromo-2 : 5-dipheny i ORGANIC CHEMISTRY. 873 liydrofuran, although the dibromide was also produced with sulphuric acid gives a mixture of a-ethyl- (A., 1926, 1121). Diphenyldimethylbutinenediol, Ax-cyclopentenylacetic acid, b. p. 138—142°/15 mm., CPhMe(OH)*C:C,CPhMe,OH, does not react with d\ri 1-01909, n\]'i 1-47525 (silver salt; chloride, b. p. an aqueous solution of hydrobromic acid, but reacts 96—98°/20 mm.; amide, m. p. 102—103°; dibromide; readily on warming with a solution of hydrobromic hydrobromide), with less a-ethylcyolopentylideneacetic acid in acetic acid. A small yield of a dibromide, acid, m. p. 80—81° (chloride, 102—106°/16— 18 mm.; m. p. 113°, was isolated, which did not decolorise a amide, m. p. 97°; dibromide-, hydrobromide). The solution of bromine in chloroform. It is not hydro «"-acid is better obtained by dehydration of the lysed at 70° by 25% aqueous potassium hydroxide, hydroxy-acid with acetic anhydride. a-Ethylcyclo- and therefore is probably CPhMe'GBr-CBrlCPhMe. penlylideneacetonitrile, b. p. 116—118°/20 mm., df' The chief product was, however, Z-bromo-2 : 5-di 0-923586, 1-47555, gives on hydrolysis the corre phenyl-2 : 5-dimetliyldihydrofuran, an oil, formed as in sponding ethyl ester, b. p. 116—118°/25 mm., d]9S the case of the diphenylbutinenediol, not by decom 0-936298, «j?5 1-47417. Hydrolysis of this ester position of the dibromide, but by an independent yields a mixture of acids in which the py-acid pre parallel reaction. Diphenyldimethylbutinenediol re dominates. a-Ethyl-A1-C2/cZopentenylacetone after sembles, therefore, the diaryl-substituted rather than equilibration with alcoholic sodium ethoxide gives, the tetra-alkyl-substituted acetylene glycol. in addition to the semicarbazone of m. p. 166— 167° J. K a y e . (Kon and Linstead, A., 1925, i, 633), a second semi Preparation of ti'iarylmethane dyes. British carbazone, m. p. 143—145°. Condensation of the Dyestuffs Corpn., Ltd., E. H. R odd, and F. W. ketone with ethyl sodiomalonate yields after hydro LDiCH.—See B., 1927, 598. lysis a liquid diketone, which, on oxidation with hypo- bromite, gives a-ethylcyclopentane-1 : 1 -diacetic acid Three-carbon system. XII. Effect of positive (silver salt). Ethyl p-hydroxy-p-methyl-a-ethyl- substituents in the a-position on the tautomer- valerate [acid, b. p. 132—136°/20 mm. (silver salt)], ism. G. A. R. K o n and B. T. N a r a y a n a n (J.C.S., yields with phosphorus oxychloride ethyl p-methyl-a- 1927, 1536—1546).—Acids, ketones, and nitriles of ethyl-A^-pentenoate [acid, b. p. 122—126°/20 mm., the general formulae RICEtX, where R is CMeEtl or df'4, 0-95884, nf* 1-45113 (silver salt; chloride, b. p. the ci/ctopentane or q/cfohexane radical and X is 76—78°/18—20 mm.; p-toluidide, m. p. 102—104°)]. •C02H, -COMe, or -CN, have been examined. It is $-Methyl-a.-ethyl-ka-pentenoic acid, b. p. 126—130°/ shown that for acids and ketones, introduction of 15— 18 mm., df* 0-95930, Kb'4 1-45193 (silver salt; the a-ethyl group favours the Py-position for the chloride, b. p. 86—90°/20 mm.; p-toluidide, m. p. double linking and slightly retards the mobility of 112— 113°; hydrobromide), is obtained from p-hydroxy- the system. The nitriles, however, are obtained in P-methyl-a-ethylpentanoic acid and acetic anhydride. the ap-form since they are produced by elimination 8-Methyl-y-ethyl-As-hexen-$-one, b. p. 72—74°/16 mm., of ethyl carbonate from cyano-esters of the type dt ~ 0-85068, Tig1 1-43908 (semicarbazone, m. p. 163— 164°), after equilibration with alcoholic sodium _Cj|>C-CR unsaturated acid. Again, the entry of a m-methyl The following are described : type I, N-phenylbenz- group into the benzoic acid molecule causes a reduc imino m-chlorophenyl ether, m. p. 71°, 2 :4 -dichloro- tion in the dissociation constant, both general and phenyl ether, m. p. 73—74°, 2:4:6-trichlorophenyl ether, alternating effects acting in the same sense. The m. p. 80—81°, o-anisyl ether, m. p. 113°, m-anisyl ether, effect of the entry of this group on the benzoic acid a viscid od, p-anisyl ether, m. p. 79—80°, p-nitro- constant should be 3-3 times as large as its effect on phenyl ether, m. p. 76—77°, a-naphthyl ether, m. p. the constant of hexahydrobenzoic acid; actually the 89°, (3-naphthyl ether, m. p. 127— 128°, p-acetylphenyl methyl group is only 11% more effective in the first ether, m. p. 94—95°; type II, N-o-chlorophenyl-, m. p. case. 65—=66° (prepared from benz-o-chloroanilideimino- Olivier has shown that the effect of the substitu chloride, b. p. 204°/10 mm., and phenol), N-m-chloro- ents in the isomeric dibromobenzyl chlorides on phenyl-, m. p. 66° (from benz-m-chloroanilideimino- the hydrolysis constant varies as the product of chloride, b. p. 211—213°/14 mm.), N--p-chlorophmyl-, the effects of the two substituents taken separately m. p. 110° (from benz-^-chloroanilideiminochloride, (A., 1926, 511). Assuming therefore that the total b. p. 220—224°/20 mm.), N-2 : i-dichlorophenyl, effect of a substituent varies as the product (or m. p. 57—58°, and N-2 : 4 : 6-trichlorophenyl-benz- the quotient if the effects are in opposition) of the iminoplienyl ether, m. p. 88-5°; N-2 : 4 : 6-trichloro- alternating effect, the general effect, and the special phenylbenzimino 2:4: 6-trichloroplienyl ether, m. p. ortho-effect in the case of o-substituents, and, further, 141° (gives on heating benzoyl-2 : 4 : 6 : 2': 4': 6'- that the general effect decreases at the same rate as hexachlorodiphenylamine, m. p. 194—195°); N-p- the alternating effect with the distance of the anisyl-, m. p. 100° (from benz-~p-anisidideiniinochloride, substituent from the affected atom, the relative m. p. 55°, b. p. 269—273°/162— 180 mm. decomp.), influence of the three effects in the case of the sub N-o-nitrophenyl-, m. p. 67—68°, N-a-naphthyl- a viscid stituted benzyl chloride has been calculated for the od, and N-methyl-benzimino phenyl ether, m. p. 30— substituents Cl, Br, I, C02H, N 02, and Me. Similar 31°; type III, 'S-phenyl-o-chloro-, m. p. 100° (from calculations have been carried out for two other o-chlorobenzanilideiminochloride, m. p. 59°, b. p. 235°/ reactions, viz., that between substituted phenols and 60 mm.), N-phenyl-'p-chloro-, m. p. 64—65° (from ethylene oxide (Boyd and Marie, J.C.S., 1914, 105, -p-chlorobenza?iilidei?ninochloride, b. p. 219°/17 mm.), 2117) and the hydrolysis of substituted ethyl -phenyl-2 : 4 : 6-trichloro-, m. p. 94—95°, N-phenyl- benzoates (cf. McCombie and Scarborough, J.C.S., p-methoxy-, m. p. 86—S7° (dimorphous), 'N-phenyl-o- 1915, 107, 155). In all three reactions and for all nitro-, m. p. 141— 142°, and N-phenyl-p-nitro-benz- substituents the general effect is greater than the imino phenyl ether, m. p. 102— 102-5°; and the follow alternating effect, the difference being smallest in ing diphenylamine derivatives : benzoyl-2 : i-dicJdoro- the case of the methyl group (about 30%), and greatest m. p. 109°, benzoyl-2 :4 : 6-trichloro-, m. p. 149°, for the nitro-group (6— 18 times). The general effect benzoyl-o-methoxy-, m. p. 117°, benzoyl-y-mdhoxy-, varies most for the various substituents but the ratio m. p. 121°, benzoyl-o-nitro-, m. p. 134°, benzoyl-p- of the general effects of two given substituents is acetyl-, m. p. 136— 137-5°, o-chlorobenzoyl-, m. p. 142— approximately constant hi the three reactions. The 143°, -p-clilorobenzoyl-, m. p. 138—138-5°, 2:4: 6-tri- temperature coefficients of the three effects in the chlorobenzoyl-, m. p. 118—119°, p-methoxybenzoyl-, case of the substituted benzyl chlorides is small and, m. p. 139— 140°, and p-nitrobenzoyl-diphenylamine, with the exception of the methyl group, negative. m. p. 156— 157°; 2:4: 6-trichlorobenzanilide, m. p. W. J. P o w e l l . 197°. N-Phenylbenzimino-o-acetylplienyl ether, m. p. Imino-aryl ethers. V. Effect of substitution 92—93°, on heating yields 1 : 2-diphenyl-4:-quinolone, on the velocity of molecular rearrangement. m. p. 268°, by intramolecular• transformation and A. W. C h a p m a n (J.C.S., 1927, 1743—1751; cf. A., elimination of water. M. C la b k . 1925, i, 1400).—The velocity of the imino-ether — Si am ide change when the substituted j\r-phenylbenz- Variations in the sweetening power of sac imino phenyl ethers are heated is investigated for the charin and of some of its derivatives. B . O ddo three types of imino-ether (I) NPhiCPh-OR, (II) and Q. M i n g o i a (Gazzetta, 1927, 57, 46o !<-)■ NR:CPh-OPh, (III) NPhlCR-OPh. The following By the action of magnesium methyl iodide on,sac substituent groups in type I are arranged in descending charin, “ C - hydroxy methylsaccharm,’ ^ order of ease of migration : o-nitrophenyl>2 : 4 : 6- triohlorophenyl > p - acetylphenyl >2:4- dichloro- m. p. 110— 111° (dibenzoyl derivative, m. p. 183- phenyl > o-chlorophenyl > m - chlorophenyl>£>- chloro- 184°; hydrochloride, soluble hi water), is preparec ■ phenyl and a- and (3-naphthyl > phenyl and o-anisyl> The 3-ethyl-, m. p. 119— 120° {diacetyl derivative, TO-anisyl > anisyl > methyl. The velocities of obtained by the action of acetyl chloride on migration of a phenyl group for different substituents reaction product of saccharin and magnesium e J attached to the nitrogen atom (type II) are in bromide, m. p. 13S°), 3-propyl-, m. p. 1-4 (r the order : p-anisyl> phenyl >p-chlorophenyl and dibenzoyl derivative), 3-phenyl-, m. p. > ‘ . oc-naphthyl > to- and o-chlorophenyl and 2 : 4-di- 3-benzyl-, m. p. 134°, analogues are similarly prepareu- chlorophenyl> 2 : 4 : 6-trichlorophenyl. For different These substances are all tasteless after heuig rce substituents attached to the carbon atom (type III) from saccharin by washing with sodium liydrox the velocities of migration are in the order : ^-anisyl solution, in which they are insoluble. > phenyl >;p- and o-chlorophenyl>p-nitrophenyl and E . W. W ig n a l l . 2:4: 6-trichlorophenyl. An electronic hypothesis is Reaction between cinnamyl chloride, maS advanced to account for the migration. nesium, and carbon dioxide. H. G ilm a n ORGANIC CHEMISTRY. 875 S. A. H a r r i s (J. Amer. Chem. Soc., 1927, 49, 1825— y-hydroxydithiobenzoate, OH-C6H4-CS2Et, m. p. 57° 1828).—Addition of cinnamyl chloride to an ethereal (or -j-iH20, m. p. 42°), which yields a benzoyl deriv suspension of magnesium through which carbon ative, m. p. 80°, and p-nitrobenzoyl compound, m. p. dioxide is bubbled affords methylatropic acid (cf. 119°, but cannot readily be benzylated. It is hydro Oglialoro, A., 1886, 468), the formation of which lysed by alkali hydroxide to ])-hydroxythiobenzoic probably indicates the rearrangement of magnesium acid, m. p. 208°, hydrogen sulphide, and ethyl sulphide cinnamyl chloride to the isomeride CPh(MgCl)!CHMe, and by hydrochloric acid to ^-hydroxybenzoic acid, and throws doubt on Rupe and Bürgin’s interpretation hydrogen sulphide, and ethyl mercaptan. It is of their results (A., 1910, i, 161). F. G. W i l l s o n . oxidised by hydrogen peroxide to ^-hydroxybenzoic Action of organo - magnesium derivatives acid. Phenetole in this reaction may be replaced on a-trisubstituted primary amides. (M m e .) by a mixture of phenol and ethyl bromide. Phenyl Ramart, (M lle.) L aclötre, and Anagnostopoulos isoamyl ether, p- and oi-bromophenetole do not yield (Compt. rend., 1927, 185, 282—284).—Whereas crystalline products; anisole gives methyl y-hydroxy- mono- and di-substituted acid amides are converted dithiobenzoate, m. p. 61°, in very small yield. Benzene, by organo-magnesium derivatives into ketones, tri ethyl bromide, aluminium chloride, and carbon substituted amides yield mainly the corresponding disulphide give ethyl dithiobenzoate. H. W r e n . nitriles. It is suggested that the amide reacts in the hydroxyimide form; AT-substituted amides do Ring-chain tautomerism in y-aldehydo-acids not react. Dimethylcampholamide, fencholamide, and S-ketoaldehydes. H. M e e r w e i n [with H. diphenylbenzylacetamide, phenylmethylethylacet- B r a k e , W. K o m a n t , and H. M o r s c h e l ] (J. pr. amide, and phenyldiethylacetamide yield exclusively Chem., 1927, [ii], 116, 229—275).—Introduction of nitriles, the last-named amide losing 2 mols. of ethane an a-alkyl group into y-aldehydo-acids greatly favours from each mol. Benzyldimethylacetamide with mag lactone formation; both tautomerides of any one nesium phenyl bromide gives benzyldimethylaceto- acid have not yet been isolated. Methyl y-aldehydo- phenone and benzyldimethylacetonitrile, but with P-phenyl-y-methylbutane-aa-dicarboxylate (I) (A., magnesium ethyl bromide the nitrile only. Dimethyl- 1920, i, 844) is hydrolysed by potassium hydroxide, giving first y - aldehydo - a - carbomethoxy - ¡5 - phenyl - y- ethylacetamide and trimethylacetamide give mainly methylvaleric acid (II), m. p. 114— 119° (decomp.), the ketones, with some nitrile. E. W. W i g n a l l . and then the corresponding dicarboxylic acid ( + H20), Preparation of ßßß-triphenylethylamine. Re m. p. 9S—99° (decomp.), which docs not form a arrangement of ßßß-triphenylpropionhydrox- lactone but is converted by boiling dilute sulphuric amic acid. L. H e l l e r m a n (J. Amer. Chem. Soc., acid into y-aldehydo-fy-phenyl-y-methylvaleric acid (III), 1927, 49, 1735—1742).— ßßß-Triphenylpropionic acid m. p. 108—109° (also -fH 20). This behaves as a (cf. Fosse, A., 1907, i, 764) was converted successively true aldehydo-acid, giving an oxime, m. p. 141-5°, into the chloride, m. p. 132°, and the amide, m. p. and a phenylhydrazone, m. p. 151-5— 152-5°, but with 192°. The latter affords, when treated hi alcoholic methyl alcohol and hydrogen chloride 8-methoxy-$- solution with aqueous sodium hypochlorite, the phenyl-yy-dimethylvalerolactone, b. p. 169-5—170-5°/ NN'-dic/jJoro-derivative, m. p. 116°, which could not 10 mm., df 1-071, nf, 1-4999, is formed. The normal be fully purified. An impure IS-brcmoamide, obtained methyl ester, b. p. 160°/10 mm., df 1-0838, w“ 1-5119, analogously, yielded $$$-triphenylethylamine, m. p. is obtained by heating the ester-acid, (II), at 130— 132° [hydrochloride, m. p. 239—240°; nitrate, decomp. 140°. With cold acetic anhydride the aldehydo-acid 237°; chloroplatinate, m. p. 1S3° (decomp.); benzoyl gives a reactive mixed anhydride, converted by derivative, m. p. 157°; urethane, m. p. 94°], when ammonia into y-aldehydo-$-phenyl-y-methylvaleramidc subjected to rearrangement by the Lengfeld-Stieglitz (-f HaO), m. p. 162°, resolidifying, decomp. 192°, and method (A., 1894, i, 415). Treatment of the above by alcohols into esters. The anhydride is stable, acid chloride with hydroxylamine hydrochloride and even at 220°, but in presence of acetic anhydride it is sodium carbonate affords fififi-triphenylpropionhydr- rapidly transformed through the triacetate into oxamicacid, m. p. lS2-5° (decomp.), the benzoyl deriv 8- acetoxy - ¡3 - phenyl - yy - dhnethylvalerolaclone, m. p. ative of which, m. p. 171-5°, yields, when boiled with 146-5— 147-5°, which regenerates the aldehydo-acid aqueous potassium hydroxide, s-di-$$$-triphenyl- on hydrolysis. The lactone is converted by hydroxyl tihylcarbamide, m, p. 218-5—219-5°. The latter yields amine into a mixture of the oxime (above) and the the above triphenylethylamine on hydrolysis with hydroxamic acid, CHO"CMe2'CHPh*CH2'C(OH).NOH aqueous-alcoholic hydrogen chloride at 150°. The (+ H 20), m. p. 145-5—148°; "and by phenylhydrazine non-production of ßßß-triphenylethylamine by reduc into y-aldehydo-$-phenyl-y-methylvalerphenylhydrazide- tion of triphenylacetonitrile (Biltz, A., 1897, i, 533) is phenylhydrazone, m. p. 186—187°. When the sodio- confirmed. F . G. W i l l s o n . derivative of (I) is heated at 100° with methyl iodide Introduction of the carbethionyl group by methyl y - aldehydo - (3-plienyl - a.y-dvnelhylbut Comparison of the last with the aldehydo-acid (III) 5 : (S-dimethoxybenzhydrazide, m. p. 165°, which gives shows that the former is much the weaker acid and on boiling with acetone and benzaldehyde acetone-2- that its physical properties are not those of a homo- hydroxymethyl - 5 : 6 - dimethoxybenzhydrazone, m. p. logue of the latter. Its chemical behaviour is similar 174°, and benzylidene-2-lujdroxymethyl-5 : 6-dimethoxy- to that of the cyclic derivatives of (III), and it is benzhydrazide, m. p. 155°. Wien meconinehydrazide is therefore regarded as 8-hydroxy-¡3-phenyl -uyy-tri- boiled with acetic anhydride, meconine is regenerated, methylvalerolactone. The corresponding free acid can but at 0° N-acetyl-2-hydroxymethyl-5 : 6-dimethoxybenz- not be isolated. The hydroxylactone is converted hydrazide,m. p. 177°, is obtained. In 3-nitromeconine, by boiling acetic anhydride into its acetate, m. p. m. p. 160° (cf. Anderson, Annalen, 1856, 98, 47), the 123-5°; by hydroxylamine (a) hi alkaline solution mobility of the 6-methoxy-group is considerably into the oxime, m. p. 168°, of y-aldehydo-p-phenyl- increased since it is eliminated by alcoholic hydrazine ay-dimethylvaleric acid; (6) in acetic acid into the hydrate solution, the chief product being 3-nitro-5- oxime-hydroxamic acid, methoxy-Q-hydrazinophthalide, m. p. 220° (decomp.), NOH:CH-CMe2-CHPh-CHMe-C(OH):NOH and a small quantity of a dihydrazide, m. p. 248° (+0-5CHCl3), m. p. 172°; and by phenylhydrazine (decomp.), which does not react with benzaldehyde. into a mixture of the phenylhydrazide (66%), m. p. 3-Nitro-5-methoxy-6-hydrazinophthalide yields ail 166-5— 16S°, and pfienylhydrazone (+H20) (33%), acetone derivative, orange, m. p. 208°, a benzylidene m. p. 176-5—177-5°, of y-aldehydo-p-phenyl-ay-di- derivative, red, m. p. 246°, and an acetyl derivative, metliylvaleric acid. Methyl y-aldehydo-$-phenyl-y- yellow, m. p. 227°. W. J. P o w e l l . methyl-a-ethyUyiitmie-aix-dicarboxylate, m. p. 114—115°, Diphenyl series. VI. Configuration of di prepared similarly to the a-methyl derivative, is phenyl derivatives. F. B e l l and P. H. R o b in s o n hydrolysed by alcoholic potassium hydroxide to (J.C.S., 1927, 1695— 1699).—Partial resolution of S-hydroxy-¡3-phenyl -yy- dimethyl - a - ethylvalerolactone, 6-nitrodiphenic acid is effected by fractionation of m. p. 97°, which is oxidised by alkaline permanganate the morphine salt, m. p. 224°, [ a ] ^ ,—87-5° in pyr to 3-phenyl-aa-dimethyl-y-ethylglutaric acid. The idine, or of quinine hydrogen 6-nitrodiphenate. The hydroxylactone is converted by hydroxylamine (a) impure d- and 1 -acids thus obtained have respectively in alkaline solution into the oxime, m. p. 179—180°, m. p. 240—245°, [a]51B1 +62°, and m. p. 239-245°, of y-aldchydo-p-phenyl-y-methyl-a-ethylvaleric acid, [a]5461 —66-7°. No resolution of 4-nitrodiphenic acid (6) in acetic acid into the hydroxamic anhydride, can be brought about. It is suggested that diphenyl CHEt-CO—N-OH , nKO derivatives should be resolvable when they have CHPh-CMe2-CH-OH’ P' ° ' substituents in the 2- and 2'-positions which, owing Whilst S-benzoyl-yS-diphenylbutaldehyde behaves to size or electrical character, are unable to pass the chemically in accordance with an open-chain structure 6'- and 6-positions respectively. Dimenthyl diphenate, (cf. A., 1919, i, 21), 8-benzovl-y-phenyl-p-propyl- m. p. 126°, [a]5461 -120-4°, and d-p-octyl hydrogen butaldehyde and S-benzoyl-y-phenyl-pp-dimethyl- diphenate, m. p. 70—73°, [a]D +51°, show no change butaldehyde (IV) (A., 1920, i, 844) frequently appear in rotation on fractionation. k-Nitrodiphenic dichlonde, to react in the tautomeric diliydropyranol form. m. p. 90—92°, Q-nitrodiphenic dichloride, in. p. 87 , Thus, the ketoaldehyde (IV) reacts instantaneously diphenic dichloride, m. p. 97°, are obtained from the with bromine, giving the 8-&mm«-derivative, m. p. acids and thionyl chloride. 4 : 4'-Dinitrodiphenic 106— 107° (decomp.), and with iodine monochloride, acid and the corresponding acid chloride on boiling and is hydrogenated in presence of platinum-black in acetic acid solution yield a double compound of in the same way as the cyclic ether (V) to e-hydroxy- 4 : 4'-dinitrodiphenic anhydride and acetic anhydride y£-diphenyl-$$-dimethylvaleraldehyde, m. p. 106— in equimolecular proportions from which 4:4 -fl*- 107-5°. With methyl-alcoholic hydrogen chloride nitrodiphenic anhydride, m. p. 233—235°, is obtained the ketoaldehyde gives 2-methoxy-^: Q-diphenyl-3 : 3- by heating. 4-Nitrodiphenic anhydride,, m. p. -Oj dimethyl-3 : A-dihydro-\ : 2-pyran (V), m. p. 121-5— 207°, is obtained by evaporating a solution of 4-nitro- 122-5°. Bromination of (V) in carbon tetrachloride diphenic acid in thionyl chloride in a vacuum. 1 c is accompanied by hydrolysis to the 8-bromoketo- following are described : 2 : 2'-dibenzamidotetrane ■ aldehyde (above). Catalytic hydrogenation gives benzidine, m. p. 201°, 2 : 2' -d i-p -toluenesulphon 2-metJioxy-4: : Q-diplmiyl-'i : 3-dimethyltetrahydropyran, amidotetramethylbenzidine, m. p. 203°, and ^-amino- m. p. 100—101° or 97— 101° (stereoisomerism ?), tetramethylbenzidine, m. p. 138°. M. C l a r k . which is hydrolysed to the s-hydroxyaldehyde. When Stereochemistry of aromatic compounds. (V) is heated at 90—145° it decomposes into a-meth- Racémisation of optically active diphenic acl s’ oxy-p-methyl-Aa-propylene and phenyl styryl ketone. and rotation of the benzene nucleus m This supports the theory that the reversible addition diphenyl system. R. K u h n and O . Albrec of substances capable of enolisation to a double (Annalen, 1927,455,272—299).—1The stereochemistry linking takes place through an intermediate cyclic of diphenyl compounds is reviewed and iMs deauc compound, e.g., CHPh:CII-COPh+CMe,:CH-OH — > from the theories of Weissenberg and of Reis (A., > 9HICPh----- O 934) that different derivatives must have ditterti _ CH2Bz-CHPh-CMe2-CHO. CHPh-CMe„-CH-OH spatial formulae. Contrary to the s^ temenr H. E. F . N o t t o n . Christie and Kenner (J.C.S., 1922, 121, 614), so Action of hydrazine on meconine and 3-nitro- d-Q : 6'-dhiitrodiphenate does not ra cem ise ™ meconine. A. T a s m a n (Rec. trav. chim., 1927, 46, kept or heated at 140— 160° in aqueous sou l , ' 534—540).—Meconine, when warmed with an alcoholic The optical activity of the acid is n o t change . solution of hydrazine hydrate, yields 2-hydroxymethyl- heating with sulphuric acid at 98°, or with alumu ORGANIC CHEMISTRY. 877 chloride at 140—150°. I-4 : 6'-Dinitrodiphenic acid, where X = C 5H10]>C. When the methylation pro [a]’” +176°, [a]” 8 +142° in 2Ar-sodium hydroxide duct obtained from the sodio-derivative of ethyl (¿-acid, ra. p. 303—304°, [ajft —212-6° in 2iV-sodium S-cyclohexancspirodicyclopcnten-S-ol-1 : 2 : 4-tricarb- hydroxide; cf. Christie, Holderness, and Kenner, oxylato is boiled with hydrochloric acid, it yields A., 1926, 518), shows a normal rotation dispersion. an acid ester (IV), methyl ethyl hydrogen 4:-methyl-5- The velocity of racémisation of the Z-acid at 73-5° cyclo/ie.rcmespiro - A1- cyclopanten - 3 - one -1:2:4- tri - and 98-2° in 2iY-sodium hydroxide has been measured. carboxylate, m. p. 92—93°, which on hydrolysis with In sulphuric acid at the same temperature the velocity alcoholic potassium hydroxide, gives 4-methyl-5- is much smaller. Racémisation is not preceded in cyclo/tea-cmespiro - (0 : 1 : 2) - dicyclopente7i-3-ol - 1 : 2- this case by énolisation (cf. Hückel, A., 1926, 1024). dicarboxylic acid (V), m. p. 214—216°. This com The reaction is unimolecular and the heat of activ pound gives a deep violet colour with ferric chloride ation of the free anion calculated from the temperature and yields a stable cyclic anhydride, m. p. 95°, reverting coefficient (kt + 10)//ci=5-2 is 26,000 g.-cal./mol. to the original acid on hydrolysis. Bromination of This is regarded as a measure of the energy required to the dibasic acid yields 2-bromo-4:-methyl-5-cyc\o- rotate the benzene nuclei into a coplanar position. Aexanespiro-(0 : 1 : 2)-dicyclope?itan-3-one~] : 2 -dicarb- The constitution of 4 : 4'-dinitrodiphenic acid is oxylic acid, m. p. 197—198°; (VI) and (VII) are proved by its decomposition in presence of copper regarded as the most probable constitutions of the bronze to 4 : 4'-dinitrodiphenyl (Willstatter and last two compounds. Kalb, A., 1906, i, 996). When the acid is converted x< -C(C02H)==9-C02Et x < C(C02H)-q-C02H into its quinine salt, it appears to undergo an asym metric transformation (cf. Leuchs, A., 1921, i, 442), CMe(C02Me)-C0 ‘ CMe------C-OH the homogeneous product (80% of theoretical) having (IV.) (V.) m. p. 207—208°, [ajg +110° in chloroform, from which X - x < -C(C02H)-9Br-C0,H i . ii‘C0> 0 the value [ajg +700° is calculated for the free acid. CHMe-CO-C-CO CMe------CO In alcohol the activity varies greatly with the con (VI.) (VII.) centration and the ratio acid/base. Cinchonidine Treatment of (I) with hydriodic acid gives 4:-methyl-5- also gives a strongly dextrorotatory salt. Only cyc\ohexanes])irocyclopenta?i-3-one-l-carboxylic acid, inactive acid is regenerated from these salts. The m. p. 114— 116° (semicarbazone, m. p. 223°). series 4 :4'-, 4 : 6'-, and 6 : 6'-dinitrodiphenic acids M. C l a r k . thus clearly illustrates the powerful effect of 6-nitro- The Reimer-Tiemann reaction with m-chloro- groups in hindering the racémisation of active phenol. H. H. H o d g s o n and T. A. J e n k i n s o n diphenic acids. H. E. E. N o t t o n . (J.C.S., 1927, 1740— 1742).—A mixture of 4-cMoro-2- Alkaline oxidation of a-nitronaphthalene. hydroxybenzaldehyde, m. p. 52-5° (copper and chromium J- H. G a r d n e r (J. Amer. Chem. Soc., 1927, 49, salts; oxime, m. p. 155°; p-nitrophenylhydrazone, 1831—1833).—Oxidation of a-nitronaphthalene with m. p. 257°; semicarbazone, m. p. 212°; benzoate, alkaline permanganate, with subsequent treatment m. p. 98-5°), and 2-chloro-4-hydroxybenzaldehyde with aniline, affords the aniline derivative of phtlial- [copper and chromium salts; p-nitrophenylhydrazone, onic acid, as previously reported for the similar m. p. 288° (decomp.); semicarbazone, m. p. 214°; oxidation of naphthalene (cf. Euson, A., 1926, 612). acetate, m. p. 51-5°; benzoate, m. p. 96-5°] in almost equal proportions is obtained from m-chlorophenol E. G. W i l l s o n . Chemistry of polycyclic structures in relation by the Reimer-Tiemann reaction. The constitutions to their homocycHc unsaturated isomerides. of the aldehydes are established by conversion of the VIII. Differing- effects of the gem-dimethyl and methyl ethers into the corresponding methoxy- sjnroci/eiohexane groupings on the direction of and hydroxy-benzoic acids and confirmed by pre blocking of an intra-annular tautomeric system paration of 4-chloro-2-methoxybenzaldehyde from 4-nitro-2-methoxytoluene and of 2-chloro-4-hydroxy- by substitution. C. K . I n g o l d and E. A . S e e l e y (J.C.S., 1927, 1684— 1689).—Ethyl 5-cycfohexane- benzaldehyde from 2-chloro-4-nitrotoluene. The spirodicyclopenten - 3 - ol -1 : 2 : 4 - tricarboxylate is following are described : 4:-chloro-2-methoxybenzalde- methylated exclusively in the unbridged form. hyde, m. p. 74° [oxime, m. p. 132°; p-nitrophenyl automerism of the spirocyclohex&ne five-carbon hydrazone, m. p. 238°; semicarbazone, m. p. 228°); nucleus is, therefore, affected by méthylation in a A-chloro-2-methoxybenzoic acid, m. p. 148°; 4-chloro- irection conforming to the general chemical differences 2-hydroxybenzoic acid, m. p. 211 (lit. 207°); retween this series and the corresponding grew- 2 - chloro - 4 - methoxybenzaldehyde (p - nitrophenyl - methyl series of intra-annular tautomeric com hydrazone, m. p. 249°; semicarbazone, m. p. 240°); pounds (cf. J.C.S., 1923,123, 853, 3303). The revised 2-chloroA-hydroxybenzoic acid, m. p. 159°. M. C l a r k . ormidæ (II) and (III) are accordingly advanced as e most probable structures for the fission products Aromatic aldehydes. I. G. F a r b e n i n d . A.-G. oi the alkylated ester (I) (cf. J.C.S., 1919, 115, 320). —See B., 1927, 572. cwcioPropane derivatives. P. B r u y l a n t s (Ann. X 199—200°, of the nitrile was isolated from the non- a¡3- and py-unsaturated amides, together with a volatde by-products. It contains one secondary third amide, m. p. indef, 70°. A third amide, simi amino-group and gives a hydrochloride, m. p. 237°, larly obtained from l-hydroxy-a-ethylc?/cZohexane-l- cMoroplatinate, decomp. 190—250°, and nitroso- acetic acid, has m. p. 108— 109°. M. C l a r k . derivative, m, p. 169— 170°. It is not attacked by a-Trimethyl- and tetramethyl-cyclohexanones. alkali, but is converted by hydrochloric acid into the Separation of ketones by fractional oximation. hydrochloride of an isomeric monoacid base, m. p. R. C ornubert (Bull. Soc. chirn., 1927, [iv], 41, 894— 123— 125° (chloroplatinate, decomp. 180°). The 901).— By successive treatment with about half density of the c?/cZopropyl alkyl ketones decreases the theoretical amount of hydroxylamine hydro on ascending the homologous series, the differences chloride in presence of sodium acetate in boiling being alternately larger and smaller as in the case of alcohol (fractional oximation), crude a-tetramethyl- the q/cZopropyldialkylcarbinols (this vol., 653). The cycZohexanone, b. p. 185— 186°/770 mm. (Cornubert, mol. refraction [Ri]na and mol. dispersion of the Ann. Chim., 1921, 16, 141), is shown to contain a scries show mean exaltations of 0-71 and approx. tetramethylcycZohexanone, b. p. 184°/735 mm., 10%, respectively. In the phenyl and benzyl cyclo- 86°/30 mm., d\n 0-892, n“ '5 1-4484 (oxiine, m. p. propyl ketones the effect is still more marked. The 151-5°). Similarly crude a-trimethylq/c/ohexanone, exaltation is ascribed to the conjugation of the cyclo- b. p. 174— 176°, consists mainly of 2 : 2 : 6-trimethyl- propyl and carbonyl groups which is favoured by and 2 :2-dimethyl-cycZohexanone, together with a little the introduction of aryl radicals. New or revised 2:6- dimethyl and 2 :2 :6 :6-tetramethyl-cycZo- values are quoted for the b. p., df, and n™, respect hexanone. The a-trimethylcycZohexanone, b. p. 176— ively, of the following cycZopropvl ketones : methyl, 17S°, consists of 2 : 2 : 6-trimethjdcf/cZoliexanone, b. p. 111-6— lll-8°/751-7 mm., 0-8983, 1-4251; ethyl, 180°/750 m m ., cZJ7'0 0-9008, n1" 1-4488 (oxime, m. p. 131-87769 mm., 0-S927, 1-4299; propyl, 151— 151-4°/ 104-5— 105°), together with traces of dimethylcycZo- 754 mm., 0-8808, 1-4325; tsopropyl, 141-0—141-4°/ hexanone. it is concluded that there is no great 761 mm.', 0-8753, 1-4299; butyl, '173-8— 174-0°/757 tendency for the introduction of a second gem- mm., 0-8788,1-4371; iso butyl, 163-8— 164-2/761 mm., dim ethyl group. The tetramethylcycZohexanone may 0-8667, 1-4330; n-amyl, 194— 195°/760 mm., 0-8721, be produced direct from either of the two dimethyl- 1-4397; phenyl (m. p. 3—3-5°), 116— 117°/10-5 mm., q/cZohexanones or from the trimethyl derivative. 1-0545, 1-5567; benzyl, 124— 125°/10 mm., 1-0261, The following constants are recorded for the d ¡methyl- 1-5374; and of cyclopropylethylisobutylcarbinol, 191 — cycZohexanones obtained by hydrolysis of the oximes 192°/762 mm., 0-8725, 1-4474, and cyclopropyl- prepared in the above way : 2 :2-dimethyl-, b. p. n-propylisobutylcarbinol, 89—90°/12 mm., 0-8674, 1 7 1 -5 °, df 0-9143, ?ig 1-4480 ; 2 : 6-dimethyl-, b. p. 1-44781 H. E. F. N o t t o n . 1 7 4 °, df 0 -9 1 4 0 , nfl 1 -4 4 7 9 . R- B rig h tm a n . Preparation of unsaturated ketones from the Chloromethylacetophenones. C. F. H. Allbk chlorides of hydroxy-acids. G. A. R. K on and a n d M. P. B r i d g e s s (J. Amer. Chem. Soc., 192/, B. T. N a r a y a n a n (J.C.S., 1927, 1546— 1549).—Cer 49, 1846).— 2-Chloro-5-methylacetophenone, b. p. tain unsaturated ketones can be obtained by the 245-8—246°/760-l m m ., Jig 1-5419, and 4-chloro-^- action of zinc methyl iodide on the chlorides prepared methylacetophenone. b. p. 254-2— 254-4°/753-4 mm., from cyclic p-hydroxy-aeids without previous dehydr 1-5521, are obtained, in 70% and 34% yields, ation of the last-named compounds. cydoPentenyl- respectively, by the condensation of acetic anhydn e acetone is obtained in this way from I-hydroxycycto- with the appropriate chlorotoluene in presence o pentane -1 - acetic acid. The action of thionyl aluminium chloride (cf. Claus, A., 1892, 1200). chloride on cyclic B-hydroxy-acids leads to formation F. G. W il l s o n . of the corresponding chloride in addition to the Ethylideneacetophenone (phenyl propenyl chlorides of the two possible unsaturated acids and ketone) and p - methoxybutyrophenone. thence, by treatment with zinc methyl iodide, to D u f r a is s e a n d M . D emontvignier (Bull. feoc. cnun., the same unsaturated ketones. Substitution of zinc 1927, [iv], 41, 843—850).—Condensation of aceto- ethyl iodide gives the corresponding ethyl ketones phenone with acetaldehyde in methyl aleono in very poor yield, owing to simultaneous formation — 10° to 10° in presence of sodium methoxide a o of the ethyl ester of the Py-unsaturated acid. In a 56% yield of p-methoxybutyrophenone, b . p- vestigation of certain cyclic a-hydroxy-acids showed 121°/8 mm., df 1 -0 3 4 9 , nfl 1-5168, which on distillation that these had no practical value for the synthesis in presence of zinc chloride at 150— 160 /1 ¿>0 n ■ of ketones, owing to the extreme instability of the gives 86% of the theoretical yield of phenyl prope ketones affords a double compound of zinc chloride pyrogallol. T. E. Ellison (J.C.S., 1927, 1720— with 2 mols. of the oxime, having the m. p. indicated : 1724).—The statements of Bargellini and Marantonio acetone, in. p. 104°; methyl ethyl ketone, in. p. 71°; (A., 1908, i, 801) and of Dutta and Watson (J.C.S., inethyl wopropyl ketone, m. p. 94°; diethyl ketone, 1912, 1 0 1 , 1238) that 2 : 4-dihydroxyphenyl styryl 51°; dipropyl ketone, 52°. The same compounds ketone and 2:3: 4-trihydroxyphenyl styryl ketone are obtained by the action of zinc chloride on the may be prepared respectively by condensation of oxime in absolute alcohol. With aldehydes, Crismer’s cinnamic acid with resorcinol and with pyrogallol in salt affords limpid liquids containing zinc and chlorine, presence of zinc chloride are shown to be incorrect. but no definite compounds could be isolated. Analog More complex colouring matters only are obtained in ous compounds with cadmium chloride or magnesium these cases. Condensation of resacetophenone and chloride could not be isolated. With acetylacetone, benzaldehyde in alcoholic potassium hydroxide Crismer’s salt gives no oxime but a compound, solution yields a mixture of 2 : 4-dihydroxyphenyl C10H14O2N2,ZnCl2, m. p. 92—93°, decomposed by styryl ketone, m. p. 133—134°, and the isomeric water to give dimethyKsooxazole. Ethyl benzoyl- 1 -hydroxyflavanone, m. p. 189° (acetyl derivative, in. p. acetate and Crismer’s salt afford only phenyliso- 98°). Similar condensations of gallacetophenone with oxazolone (cf. Haller and Bauer, A., 1911, i, 568). Re benzaldehyde, m-hydroxybenzaldehyde, and salicyl- duction of the phenyh'sooxazolone with sodium and aldehyde ydeld respectively 2:3: A-trihydroxyphenyl alcohol affords ¡3-phenylalanine. R. B r i g h t m a n . styryl ketone, m. p. 165— 166°, 2:3: 4-trihydroxy- Hydrogenation of distyryl ketone and of phenyl 3-hydroxystyryl ketone, m. p. 219—220°, and di-p-phenylethyl ketone. V. I f a t i e v and O r l o v 2:3: i-trihydroxyphenyl 2-hydroxystyryl ketone, m. p. (Bull. Soc. chim., 1927, [iv], 41, 862—S64).—Hydro 224—225° (decomp.). The action of anhydrous genation of distyryl ketone in benzene solution at hydrogen chloride on an ethereal suspension of the 170— 180°/70— 100 atm. in presence of 15% of nickel last-named compound causes slow conversion into oxide affords di-p-phenylethyl ketone, b. p. 335— 2' : 3' : A'-trihydroxy-2-phenylbenzopyrylium chloride. 340°/760 mm., 209°/10 mm., m. p. 13— 14° (oxime, M. Clark. m. p. 91°), the yield being 60% in 15% solution, 25% Action of substances containing an active in 35% solution, and 10% in 50% solution. In 20% methylene group on urotropinę (hexamethylene- alcoholic solution the yield is 20%. In cj/cZohexane tetramine). II. M. V. I o n e s c u and V. N. the reduction does not take place. In presence of Georgescit (Bull. Soc. chim., 1927, [iv], 41, 881— copper oxide as catalyst a tarry mass results. Hydro 894; cf. this vol., 651).—Deoxybenzoin, indene, and genation of di-|3-phenylethyl ketone in q/cZohexane at fluorene do not decompose hexamethylenetetramine 240° affords ae-dic?/cZohex\dpentane, b. p. 315°, d° in alcoholic solution. l-Phenyl-3-methyl-5-pyxazolone 0-8836, n° 1-478. R. B r i g h t m a n . affords in about 70% yield methenylbis-l-phenyl-3- methyl-5-pyrazolone (I), m. p. 180° (yellow mom- Reality of the semipinacolinic transposition. Study of anisyl methyl ethyl glycol. (M lle.) J. ■N—CMe'v.p.rnqr .pTx^CMe.N bromine in the presence of anhydrous sodium acetate methoxy - 3 - methyldiphenylmethane - 6 - carboxylic acid, and a little ferric chloride affords mainly 2 :4 -di- m. p. 103— 104°, in good yield, together with 2 : 4'-di- bromo -1 -methoxyanthraquinone, m. p. 235°, with methoxy-3-methylphenylphthalide, m. p. 78—79°. The smaller amounts of i-bromo-1-methoxyanthraquinone, former gives with sulphuric acid (d 1-84) 2 :5 -di- m. p. 148— 151°. The monohalogenomethoxyanthra- methoxy-6-methyl-9-anthrone, m. p. I l l —112°, which quinones are converted by copper bronze in boiling is oxidised by chromic and acetic acids to 2 : 5-di- nitrobenzene into 4 : A'-dimethoxy-l : 1'-dianthra- methoxy-6-methylanthraquinone, m. p. 192°, not quinonyl, which is converted by boric and concen 182° as previously stated (J.C.S., 1921, 119, 1339). trated sulphuric acids at 150° into 4 : 4'-dihydroxy- This is demethylated by aluminium chloride at 200° 1 : l'-dianthraquinonyl. The latter compound is to 2 : 5-dihydroxy-6-methylanthraquinone, which is brominated in nitrobenzene at 120— 130° to 3 : 3'- converted by potassium hydroxide at 220—230° in dibromo-i : -dihydroxy-\ : l'-dianthraquinonyl (potass presence of sodium arsenate into 1:2: 5-trihydroxy- ium salt), also obtained from 3 : S'-dibromo-i : 4:'-di 6-methylanthraquinone, m. p. 275°, identified with me thoxy- 1 : l'-dianthraquinonyl; replacement of the morindone (cf. Jacobson and Adams, A., 1925, i, 273) by bromine atoms in this compound by the methoxy- or conversion into its triacetyl derivative. hydroxy-group could not be effected. The following H. E. F. Notton. compounds are incidentally described : 4 : 4'-di a-Aroyl-p-naphthols and condensation pro me,thoxymesobenzdianthrone (I), from 4 : 4'-dimetIioxy- ducts of the benzanthrone series. I. G. Fak- 1: l'-dianthraquinonyl in concentrated sulphuric acid b e n i n d . A.-G.—See B., 1927, 550. and copper bronze, converted by the action of sun Manufacture of [hydrogenated] anthraquinone light in the presence of chlorobenzene into 4 :4 '-di- derivatives. I. G. E a r b e n i n d . A.-G.—See B., methoxymesonaphthadianthrone (II), 3 : 3' - dibromo- 1927, 597. Betulin. II. R. V e s t e r b e r g (Ber., 1927, 60, P. OMe P. OMe [5], 1535—1536; cf. A., 1923, i, 590).—The two acetyl (II.) groups of betulin diacetate are retained with such (I.) r ( varying resistance to hydrolysis that the possibility of K preparing betulin monoacetate is indicated. Boiling w . 2 W- formic acid converts betulin monoacetate into allo- 4:4'- diniethoxyracsobenzdianihrojie, 3:3'- dibromo- betulin monoacetate. Betulin diacetate is readily 4 : 4 '-dimethoxymesonaphthadianthrone. 4 : 4 '-Di hydrogenated in glacial acetic acid solution in the hydroxy-1 : l'-dianthraquinonyl suspended in acetic presence of platinum to dihydrobetulin diacetate, m. p. acid is converted by nitric acid (d 1-48) into a nitro- 253°, [a]™ -6-50°, which is hydrolysed to dihydro 4 : 4' - dihydroxy -1 : l'-dianthraquinonyl; a dinitro- betulin, m. p. 277°, [a]g -19-14°. The latter com derivative could not be prepared. pound is transformed by formic acid into the corre 1 : 2-Diketo-l : 2-dihydroanthracene is converted sponding diformate. H. W r e n . by sulphuric acid into an amorphous quinhydrone, Reactions of carone. K. N. M e n o n and J. L. which is oxidised by chromic acid in glacial acetic acid S im o n s e n (J. Indian Inst. S c i., 1927, 10A, 1— to 3:4:3': 4'-tetrdketo-Z : 4 : 3': 4'-tetrahydro-1 :1'- cZ-Carylamine, b. p. 86— 89°/15 mm., [«Jli + l7-i'’3 ® dianthracene ; the corresponding azine formed by the alcohol, prepared by Baeyer’s method (A., 1895, i, 15') is converted by nitrous acid in o action of o-phenylenediamine is described. The CHMe ketone is transformed by reductive acetylation into 1 -carol (annexed formula), b. p. 141-— 3:4:3': 4' - tetra -acetoxy -1 : 1'-dianthracene, which 142°/100 mm., dg 0-9181, *8 M7-, Ki CHOH could not be caused to crystallise. The latter sub bile, I [a]“ —42-92, which has the abnormally stance is oxidised by chromic acid to 3 : 4 : 3' : 4'- high mol. refraction, [R{\d h 2| x c h tetra-acetoxy-1 : l'-dianthraquinonyl, which is con A is only slowly oxidised by alkaline verted by acids or alkalis into 3:4:3': 4'-tetra- permanganate; w i t h chromic acid i hydroxy-1 : l'-dianthraquinonyl [iiializarin] (potassium gives carone. It is dehydrated ) salt). The action of copper bronze and concentrated magnesium methyl iodide to a mixture containing sulphuric acid on 3:4:3': 4'-tetrahydroxy-l : l'-di principally doubly unsaturated monocyclic ny anthraquinonyl leads to the production of 3 : 4 : 3' : 4'- carbons. This gives with hydrogen chloride m -ac® ietrahydroxymcsobenzdianthrone (3:4:3': 4 '-tetra- acid a little terpinene clihydrochloride and distilsmw0 hydroxyhelianthrone), which is converted with difficulty main fractions, (a) b.p.172— 174°,0-839-, Wi> > by exposure of its solution in concentrated sulphuric [«Jg -46-52°, and (b) b. p. 180—190°/683 mm 4 acid to light into 3:4:3': A'-letrahydroxymeso- 0-8624, n? 1-4745, [cc]g -58-48°. Sodium Z-caryk>ado naphtliadianthrone. A strong positive colour change is converted by carbon disulphide into oily I-? J such as is usual with similar enlargements of the carylxanthate, which decomposes on distillation * molecule does not occur with alizarin and 3 : 4 : 3' : 4'- atmospheric pressure into a hydrocarbon, b. p. tetrahydroxy-1 ; 1'- or -2 : 2'-dianthraquinonyl. 170°, df0 0-8551, »8 1-473, [«]„ -5-96° maccitaoag H. W r e n . (hydrochloride, m. p. below —15 ), aPParmai]v Synthesis of morindone. R. B hattacharya identical with A4-carene. (Z-Caronc behaves no , and J. L. S i m o n s e n (J. Indian Inst. Sci., 1927, 10A, (cf. A., 1926, 1042) towards hydrogen cyanide, 6—9).—Reduction of 2 : 4'-dimethoxy-3-methyl- an oily cyanohydrin from which it is quan l benzophenone-6-carboxylic acid by the method of regenerated by potassium hydroxide. Scholl and Neovius (A., 1911, i, 452) affords 2 :4 ’-di- with ethyl sodiocyanoacetate. H. J • ORGANIC CHEMISTRY. 883 Catalytic action of boroacetic anhydride in the Azo-dyes from aminodiphenylene oxide. E. combination of organic acids with pinene and G l i e t e n b e r g , and G r a s s e l l i D y e s t u f e C o r p .—See nopinene. D u p o n t and P a s c a u d (Bull. Inst. Pin, B., 1927, 627. 1926, 437).—Interaction of a mixture of ¿-pinene a-[3-]Phenylcoumarins. G. B a r g e l l i n i (Gaz- (6S g.), acetic acid (50 g.), boron trioxide (10 g.), and zetta, 1927,57,457— 461).—The synthesis of 3-phenyl- acetic anhydride (15 c.c.) is almost complete after coumarin hy the condensation of salicylaldehyde with 1 hr. at the b. p. The product contains 22-8 mols. sodium phenylacetate in the presence of acetic of secondary alcohols (mainly bomeol, with some anhydride (Oglialoro, A., 1880, 164) is extended to fenchol), 12-2 mols. of tertiary alcohols, and 65-0 mols. hydroxycoumarins by the use of di- and tri-hydroxy- of monocyclic hydrocarbons per 100 mols. of pinene. aldehydes; the acetoxycoumarins are obtained, and The interaction is appreciable at the ordinary tem are hydrolysed to the hydroxycoumarins; these have perature. In the presence of formaldehyde or oxalic also been methylated. Of the substances described by acid polymerisation of the hydrocarbon takes place. Jacobson and Ghosh (A., 1915, i, 442, 831, 832) C h e m i c a l A b s t r a c t s . and by Ghosh (A., 1916, i, 281) as y-pyrones, and Production of terpineol from a-pinene in acid regarded by Robinson and Baker (A., 1925, i, solution. F. G . G e r m u t h (Amer. J. Pharm., 1927, 1300) and by Baker (A., 1926, 74) as a-pyrones, 99, 402—405).—The conversion of a-pinene into “ 7 : 8-dihydroxy-3-phenyl-y-benzopyrone,” m. p. terpineol in glacial acetic acid solution in presence of 215°, acetyl derivative, m. p. 184° (Ghosh, loc. cit.), is beuzenesulphonic acid (+1-5H20) is aided by heating probably identical with 7 : 8-dihydroxy-3-phenyl- and somewhat retarded by addition of water. coumarin, m. p. 213—215° (7 : 8-diacetoxy-, m. p. E. H. S h a r p l e s . 180°, 7 : 8-dirnethoxy-3-phenylcoumarin, m. p. 142— Camphor oils. VIII. Catalytic action of 144°, prepared by use of diazomethane), now obtained Japanese acid clay on cineole. K. O n o and S. from 2:3: 4-trihydroxybenzaldehyde. The “ 7-hydr- Miy a z a k i (Bull. Chem. Soc. Japan, 1927,2,207—209; oxy-3-phenylbenzo-y-pyrone,” m. p. 131° (Jacobson cf. A., 1925, i, 941; this vol., 156, 464).—Japanese and Ghosh, loc cit., 1057), is not, however, identical acid clay dehydrates cineole, yielding dipentene, with 7-hydroxy-3-phenylcoumarin, m. p. 206—208° p-cymene, and dipinene. H. B u r t o n . (7-acetoxy-, m. p. 182— 184°, 1-methoxy-, m. p. 118— Camphene and the Friedel-Crafts synthesis of 120°, derivatives), obtained from 2 : 4-dihydroxy- ketones. P. L i p p , P. K ü p p e r s , and M. H o l l (Ber., benzaldehyde, and may be a true y-pyrone. 5 : 1-Di 1927,60, [5], 1575— 1581).—The action of aluminium hydroxy-, m. p. 258—260°, 5 : 7-diacetoxy-, m. p. 155— chloride and acetyl chloride on camphene in the 156°, and 5 : 7-dimethoxy-3-phenylcoumarin, m. p. 180°, presence of anhydrous ether gives much resinous are also described. E. W . W i g n a l l . matter, tsobornyl chloride, and cc-acetylcamphene (I), Preparation of 4 : 6-dihydroxy-a- (j>-hydroxy- b. p. 76°/3 mm. [semicarbazone, decomp. 199—200-5° phenyl)coumarin [5:7: 4/-trihydroxy-3-phenyl- (corr.)], which could not be obtained if carbon coumarin]. G. B a r g e l l i n i and (S i g n a .) L. M o n t i disulphide was used as solvent. Replacement of (Gazzetta, 1927, 57, 462—464).—The synthesis by duminium chloride by anhydrous magnesium bromide Baker and Robinson (A., 1926, 1253) of 5 : 7 : 4'-tri or of acetyl chloride by acetic anhydride does not give hydroxy-2-methylisoflavone, identical with methyl- greatly improved results. The constitution of the prunetol, proved that prunetol (genistein) is not, as ketone is established by its preparation from the Bargelhni (A., 1926, 302) had suggested, a coumarin. magnesium compound of getber with bis-&s-carbonyl-0 -tolylmethylhydrazine, is unexpectedly inferior to the latter in dyeing pro (CGH4Me-NMe-N:CO-)2, m. p. 160°. This last sub perties and gives a less intensely coloured black stance when heated with aniline in decahydronaphth- chromium lake. The unusual ease with which it alene solution yields the dimethylbenzpyrazolone undergoes 5-acylation is explained by the observation together with a small quantity of what is probably that the 6-acyl derivatives, obtained in pyridine solu 4-phenyl-1 -o-tolyl -1 -methylsemicarbazide. o-Tolyl- tion are transformed by acids into the corresponding ethylcarbamyl chloride, b. p. 145°/12 mm., m. p. 38°, 5-acyl derivatives. o-Naphthazarin and its 6-acyl is converted into the azide, which on decomposition derivatives give a positive reaction with boroacetic yields 7-methyl-l-ethylbenzpyrazolone, m. p. 175°, anhydride. It is reduced by stannous chloride and bis-ELS-carbonyl-o-lolylethylhydrazine, m. p. 149°, and hydrochloric acid to 1:4:5: 6-tetrahydroxynaphtha- a substance, in. p. 39°. The carbonyl compound is lene, m. p. 180° (decomp.) (tetra-acetate, m. p. 202°), converted by boiling aniline into the pyrazolone, and oxidised by manganese dioxide and sulphuric acid diphenylcarbamide, and 4 -phenyl-1 -o-tolyl-1-ethyl- to naphthapurpurin (monopyridine salt), identical semicarbazide, C0H4Me,NEt,NH-CO,NHPh, m. p. with the products obtained by Jaubert (A., 1900, i, 129°, aiso obtained from o-tolylethylhydrazine and 42) from naphthazarin and by Thiele and Winter phcnylcarbimide. H. B u r t o n . (A., 1900, i, 504) from naphthazarin diacetate. 1 :8-Naphthyridine and its derivatives. G. Hydroxynaphthaquinones in which the hydroxyl and R o l l e r (Ber., 1927, 6 0 , [.B], 1572— 1575; cf. this carbonyl groups are adjacent are more volatile than vol., 367).—The conversion of 2 : 4-diehloro-l : 8- those with hydroxyl groups in other positions. naphthyridine into 1 : 8-naphthyridine is accom H. E. F N o t t o n . panied by considerable difficulty and is most easily a-Hsematin, Kuster’s tetramethylhsemato- effected by hydrogen in the presence of palladised porphyrin, and Nencki's hsematoporphyrin. 0. charcoal whereby a mixture of 1 : 8-naphthyridine Schumm (Z. physiol. Chern., 1927, 168, 1—10).— (identified as the corresponding chloroaurate, decomp. When a-hsematin is heated with methyl alcohol con 225°) and a dihydronaphthyridine (picrate, m. p. taining 1—2% of hydrochloric acid, and iron removed 173—175° after softening) is produced. Methyl from the product, a “ porphyrin ” is formed which ia 2 : 4-dihydroxy-l : 8-naphthyridine-3-carboxylate is regarded as a derivative of Nencki’s haematoporphyrin. converted through the corresponding amide, m. p. Two different substances are obtained when this 315° (decomp.), into 2 : i-dichloro-3-cyano-l : 8- porphyrin is heated for 1 hr. with 25% hydrochloric naphthyridine, m. p. 212° after softening. 2 :4 -Di- acid, and, by spectroscopical investigation, these methoxy-l : 8-naphthyridine m. p. 145— 146° after two products are identified as JVencki’s haemato- softening at 144°, is obtained from 2 : 4-diehloro-l : 8- porpliyrin and hsematerie acid. Kuster’s tetra- naphthyridine and methyl-alcoholic sodium meth- methylhsematoporphyrin and Nencki’s hsemato- porphyrin give the same products. A state of equili oxide. H. W r e n . brium is probably reached, and after removal of the Preparation of [naphthaphenazine] vat dyes. hsematerie acid, a further yield of this acid is obtained I. G. F a r b e m n d . —See B., 1927, 578. by heating the remainder with hydrochloric acid. Naphthazarin and 5 : 6-dihydroxy-1 : 4-naph The iron-free haematin derivative is p ro b a b ly the tha quin one. 0. D i m r o t h and H. Roos (Annalen, methyl ester of a methylhsematoporphyrin. When 1927,456,177— 192).—The constitution of 1 : 4 : 5 : 8- heated with glacial acetic acid for several hours, tetranitronaphthalene (A., 1926, 297) is further Nencki’s haematoporphyrin is mainly transformed into established by its reduction by stannous a product which is identified spectroscopically as chloride in presence of formic acid (cf. hsematerie acid, and this is regarded as a further Sachs, A., 1909, i, 426) to brownish-red distinction between this haematoporphyrin ana diperimidine dihydrochloride, which is coproporphyrin. A. W o rm all. oxidised by ferric chloride to diperim- idinequinone (I, X = H ). When the Sim ple m ethod of preparation of the iron salt latter is boiled with 20% hydrochloric of tetramethylhEematoporphyrin. H. F isosee acid it yields chhrodiperimidine hydro and F. L i n d n e r (Z. physiol. Chem., 1927,168, J9- chloride which is oxidised to yellow 170).—This compound was prepared by heating hsemm chlorodiperimidinequinone (I, X=C1). with methyl alcohol and sulphuric acid, treating ® Similarly a second chlorine atom may reaction mixture with hydrochloric acid, cooling, an be introduced. filtering. On keeping, the filtrate gave the iron sa , Nitration of 6 - hydroxy -1:4- naplithaquinone in. p. 185°, as tetragonal plates, or occasionally a (Fischer and Bauer, A., 1916, i, 71S) affords principally pointed prisms. Crystallisation from chloroform the 5-?u'iro-derivative. This is reduced by stannous methyl alcohol gave only tetragonal plates, not rue chloride and hydrochloric acid to 5-amino-1 : 4 : 6- ing at 300° (in one case m. p. 225° was observe )■ irihydroxynaphthalene hydrochloride, which is oxidised These variations hi m. p. are discussed with re^ by ferric chloride in dilute aqueous solution to 5 : 6-di to the possibility of isomeric forms, but a com p a n hydroxy-l : ‘i-naphthaquinone {o-naphthazarin), m. p. with the salt obtained from tetramethylh®ma 201—202° [pyridine salt; 5-acetate, m. p. 155—160° porphyrin and ferric chloride in acetic acid is nnpo (decomp.); 6-acetate, m. p. 140— 145°, sintering from ble, since this has no m. p. On oxidation with c ° 130°; 5 : 6-diacetate, m. p. 152° (decomp.); 5-benzoate, acid, the iron salt of tctramethylhaimatoporphjTi m. p. 160— 170°; 6-benzoate]. This substance, which behaves like tetramethylhsematoporphyrm, an has the formula previously ascribed to naphthazarin, two compounds yield the same methoxylatea n ORGANIC CHEMISTRY. 887 (m. p. 64°). Iron can be removed from combination phide or 2 : 4 : 2' : 4' - tetrachloro - 6 : 6'-dinitrodi- with tetramethylhsematoporphyrin, with simultaneous phenyl disulphide. F. G. W i l l s o n . hydrolysis, by hydrobromic acid in acetic acid, and Thiazoles. II. Nitration and reduction of crystalline hajmatoporphyrin is obtained. The iron 2-thiolbenzthiazole and its substituted deriv salt can also be reduced readily to mesoporphyrin. atives. J. T e p p e m a and L. B. S e b r e l l (J. Amer. Attempts to effect addition of methyl alcohol by heat Chem. Soc., 1927, 4 9 , 1779—1785; cf. preceding ing with hsemin and acids other than sulphuric acid abstract).—Treatment of l-thiolbenzthiazole with or hydrobromic acid, were unsuccessful. Proto nitric and sulphuric acids affords 5-?iiiro-]-thiolbenz- porphyrin, heated with methyl alcohol and sulphuric thiazole, m. p. 255—257°, which is reduced by sodium acid, yielded protoporphyrin ester quantitatively hydrosulphide to the 5-amiwo-derivative, m. p. 260°, and no tetramethylhsematoporphyrin. Coprohsemin, the structure of the latter being established by its esterified by hydrochloric acid and methyl alcohol, identity -with the 5-amino-l-thiolbenzthiazole, m. p. gave the ester of coprohajmatoporphyrin quan 263°, obtained by treatment of the tin-hydrochloric titatively. Protoporphyrin, prepared from haemo- acid reduction product of 5-nitro-2-aminothiophenol chromogen and free from mesoporphyrin, on oxid with sodium hydrosulphide in presence of carbon ation gave traces of methylethylmaleinimide. disulphide. 5 - Benzylideneamino -1 - thiolbenz thiazole, Spectroscopic data for deuteroporphyrin and various m. p. 226°, is described. Diazotisation and applic derivatives (the iron salt, copper salt, ester, copper ation of the Sandmeyer reaction to 5-amino-l-thiol salt ester, and the dibromo-ester) are given. benzthiazole resulted in the formation of yellowish- A. W o r m a l l . brown 5-chloro-l-thiolbe7izthiazole disulphide, ■which Thiolthiazoles. I. J. T e p p e m a and L. B. was reduced directly with aqueous sodium hydro Sebrell (J. Amer. Chem. Soc., 1927, 4 9 , 1748—1758). sulphide to 5-chloro-l-thiolbenzthiazole, m. p. about —Reduction of 2 : 2'-dinitrodiphenyl disulphide with 245°. The latter is also obtained in small yield by aqueous ammonium or sodium hydrosulphide, or treating l-thiolbenzthiazole disulphide with chlorine with sodium hyposulphite in aqueous or- alcoholic in chloroform solution in presence of iron, followed solution, yields the corresponding 2 : 2'-diainino- by reduction with sodium hydrosulphide. Nitration derivative, which affords l-thiolbenzthiazole in 32% of 4-chloro-1 -thiolbenzthiazole yields a miro-derivative, yield when boiled with carbon disulphide. A 96% m. p. 190—192°, from which the corresponding amino- yield of l-thiolbenzthiazole is obtained by treating compound, m. p. 240° (benzylidene derivative, m. p. the 2 : 2'-dinitrodiphenyl disulphide with aqueous 242°), is obtained by reduction with tin and hydro sodium or ammonium hydrosulphide, but not with chloric acid. Treatment of m-tolylenediamine di sodium hyposulphite, in presence of carbon disul sulphide with sodium hydrosulphide in presence of phide. It is concluded that the formation of the carbon disulphide affords 4:-amino-l-thiol-5-methyl- thiazole derivative is due to the interaction of nascent benzthiazole, m. p. 220° (benzylidene derivative, m. p. o-aminothiophenol with nascent carbon disulphide 253°), from which the corresponding 4-c/j/oro-deriv- (the former being derived from the reduction of the ative was prepared by the Sandmeyer reaction. disulphide, the latter from dissociation of sodium F. G. W i l l s o n . trithiocarbonate formed from the carbon disulphide Modified Kjeldahl method for the determin and the sodium sulphide or hydrosulphide), and this ation of nitrogen in alkaloids with the piperidine conclusion is supported by the production of l-thiol grouping. A. G u i l l a u m e (Bull. Sci. pharmacol., benzthiazole in 87-5% yield direct from o-chloro- 1927, 4; Ann. Chim. anal., 1927, [ii], 9 , 202—203).— nitrobenzene by treatment with sodium hydrosul By using a mixture of 5 g. of sulphuric acid, 5 g. of phide in presence of carbon disulphide. 1 : 4-Di- potassium sulphate, and 15 c.c. of 50% phosphoric chloro-2-nitrobenzene affords similarly 4-chloro-l- acid and heating for 3-5 hrs., 0-00651 g. of nitrogen Ihiolbenzthiazole, m. p. 192°, whilst 4-bromo-3-nitro- was found in sparteine (theory 0'0066); with 1 c.c. of benzenesulphonic acid yields sodium l-thiolbenzthi phosphoric acid and heating for 4-5 hrs., 0‘00672 for azole - 4 - sulphonate. 1 - Chloro -2:4- dinitrobenzene creatine (theory 0-00673); for 3 hrs. with 1 c.c. of yields, when treated similarly, dithiolbenzdithiazole, acid, 0-00742 for nicotine (theory 0-00746); under p. not below 270°, but 4-amino-l-thiolbenzthiazole, the same conditions 0-01148 for pilocarpine (theory p. 216°, can be obtained by reduction of 2 : 4 :2': 4'- 0-01145); for ¡¿-pelletierine with 3-5 hrs. 0-0062 (theory tetranitrodiphenyl disulphide with tin and hydro 0-00611); for pelletierine unsatisfactory results were chloric acid, followed by treatment with sodium obtained. I>- G. H e w e r . hydrosulphide and carbon disulphide as above, probably through the intermediate formation of 2 : 4- Sparteine. R. W olffenstein and J. R e i t m a n n rainothiophenol. 2-Chloro-3-nitrotoluene affords (Biochem. Z., 1927, 186, 269—277).—Sparteine is analogously 1-thiol-G-methylbenzthiazole, m. p. 184°, oxidised by sodium hypobromite to a very stable whilst 4-chloro-3-nitrotoluene yields \-thiol-i-methyl- dehydrosparteine, C15H24N2, m. p. 173°, [<*]” —255-0° oenzlhazole, m. p. 171— 173°, from which it is con- in chloroform, which decolorises acid permanganate c udcd that Sebrell and Boord’s product, obtained but cannot be reduced by zinc or tin and hydrochloric roni w-toluidine (A., 1924, i, 89), is a mixture of acid, and does not add hydrogen chloride or bromide e 4- and 6-methyl derivatives. 4-Chloro-3-nitro- when heated with the aqueous solutions of the latter enzoic acid affords analogously l-thiolbenzthiazole-4- in a sealed tube at 100°. It gives a hydrochloride and a perbromide, Ci5HMN2Br6 (cf. spartyrine, A., W W p i(\acid) m- P- not below 270°, but 1-thiol- z nazoles could not be obtained in this way from 1905, i, 544)- I t is catalytically reduced in presence ■ 0 • 4 .5 -tetrachloro-2 : 2'-dinitrodipkenyl disul of platinum-black to sparteine, b. p. 325°, [*]d 888 BRITISH CHEMICAL ABSTRACTS.----A. —49-8°, in chloroform (picrate, m. p. 201°, [a]5J 270°, which has [a]i] +138-S° in pyridine, in which — 13-6° in chloroform). The bearing of this work yohimboaic and tsoyohimboaic acids have [ajg +79-2° on the structure of sparteine and dehydrosparteine and +147-0°, respectively. Quebrachoic anhydride is discussed. P. W. C lutterbttck . has m. p. 298°. Ethyl quebrachoate hydrochloride has m. p. 304— 305° (decomp.); ethyl quebrachoate, in. p. Preparation of derivatives of methylhydr- 189°, is not affected in m. p. by ethyl yohimboate. astinine. E. M e r c k C h e m .E a b r .—SeeB., 1927,572. H. W r e n . Scopinium derivative : reduction to \j/-s copine Strychnine and brucine. IV. G. R. Clem o, and degradation to n t-hydroxyb enzaldehyde. W . H. P e r k i n , jun., and R . R o b in s o n (J.C.S., 1927, M . P o l o n o v s k i and M . P o l o n o v s k i (Compt. rend., 15S9—1627; cf. ibid., 1910, 97, 305; A., 1924, i, 1927, 185, 277—279; cf. Willstatter and Berner, A., 1337; 1925, i, 831).—The chemistry of strychnidine 1923, i, 701).—By the action of hydrogen peroxide (Tafel, A., 1892, 1012; 1898, i, 703) is investigated. on scopolamine, the hydrate of the 2V-oxide (I) is Strychnine [methosulphate, decomp. 2S2°; metho- presumably first formed, followed by migration of bromide, m. p. 320° (decomp.)] is reduced by an the tropyl group, OH-C8Hs-CO- (for which Tr is improved electrolytic method to a mixture of strych written), from a ¿'-oxygen to an 2V-oxygen atom, to nidine, m. p. 246° (methosulphate; methochloride, form scopinium tropate (II). decomp. 310°; methobromide; methiodide; hydriodide, decomp. 305°), and tetrahydrostrychnine, m. p. 202°, OH---- CH CH„ OH-CH- -0H, Me easily separated by crystallisation from benzene. Since M — 0—CH strychnidine methosulphate is obtainable both from strychnidine and by electrolytic reduction of strychnine I -CH, methosulphate, the nitrogen atom methylated is not the amide nitrogen atom. It is converted by methyl- alcoholic potassium hydroxide into methoxymetkyl- This is converted by hydrobromic acid into dihydrostrychnidine, C23H30O2N2, m. p. 125—120°, scopinium bromide, m. p. 209—210°, neutral to litmus; b. p. 235—237°/l mm. (crystallographic data by the quaternary base (nitrate, m. p. 203°) is unstable. T. V. B a r k e r ), a mono-acid base, giving a hydriodide, The bromide is not reduced by sulphur dioxide, methiodide, m. p. 278° [(decomp.); +H 20, m. p. 175° but is converted by zinc and hydrochloric acid into (decomp.)], and methohydroxide, m. p. 117°. The the hydrobromide of a strong tertiary base, which base is converted by methyl iodide in inethyl alcohol is a geometrical isomeride of scopine (Willstatter, into two oxymethoxymethyldihydrostrychnidines, loc. cit.), and is named {¡/-scopine (III), m. p. 126° C23H30O3N2, (A), m . p . 235°, a n d (B), m . p . 270° B (hydrochloride, m. p. 257— is also obtained from the base by the action ot dilute j)H’(pH (pH2 258°; picrate, m. p. 229°; nitric acid or of acetic anhydride, and from A by NMe HO'CH chloroplatinate, m. p. 223°; boiling with xylene, alcohol, etc. Methoxymethyl- }H*CH------CH2 chloroaurate, m. p. 237— dihydrostrychnidine combines slowly in boiling (HI) 238°). i/r-Scopine gives an benzene with 2 mols. of methyl sulphate, giving two oily O-acetyl derivative dimethosulphates, from which two dimethiodides, one (picrate, m. p. 187°; chloroaurate, m. p. 203°), and a crystalline, m. p. 297° (decom p.), are obtained. Ihe methiodide, m. p. 249°, which is degraded to a mixture crystalline dim ethiodide gives with silver chloride a of i/f-scopine with other basic substances. ip-Scopinc dimethochloride, m . p . 255—257° (d e co m p .), whic 1$-oxide, C8H1303N,3H20, m. p. 177°, forms a hydro regenerates the original base when treated with alka i, bromide, m. p. 188°, acid to litmus; it is reduced by and must be C20H22O(OMe)(IKMe2)<^^ ^ 2e|ci2- Oxid sulphur dioxide to ^-scopine.' An attempt at resolu tion of i¡/-scopine d-tartrate, m. p. 181°, gave negative ation of methoxymethyldihydrostrychnidine with results, in agreement with the formula (III). alkaline hydrogen peroxide gives the amino-aci , On heating the reaction product of scopinium methoxymethylslrychnidonic acid, C21H280 5^2, w ra bromide and moist silver oxide, methylamine is forms an craAycZro-compound, C21H2604N2, m. p. * • evolved, and m - hydro xy b enzald ehyde is obtained, By the action of ethyl-alcoholic potassium hydrox with i/i-scopine. E. W . W i g n a l l . on strychnidine methosulphate the correspon ng Quebracho alkaloids. I. G. H a h n (Ber., 1927, ethoxymethyldihydrostrychnidine, m. p. 98 , me ’ 60, [5], 1681— 1684).—Although quebrachine and Methyl-i/r-strychnidine, C20H 21O(!NM e)^V. -, m. p. yohimbine are very closely similar in themselves and their salts, their supposed identity (cf. Eourneau 203—204°, distillable in a vacuum [hydriodide, m. P- and Page, A., 1914, i, 862) cannot be maintained. 265—270° (decomp.); methiodide,m.p. 312° (decomp), Quebrachine hydrochloride, isolated from the total methochloride, m. p. 202—203°], is obtained (i) . alkaloids of Cortex Quebracho bianco, has [a]5f +102-8° distilling the mother-liquors from the prepara wn in water, w'hereas yohimbine and isoyohimbine methoxymethyldihydrostrychnidine, (ii) by hea b hydrochlorides have [ajg +103— 104° and +103-8°, the dimethochloride (m. p. 255-257°) of this base, respectively. Quebrachine, m. p. 235°, has [oc]JJ or (iii) by heating methylneostrychnidinium c i° +54-2° and +107-9° in alcohol and pyridine respect (see below). Methyl-^-strychnidine is not chin w ively, wherea-s the similar figures for yohimbine are by electrolytic reduction, but is oxidised by Pe™ ‘ M d 4-53-6° and [a]$ +84-1°. Quebrachine hydro ganate in acetone at 15° to a diketone, chloride is hydrolysed by alcoholic sodium hydroxide C21H2,OsN2, m . p . 152° [monoxime, d e c o m p . 1 7 0 -i^ - to quebrachoic acid, C20H24O3N2,H2O, decomp. 269— disemicarbazone, m . p. 252° (decomp.)], whic i ORGANIC! CHEMISTRY. 889 verted by methyl-alcoholic potassium hydroxide at sulphuric acid, gives on treatment with barium 100° into the isomeric aJiostrychnidone, decomp. carbonate methylstrychnidinium hydrogen carbonate, 260—265°, stable to permanganate and giving no C22H270N2,HC03,H20, which with methyl-alcoholic oxime or semicarbazone. potassium hydroxide yields methoxymethyldihydro- When boiled with dilute sulphuric acid, methoxy- strychnicline, m. p: 126°. C. H o l l in s . methyldihydrostrychnidone loses methyl alcohol and gives a solution of two isomeric methylneostrych- Strychnine and brucine. V. J . M . G u l l a n d , nidinium sulphates, from which are obtained two W. H. P e r k i n , jun., and R . R o b in s o n (J.C.S., 1927, iodides, C22H27ON2I, A., m. p. 300° (decomp.), and 1627—1662; cf. preceding abstract).—Tafel’s “ tetra- B, m. p. 277° (decomp.); the corresponding chlorides, hydrobrucine,” m. p. 200—201° (A., 1902, i, 53), is A, m. p. 270° (decomp.) (crystallographic data by identical with the same author’s “ brucicline,” m. p. T. V. B a r k e r ), and B, m. p. 255° (decomp.), are 198° (impure), and the latter name is adopted. described. Brucine is reduced electrolytically at 17—18° to a mix Electrolytic reduction of methoxymethyldihydro- ture of brucidine, m. p. 203—203-5° [dihydrochloride, strychnidine gives methoxymethyltetrahydrostrychn- m. p. 310° (decomp.); dihydriodide, m. p. 255° idine, C,i3lI3202N2, m. p. 220—222°, b. p. 230—235°/ (decomp.); methosulphate, m. p. 291° (decomp.); 1 mm. As a mono-acid base this compound forms a methiodide, m. p. 322° (decomp.)], and tetrahydro- hijdriodide, m. p. 235° (decomp.), and with difficulty brucine, m. p. 177° [dihydrochloride, m. p. 305° a methiodide (a), m. p. 227° (decomp.), from which (deeomp.); dihydriodide, m. p. 225° (decomp.); the methochloride (a) is obtained. The base yields methiodide, m. p. 290° (decomp.); nitrosoamine, m. p. two stereoisomeric series of dimetho-salts, (A) and 213—214° (decomp.); nitrosoamine hydrochloride, m. p. 288° (decomp.)], separated by crystallisation (5), C20H21O(OMe)(:mie2)< 9 ^ | x 2. The dirnetho- from methyl alcohol and ethyl acetate. Tetra- mlphate (A), formed together with the more soluble hydrobrucine is converted into brucidine by dehydr (B) isomeride by long boiling with methyl sulphate ation with phosphoryl chloride. in benzene, is converted into the dimethiodide (A), Brucine methosulphate, m. p. 278° (decomp.; m. p. 315° (decomp.), and thence into the dimetho- Leuchs and Anderson, A., 1911, i, 1018, give 26S°), chloride (4), which when heated gives methyl-^- gives the methiodide, m. p. 295° (decomp.; cf. Claus dihydrostrychnidine (below). The soluble dimetho- and Röhre, A., 1881, 749; Hanssen, A., 1885, 63), sulphate is similarly converted into the dimethiodide from which the methohydrogencarbonate, m. p. 202— (B), decomp. 165°, and the dimethochloride (B), which 203° (decomp.), is prepared. Methylbrucine, m. p. when heated gives methoxymethyltetrahydrostrych- 300° (decomp.), obtained from brucine methosul nidine. The dimethiodide (B ), when boiled in dry phate and hot dilute sodium hydroxide, is electro mesitylene, loses methyl iodide and yields a methiodide lytically reduced in dilute sulphuric acid, giving on (6), decomposing at 325° into methoxymethyltetra- treatment with barium carbonate brucidine metho- hydrostrychnidine. It is suggested, from their hydrogencarbonate, C25H3206N2,2H20, m. p. 265° behaviour with diazo-salts, that the methiodide (a) (decomp.), convertible by 30% potassium hydroxide solution into brucidine methohydroxide, (+2H 20), m. p. is C20H24O(OMe)(;NMe2)<^9®2jl , the b isomeride 268° (decomp.). Brucidine methosulphate when heated with methyl- being C20H2,O (OMe) (:N M c)<9^J. I. alcoholic potassium hydroxide yields methoxymethyl- dihydrobrucidine, C25H3404N2, m. p. 115°, b. p. 265— Methyl-q-dihydrostrychnidine, C20H230(!NMe)<^9'^') 267°/l*5 mm. [dihydriodide,m.j). 217—218° (decomp.)]. It gives at 100° a methiodide (A), m. p. 190° (or, ni- p. 212° [methiodide, m. p. 330—335° (decomp.); -fO-5EtOH, 179°), together with a little oxymethoxy- methochloride, m. p. 315° (decomp.)], results when the meihyldihydrobrucidine, C25H3105N2, m. p. 277° dimethiodide (B) or methylneodihydrostrychnidine (decomp.), and an intermediate iodine-free substance, chloride (below) is heated. m. p. 210—218°; a dioxymethoxymethyldihydro- By heating methoxymethyltetrahydrostrychnidine brucidine (X ), C25H3406N2, m. p. 270° (decomp.), may nydriodide cautiously at 230°, water and methyl also be isolated. The methiodide (A) and metho alcohol are evolved and methylncodihydrostrychn- chloride (A) regenerate methoxymethyldihydro- idmiuni iodide, C22H29ON2I, m. p. 350° (decomp.), is brucidine by the action of methyl-alcoholic potassium formed. The chloride has m. p. 345° (decomp.). hydroxide. A dimethiodide (A), m. p. 215°, is formed Methylstrychnine (Tafel, A., 1890, 1447), m. p. slowly at 140°; a methosxdphxxle (A), m. p. 231— •>18—320° (decomp.), readily obtained by adding 232° (decomp.), and, more slowly, a dimethosul- potassium hydroxide to a solution of strychnine phale (B) at 100°. The latter is converted into a fflethosiilphate, l°ses methyl alcohol when heated dimethiodide (B), m. p. 290° (+0-5H20, decomp.), Jn ^vacuum, giving normethylstrychnine, C21H2202N2 and a dimethochloride (B), which in boiling nitro [imhiodide, m. p. 315° (decomp.); methochloride, benzene loses methyl chloride and gives the metho m'fv.' i -^composition of methylstrychnine by chloride (B), m. p. 164° (decomp.); the corresponding • /i | c°l^°lic potassium hydroxide at 250° yields methiodide (B), m. p. 291° (decomp.), has only been “ ,0 ’ P- 52°, and a little carbazole, m. p. 236°; obtained from the methochloride. By the successive £ oy soda-hme carbazole and an oil, b. p. 93°/25 mm. action of silver sulphate and methyl-alcoholic potass P* wbich is probably an ethylindole. ium hydroxide on the dimethiodide (B) methoxy- 3 strychnine, electrolytically reduced in dilute methyldihydrobrucidine is regenerated, but when 890 BRITISH CHEMICAL ABSTRACTS.— A. the dimethochloride (B) or metbylneobrucidinium methyltetrahydrobrueidine dihydrochloride is heated chloride (below) is heated the product is methyl-^- in mesitylene at 180°. brucidine, C24H30O3N2, m. p. 198—199° [dihydriodide, Methoxymelhyltetrahydrobrucidine dimethohydrogen- m. p. 259° (decomp.); methiodide, m. p. 297° (de carbonate (A), m. p. 92—94° (+5H 20; 103—104° in comp.)]; from the dimethochloride (B) there is sealed capillary), is prepared from the dimethiodide also formed, when inorganic salts are present, a (A). The isomeride (B), m. p. 109° (+6H 20), from substance which seems to be an important fission the dimethiodide (B), yields when heated at 135° product of the brucine molecule. Methyl-^-brueidine the viethohydrogencarbonate (B), and at higher tem is unchanged by electrolytic reduction and by hydro peratures methyl- Spectrophotometric determination of pigments Chem., 1927, 73, 627—650).—Addition of lithium in the presence of coloured impurities. A. T r e i b s sulphate to the original reagent of Folin and Looney (A., (Z. physiol. Chern., 1927, 168, 68—91).—Extinction 1922, ii, 539) prevents the formation of turbidity coefficients have been determined for pyridine solu during the colorimetric determination of tyrosine; tions of liæmin, hæmoehromogen, coproporphyrin, a large excess of the modified reagent may therefore and the copper salt of coproporphyrin in 0-lAT-sodium be used, and, in this way, true proportionality of hydroxide. Pyridine, specially purified by warming colour development is obtained both with tyrosine with chromium trioxide, treating with potassium and tryptophan. Moreover, the degree of colour hydroxide, and distilling in a vacuum over potassium given by these two substances is in inverse proportion hydroxide, must be used for the determinations, to their mol. wt., so that standard solutions of tyrosine but the presence of 10% of water in the pyridine may be used for the determination of tryptophan. does not affect the extinction coefficients of hæmo Tyrosine itself is, however, more conveniently chromogen and coproporphyrin. Mixtures of hæmin determined by a modification of Millon’s reaction and coproporphyrin give additive effects. Details (described). are given of the determination of the concentration Figures are given for the tyrosine and tryptophan of hæmin and coproporphyrin in pyridine extracts of content of a number of proteins determined in this yeast, and of the procedure for the determination of way; in general, the figures are higher for tyrosine hæmin in yeast. A. W o r m a l l . and lower for tryptophan than those obtained by the method of Folin and Looney (loc. cit.). A method Determination of tyrosine and tryptophan in for purifying mercuric sulphate is described. proteins. 0. F o l i n and V. C io c a l t e t j (J. Biol. C. R. H a r in g t o n . Biochemistry. Variations in the p u and hydrogen carbonate of morphonuclear leucocytes, rabbit’s blood platelets, the plasma and of the alveolar carbon dioxide bacteria, and spermatozoa (human and guinea-pig). during forced breathing. E. H. L e p p e r and M. The influence of immune-serum on the surface of cells M a r t l a n d (Biochem. J., 1927, 21, 823—830).— has been studied and it is found that the hsemolytic During forced breathing the pa of the blood rises amboceptor attaches itself mainly to the alcohol- rapidly, reaching a maximal increase of 0-20—0-24 soluble material of the red blood-cell surface, whilst in 10— 15 min. When forced breathing is stopped the the agglutinin probably attaches itself in the first pn falls rapidly, returning to normal within 5 min. place to the protein; the binding of anti-bodies is The rise in the pa corresponds with the alteration similar to that of agglutinin. No difference can be found in the concentration of the hydrogen carbonate observed between the interfacial behaviour of a of the plasma and the tension of carbon dioxide in denatured “ immune ” globulin and that of maximal the alveoli respectively. S. S. Z i l v a . sensitised acid-fast bacteria, both in sodium chloride Influence of meals on the rise of the hydrogen- solution, and this is regarded as support for the view ion concentration of the blood during hyperpncea. that maximal sensitised bacteria are coated with a film of denatured globulin. A. WoBMALL. E. H. L e p p e r and M . M a r t l a n d (Biochem. J., 1927, 21, 831—833).—In forced breathing experiments Sulphurous compounds of haemoglobin. carried out 3 or more hrs. after meals the pa of the D a l l a V o l t a (Arch, anthrop. crim. Lombroso, 19-6, blood rises more slowly and the maximum change is 46, No. 4 ).—When a few drops of freshly-prepared less than in similar experiments performed within ammonium sulphide solution saturated with hydroxyl- 2 hrs. after food. Under the former conditions the amine hydrochloride or sulphate are added to a dilute alveolar carbon dioxide cannot be reduced to the same solution of oxidised blood, an olive-green colour is extent by the same rate and depth of respiration. produced; the two typical absorption bands o S. S. Z i l v a . oxyhsemoglobin fade, and a wide band appears va.the Dispersed phase of the blood-corpuscles. R. orange. The compound produced is termed chloro- E g e (Biochem. J., 1927, 21, 967—970).—By means of haimoglobin. The formation of a green coloration on various methods of determination, the volume of the injection of a saturated solution of hydroxylanune dispersed phase of the blood-corpuscle is found to into putrefying cadavers (the reaction indicating ; t c approach very nearly to the percentage of dry matter first stages of gaseous putrefaction) shows tna of the blood-corpuscles, which result is not in accord hydrogen sulphide and ammonia are p r e s e n t m putre ance with those obtained by Gough (A., 1924, i, 583). fied tissues. If a saturated aqueous solution S. S. Z i l v a . hydroxylamine is saturated with h y d r o g e n sulptu Structure of the cell membrane on the basis of and added to a blood solution, there is formed oxyge - a new method of surface tension determination. ated sulphohsemoglobin, which rapidly changes S. Mtjdd and E. B. H. Mudd (Biochem. Z., 1927, hsematin, but not to chlorohsemoglobin. 186, 37S—390).—The methods of the authors (J. C h e m ic a l A b s t r a c t s . Exp. Med., 1924, 40, 633; 1926, 43, 127) have been Complex carbohydrates in blood. I. E ec used for mammalian red blood-cells, human poly of taka-diastase and of emulsin on re ucin., BIOCHEMISTRY. 893 power of blood. E. G a b b e (Biochem. Z., 1927, cases. From the rate of disappearance of the phos 187, 57—71).—The reducing power of blood was phate ions it is concluded that the lead particles are increased 30—40% by the action of taka-diastase at rapidly oxidised to the hydroxide, which in its turn jjir 5-3; the effect was not obtained with plasma but quickly combines with the phosphate. About 90% was obtained in still higher degree with suspensions of of the combined phosphate is thus removed from the washed red blood-corpuscles. Similar, but somewhat solution. The remaining 10% combines at a much less marked effects were obtained with emulsin. slower rate with the lead carbonate in suspension. C. R. H a r in g t o n . The results obtained with a suspension of lead carbon Catalase content of blood at high altitudes. ate alone show that the velocity of this latter reaction A. I. A l e x e e v (Biochem. Z., 1927, 1 8 7 , 92—97).— is not governed by the rate of diffusion of the phosphate The catalase content and the viscosity of the blood of ions to the reaction surface of the particles but by the inhabitants of high altitudes both undergo a reduction slow chemical reaction at the surface. No detectable of about 12% between morning and evening. amount of ionic lead was found in the small volume of C. R. H a r i n g t o n . ultrafiltrates from the mixture of serum or Ringer Inorganic sulphates in human blood. R. F. solution and the lead suspension. The rate of settling Loeb and E. M. B e n e d i c t (J. Clin. Invest., 1927 , 4, of lead suspension at the ordinary temperature and 33—6).—The normal sulphate content of human at 37-5° is in the following order : Ringer’s solution> blood-serum varies between 0-40 and 1-00 milliequiv. water, serum > phosphate solution. The particles per litre. In nephritis with nitrogen retention, the of the lead suspension are negatively charged. sulphate increases and may reach 10 milliequiv. per S. S. ZlLVA. litre. C h e m i c a l A b s t r a c t s . Physico-chemical investigation of irradiated Solubility and distribution of chloroform in proteins. I. Changes of serum-alhumin during ultra-violet irradiation and their relationship to blood. H. WiNTERSTEiii and E. H i r s c h b e r g (Bio chem. Z., 1927, 1 8 6 , 172— 177).—The maximal heat-coagulation. M. S p i e g e l -A d o l f (Biochem. solubility of chloroform at the ordinary temperature Z ., 1927, 1 8 6 , 181— 193).—Serum-albumin, free from in distilled water is 0-55%, in physiological saline, electrolytes, coagulates under the action of ultra 0-50%, hi serum, 0-56—0-77%, and in whole blood, violet light in the same way as by heating but the 0-75—0-86%. Near saturation, the corpuscles con coagulum cannot be converted into a water-soluble tain twice as much chloroform as the plasma, whereas product by treatment with sodium hydroxide and at low concentrations the corpuscles may contain dialysing as with the heat-coagulum. Serum- four to six times as much as the plasma. albumin can be salted out after irradiation in presence of hydrochloric acid, but not after heating in presence P. W. C l u t t e r b u c k . Hydrolysis of blood pigments by alkali. H. of acid. On the other hand, serum-albumin heated or irradiated in presence of sodium hydroxide shows W aelsch (Z. physiol. Chem., 1927,1 6 8 , 188— 195).— By careful hydrolysis of washed ox corpuscles with the same behaviour to neutral salts. The presence 1'5% sodium hydroxide at 85°, followed by acidific of larger concentrations of neutral salts does not ation and electrodialysis, a pigment has been separated prevent the coagulation of serum-albumin during which contains the whole of the iron and probably irradiation but the presence of multivalent ions does the whole of the prosthetic portion of the original inhibit precipitation. Potassium thiocyanate, in opposition to its effect on heat-coagulation, is able hemoglobin, still in combination with small amounts neither to inhibit the coagulation by ultra-violet light of amino-acids derived from the globin portion of the nor to bring the coagulum into solution. conjugated protein. Proline and alanine have been P. W. Cl u t t e r b u c k . identified as forming the greater part of these amino- Destruction of organic substances for micro acids. By boiling oxyhsemoglobin solution with 2% determination of phosphorus in blood. M, sodium hydroxide for 96 hrs., 26% of the globin- M a c h e b c e u f and G. Zw il l in g (Bull. Soc. Chim. biol., mtrogen is obtained as free ammonia. H. D. K a y . 1927, 9, 697—699).—A mixture of 2 c.c. of serum Absorption in the ultra-violet by porphyrins. and 1 c.c. of sulphuric acid is heated for 10 min. ». H au sm an n and O. K r u m p e l (Biochem. Z., 1927, To the cooled solution 2 c.c. of nitric acid are added “ 6, 203—212).—The ultra-violet absorption spectra and heating is continued for 15 min. until the nitrous of acid and alkaline hsematoporpliyrin, of the tetra- fumes disappear. After cooling, 0-2 g. of powdered fflethyl esters of haematoporphyrin and coproporphyrin potassium permanganate is added, and the mixture j of the octamethyl ester of uroporphyrin in chloro- heated gently after the initial reaction has subsided. orm are described. P. W. C l u t t e r b u c k . If the product is not colourless a further 0-2 g. of i?^racti°n of a finely-divided lead suspension permanganate may be added and the mixture heated ? blood-serum, Ringer solution, and aqueous to complete the destruction of the organic material. » t e solution. J. B r o o k s (Biochem. J., For each 0-2 g. of potassium permanganate used 766—776).—The final values obtained for 0-11 c.c. of sulphuric acid must now be added before e ratio g.-atoms of phosphorus bound to g.-atoms determination of the phosphorus as ammonium tert Pr,escnt correspond with the formation of the phosphomolybdate (cf. A., 1926, 1067). In hosphate in the aqueous phosphate solution. W. O. K e r m a c k . witwP1 S0luti0n and serum the ratio corresponds Micro-determination of phosphoric acid com instp secondary phosphate. Using lead acetate bined as ester in blood and serum. M . M a c h e fonno i • suspension the secondary phosphate is b c e u f (Bull. Soc. Chim. biol., 1927, 9, 700 702).— m serum and the tertiary salt in the other two The proteins are precipitated by trichloroacetic acid 894 BRITISH OHEMIOAL ABSTRACTS.— A. and the total phosphoric acid in the filtrate is deter diet has a marked influence on the serum plasmalogen, mined by the application of the nitrosulphuric acid and with the dog a meat-free diet causes the value to ammonium molybdate method of the author (cf. A., fall to a low minimum; a vegetable diet has no 1926, 1067). The inorganic phosphate in the filtrate influence. Age is another important factor, since is determined by the addition of sulphuric acid, calves give distinctly lower values than do the ox and ammonium nitrate, and, after brief heating on the cow. A. W o r m a l l . water-bath, of ammonium molybdate. The phospho- Magnesium content of normal rats at different molybdate which separates is determined as previously ages. G. M e d e s and G. J. H u m p h r e y (J. Biol. described (cf. this vol., 370). The difference between Chem., 1927, 74, 149— 151).—The absolute amount the two determinations gives the amount of the of magnesium in growing rats increased up to 90 phosphoric esters present. W. 0. K e r m a c k . days of age, whilst the relative amount decreased after Colorimetric determination of sodium in 0-1 60 days; differences between the sexes were insignifi c.c. of serum or blood. S. Y o s h im a t s it (Tohoku cant in comparison with the age variations. J. Exp. Med., 1927, 8, 496—500).—Sodium is pre C. R. Hartngton. cipitated as pyroantiinonate, which is dissolved in Arginine content of some proteins and of hydrochloric acid; the antimony is converted into normal organs and organs showing amyloid the sulphide with sodium sulphide, and determined degeneration. O. F u r t h and 0. D eutschberger colorimetrically. The deviation from Kramers’ (Biochem. Z., 1927, 186, 139— 154).—The method of method is ± 3 % . C h e m i c a l A b s t r a c t s . Kossel and Gross (A., 1924, ii, 211) for the determin Body-fluid of the silkworm. S. B it o (Bull. ation of arginine in pure proteins is modified and made Agric. Chem. Soc. [Japan], 1926, 2, 167).—The com applicable to its determination in organs. The argin position varies with the stages of metamorphosis; ine contents of the following are: gelatin, 9%; sugar, cholesterol, and lecithin are present. The blood hemoglobin, 4-4%; fibrin and Witte’s peptone, 7%; of the female is higher in organic and lower in inorganic serum-albumin and globulin, 6-1%, caseinogen, 5-2%; substances than that of the male. The magnesium egg-albumin, 6% ; egg-globulin, 4-1%; legumin, and phosphorus contents are high, and those of 11-4%; keratin, 4-7% ; fibroin, 1-5%; sericin, 4-3%; potassium, sodium, calcium, silicon, and sulphate pancreatic nucleoprotein, 10%; human kidney, liver, are low. The manganese content is higher than in and spleen, between 6-5 and 8-1%. Organs showing mammals. C h e m i c a l A b s t r a c t s . amyloid degeneration have the same arginine content as normal organs (cf. A., 1925, i, 1505; 1926, 967). Behaviour of vitally important amino-acids P. W. Clcjtterbtjck. during the incubation of the hen’s egg. II. Lithium and strontium in human teeth and Cystine and cysteine. Changes in creatine and bones. A. D e s g r e z and J. M e t im e r (Compt. rend., creatinine during the incubation of the hen’s egg. 1927, 185, 160—163).—When the calcium in the ash Y . S e n d j u (J. Biochem. [Japan], 1927, 7, 175—180, of human bones or teeth is separated into phosphate 181— 189).—The cystine content of the hen’s egg and carbonate portions, lithium is found (spectro- diminishes during incubation, and is practically absent graphically) in the phosphate and strontium in the from the yolk after the 19th day, when the entire carbonate fraction. These elements thus probably cystine content is in the embryo. - The creatinine pass from the blood into the tissues without changing' of the albumin and yolk disappears after the 14th their chemical state (cf. A., 1923, i, 403). day, whilst that of the embryo increases steadily. B. W. Anderson. The creatine content of the embryo also increases. Crystalline lens. II. Modifications of the C h e m ic a l A b s t r a c t s . ultramicroscopic structure of the crystalline lens Plasmalogen. II. Occurrence of plasmalogen by salts, alkalis, and acids. D. C a t t a n e o (A i in animals. K. I m h a u s e r (Biochem. Z., 1927,186, R. Accad. Lincci, 1927, [vi], 5, 711—716).—Lltra- 360—375).—The aldehyde, plasmal, is widely dis microscopic observations have b e e n made oi tributed as the precursor (plasmalogen) and is found modifications produced in the crystalline lens by o in the cells of all animal organisms. The plasmalogen action of hypertonic, isotonic, and hypotonic so u- contents of various tissues and organs of several tions of sodium hydroxide, hydrochloric acid, ai animals, including man, have been compared and sodium chloride. Lunt. similar results have been obtained with different Alcohol content of normal placental tissue. animals. The white matter of the cerebellum, and the suprarenal cortex are specially rich in this sub W. D. M c N a l l y , H. C. E m b r e e , and C. A. tfuw (J. Biol. Chem., 1927, 74, 219— 222).—The tissue was stance, and, in general, a high plasmalogen content is found for organs rich in lipins. Using the colour minced, acidified with tartaric acid, and subje reaction of Feulgen and Imhauser (this vol., 369), the to steam-distillation; the distillate was fractiona plasmalogen content of the sera of different animals and the fraction containing volatile substances^ has been determined and the effect on these values of distilled in presence of silver nitrate and soc certain factors studied. Significant differences are hydroxide; the alcohol in the final distillate w as c e observed, the highest values being obtained with the mined by a modification of the method of _ ox and cow, the lowest with the sheep, goat, pig, and (A., 1913, ii, 800). Normal placenta contains 0-0UU» rabbit, whilst human serum gives medium or moder 0-0052% of alcohol. C. R. Hamngtos. ately high values. No great differences are observed Enzymes of the skin. VIII. J- W between the sexes, although the female animal usually Formation of lactic acid in the skin and e gives a slightly higher value than the male. The thereon of various rays. T. I k e b a t a ( i° BIO CHEMISTRY. 895 Z., 1927, 186, 43—53).—Fresh skin of normal and mixture is boiled with two portions of 15 c.c. each of diabetic human subjects and of normal guinea-pigs freshly-prepared chlorine water, which converts the and, to a less extent, skin of the cadaver can form silver iodide into silver chloride and iodic acid. When lactic acid from carbohydrate, most readily from all the chlorine is expelled the precipitate is separated, lsevulose. Insulin does not influence this power to the filtrate cooled, treated with 20 c.c. of phosphoric form lactic acid in the case of fresh human skin, but acid, 20 drops of 10% potassium iodide solution, increases it in the case of the skin of diabetics and of and 2 c.c. of a 1% starch solution, and the liberated the cadaver. This power is reduced somewhat by iodine is titrated with 0-1 A'-thiosulphate solution. irradiation with normal sunlight, the injury being A. R. P o w e l l . greater with strong artificial sunlight and greatest Lactic acid content of cerebrospinal fluid. A. with X-rays (cf. A., 1926, 94, 865, 1060). W ittgenstein and A. G a e d e r t z (Biochem. Z., 1927, P. W. C l u t t e r b u c k . 187, 137—145).—The normal lactic acid content of Preparation of vital neutral-red. M. P h i l l i p s the cerebrospinal fluid of man and the dog is 13—16 and B. C o h e n (Stain Tech., 1927, 2, 74—-79).—- mg.% as compared with 15— 18 mg.% for the blood- Neutral-red iodide, suitable for vital staining, was serum. The lactic acid of the serum is completely prepared by condensing nitrosodimethylaniline hydro diffusible. After muscular work the lactic acid con chloride with m-tolylenediamine. The indamine, tent of the cerebrospinal fluid does not rise so much tolylene-blue, so obtained was oxidised to neutral-red as that of plasma, but takes longer to return to the (eurhodine) by passing a current of air through a normal level. Intrathecal injection of calcium lactate boiling aqueous 2-5% solution for 2 hrs. The neutral- caused no physiological disturbances; injection of red was purified by conversion into its double salt with lactic acid, however, caused death of the animal with stannous chloride, from a solution of which the iodide the symptoms of acidosis. C. R. H a r in g t o n . of the dye was precipitated by means of potassium Influence of the age of the cow on the yield and iodide. After repetition of this precipitation it was quality of the milk. M. K. W h i t e and T. J. finally reerystallised from 95% ethyl alcohol. D r a k e l e y (J. Agric. Sci., 1927, 17, 420—427).—The H. W. D u d l e y . yield of milk of all breeds of cows at first increases Surface activity of trypan-blue at various rapidly with age, reaches a maximum, and then limiting surfaces. N. O k u n e v (Biochem. Z., gradually diminishes; the percentage of fat in the milk 1927,187, 37—50).—Trypan-blue shows no capillary increases slightly and then decreases, and the per activity at a water-air surface, but shows such centage of solids-not-fat decreases continuously with activity in increasing degrees at water-olive oil, age. C. T. G i m in g h a m . T'ater-benzene, and water-light petroleum surfaces; the bearing of these observations on the phenomenon Efiect of temperature on some of the properties of vital staining is discussed. C. R. H a r in g t o n . of caseinogen. V. P e r t z o f f (J. Gen. Physiol., 1927, 10, 961—984).—The solubility of caseinogen Vital staining and adsorption. H . A. K r e b s in a solution of base is approximately constant and D. N a c h m a n s o h n (Biochem. Z., 1927, 186, 478—484).—With acid dyes, mainly azo and triphenyl- between 21° and 37°, the corresponding combining methane compounds, a parallelism, similar to that weight being 2100. The solubility varies between existing for basic dyes, has been found between 37° and 60°, but is again approximately constant adsorption on kaolin and staining of paramcecia. between 60° and 85° at a value corresponding with a The vital staining power is not a function of the combining weight of 3700. The maximum amount ‘'lipoid solubility,” and the main factor concerned of caseinogen which dissolves in 1000 c.c. of water at 5° contains 7 mg. of nitrogen. W. 0. K e r m a c k :. is adsorption. A. W o r m a l l . Stain solubilities. II. W . C. H o l m e s (Stain Effect of rennin on caseinogen. I. Solubility Tech., 1927, 2, 68—70; see also this vol., 593).—The of casein in sodium hydroxide. V. P e r t z o f f (J. solubilities of 23 biological stains in water and in Gen. Physiol., 1927, 10, 987— 1004).—Casein pre alcohol are tabulated. To obtain trustworthy figures pared by the action of rennin (or pepsin) on milk was for solubility it is essential that the dyes examined purified by repeated dissolution in sodium hydroxide should be free from inorganic salts. H . W . D u d l e y . solution and reprecipitation by acid at the point of minimum solubility. The resulting product is free Detection [and determination] of very small from active enzymes. The casein which dissolves in quantities of iodine [in urine and organs]. H. 1000 g. of pure water at 5° contains 7 mg. of nitrogen hscHESBREXNER (Pharm. Ztg., 1927, 72, 984—986).— (cf. preceding abstract). The solubility of casein in feolids (about 2 g.) are fused in a nickel crucible at the base at 5° corresponds with a combining wt. of 810, lowest possible temperature with sodium hydroxide whereas at the same temperature the solubility of and a sufficient quantity of sodium nitrate to oxidise caseinogen corresponds with a combining wt. of 1300. completely the organic matter, the product is ex- At 23° the corresponding combining wts. are respect racted with water and the solution just neutralised ively 1450 and 2100. These results support the view with sulphuric acid and treated with 1 c.c. of Ar-sulph- that a chemical change occurs when caseinogen is unc acid. Liquids, such as urine, are acidified with acted on by rennin. W. 0. K e r m a c k . tric a°id. In both cases the solution is treated ^th an excess of silver nitrate and set aside in a dark Formation of acid in milk by heating. E. 0. p ace for 24 hrs. The precipitate of silver chloride W h i t t i e r and A. G. B e n t o n (J. Dairy Sci., 1927, , 10cude is collected, -washed, and suspended in 10 126__138).—The rate of formation of acid in milk er c°utaining 1 c.c. of JV-hydroclilorie acid. The on heating is a direct function of the time and temper- 896 BRITISH CHEMICAL ABSTRACTSA. ature of heating and of lactose concentration, and is Influence of “ synthalin ” on the respiratory unchanged by coagulation of casehiogen. Lactose is quotients of diabetics. A. L u b l i n (Arch. exp. the principal source of the acid. Addition of sucrose Path. Pharm., 1927, 124, 118—128).—Diabetics to has no effect. C h e m i c a l A b s t r a c t s . whom “ synthalm ” has been given by mouth show Micro-determination of carbamide in urine an increase in the respiratory quotient following the K e r m a c k . without the use of urease. W. L a u b e n d e r (Bio- administration of dextrose. W. 0. chem. Z., 1927, 186, 158—171).—A magnesium Protein-sugar in different pathological con chloride method for the determination of carbamide ditions. X. C h a h o v i t c h , V. A rnovljevitch , and in urine is described. The results for human, rabbit, (M l l e .) M . V i c h n j i t c h (Compt. rend., 1927, 184, and dog urine agree satisfactorily with those obtained 1495—1496).—An increase of both the free and by the urease method. The method determines protem-sugar in the blood occurs in cases of pulmonary 1-4— 10-8 mg. of carbamide with an error of 1-5% tuberculosis, cancer of stomach, peritonitis, pleurisy, and is adapted for urines containing sugar and urease pneumonia, bronclio-pneumonia, chronic nephritis, poisons. P. W. C l u t t e r b u c k . cirrhosis of the liver, malaria, typhoid fever, and Determination of oxalic acid in urine. G. M. dyspepsia, evidence of malnutrition occurring in all zu H o r s t e (Z. physiol. Chem., 1927, 168, 196—200). cases. Protein hyperglycsemia is thus only a general —Oxalic acid is precipitated from the urine by addi expression of disturbed metabolism. tion of calcium chloride and suitable adjustment of R . BRIGHTMAN. the reaction. The impure calcium oxalate is centri Iodine content of the thyroid in relation to its fuged off, dilute sulphuric acid is added, and the free histological structure and activity. C. A b e lin oxalic acid distilled off direct from the centrifuge tube (Arch. exp. Path. Pharm., 1927, 124, 1—40).—The under reduced pressure. The sublimate is dissolved iodine contents of a large number of thyroids, normal in hot water and titrated in the usual way with and pathological, have been determined and the results potassium permanganate solution. Known quantities are compared with the histological findings and with of oxalic acid (of the order of 2—7 mg.) may thus be the effect of the thyroid on the rate of metamorphosis recovered almost quantitatively from urine. of the tadpole. W. 0. K erm ack . H. D. K a y . Deposition of lipins in the walls of the aorta in Oxyhsemoglobin dissociation curves of whole infants. N . N. K o u b l e (Arkh. B iol. Nauk, 1926, blood in ansemia. D. W. R i c h a r d s , jun., and 26, 163— 180). C h e m ic a l A bstracts. M. L . S t r a u s s (J. Clin. Invest., 1927, 4, 105—126).— The curves were normal at j>n 7-24 and 7-44, and Distribution of alkalis in the serum of infants. subnormal at ¡hi 7-64. C h e m i c a l A b s t r a c t s . Z. v o n B 6 k a y (Magyar Orvosi Arch., 1927, 28,1—5)- Effect of partial pancreatectom y on the sugar —In premature birth, rickets, and tetany combined with rickets the hydrogen carbonate in the serum is excretion threshold. G. E d a (J. Biochem. [Japan], 1927, 7, 79—99).— On removal of one half to one third subnormal. At the carbon dioxide tension of the of the pancreas, the threshold of sugar elimination is blood, 60% of the serum alkali is combined as sodium increased simultaneously with diminution of sugar hydrogen carbonate and 40% as sodium albuminate; assimilation, although not necessarily immediately. at that of the air the percentages are 44 and 56, respectively. C h e m ic a l A bstracts. C h e m i c a l A b s t r a c t s . Relation between the metabolism of dextrose Calcium and phosphorus metabolism. IV. and fats in diabetes. N. R. D h a r (J. Physical Influence of free fatty acids in the intestine on Chem., 1927,31,1259— 1262).—A theoretical paper in the absorption and excretion of the mineral which the oxidation of fats, carbohydrates, and elements. V. Infantile rickets. Excretion ana protein is discussed. L. S . T h e o b a l d . absorption of the mineral elements, and influence Ketone excretion, D : N ratios, and glycogen of fat in the diet on mineral metabolism, o. • contents of liver and muscles of fasting, depan- T e l e e r (Quart. J. Med., 1926,20,1—25).—Conditions creatised dogs. I. G h a t k o f f (J. Biol. Chem., permitting a consistent excess of free fatty aci s 1927, 74, 203—218).—Dogs were depancreatised and in the intestine facilitate the absorption of phosphorus. allowed to recover from the operation under the In infantile rickets, the percentage of mineral aci s, influence of insulin; the physiological response to magnesia, lime, and phosphoric acid in the iffica the withdrawal of insulin and of food was then solids is increased; excess of mineral matter i observed. The D : N ratios reached after 3 days excreted in the faeces chiefly as calcium phospna • without insulin were in some cases higher than those The amount of combined fatty acids is low, observed in phloridzinised dogs; the magnitude of urinary phosphorus is less than the fffical phosplior■ . the ratio was, however, dependent on the state of Metabolic changes accompanying healing arc nutrition of the animal, rising with increase hi weight scribed; alterations in the mode of excretion of the dog. Following withdrawal of insulni, the healing progresses are due to increased absorp 101 glycogen content of the liver was 0-3% on the third minerals from the intestine. ’ and 0-06% on the fifth day, whilst that of the muscles C h e m ic a l A b s t r a c t s . was 0-45% and 0-35% respectively. Excretion of Rickets. Calcium absorption in relation t ketones ran approximately parallel to that of dextrose, gastric acidity. L . W i l l s , P . S a n d e r s o n ,_and and, in relation to the body-weight, was similar to the P a t e r s o n (Arch. Dis. Childhood, 1926, 1, 24o- ■- b ketone excretion observed in human diabetics. —Calcium retention is reduced by miik contain^ C. R. H a r i n g t o n . hydrogen chloride or ammonium chloride. ^ BIOCHEMISTRY. 897 acid milk causes a slight loss of calcium and rise in by simultaneous administration of insulin, but was gastric acidity. There is no causal relation between not affected by variations in renal excretion induced calcium metabolism and gastric acidity. by administration of tartrates, uranium salts, or Chemical Abstracts. phloridzin, or by hepatic insufficiency resulting from Distribution of oxygen in individual organs as poisoning with chloroform or phosphorus. shown by experiments with angiostomised dogs. II. Although the rate of disappearance of galactose E. S. L o n d o n and L. M. R a b i n k o v a (Biochem. Z., from the blood was increased by simultaneous admin .1927, 1 8 6 , 155— 157).—The blood of the portal, istration of dextrose, the effect was probably due to splenic, renal, and pancreatico-duodenal veins is, increased urinary excretion rather than to increased during digestion, poorer in nitrogen than during the metabolism of the galactose; the metabolism of the fasting condition. The blood of the right and left latter was not affected by previous treatment of the renal veins contains different amounts of oxygen. animals with dextrose or with galactose itself. P. W . Cltjtterbtjck. C. R. Harington. Mechanism of cellulose digestion in the Formation of lactic acid after severe haemor ruminant organism. H. E. W o o d m a n (J. Agrie. rhage. Rate of disappearance of sodium lactate Sci., 1927,1 7 , 333—338).—To explain cellulose diges injected intravenously and its effect on sugar and tion in ruminants, it is suggested that, by the action inorganic phosphate of the blood. C. R i e g e l of bacteria, dextrose, or a sugar capable of hydrolysis (J. Biol. Chem., 1927, 74, 123—134, 135—148).— to dextrose, is formed from cellulose by hydrolysis. Haemorrhage, in dogs, resulted in an increase in Assuming that further bacterial breakdown will be the lactic acid content of the blood; the extent of no greater than in the case of the digestible nitrogen- the increase varied directly with the severity of the free extractives of the food, this explanation is in haemorrhage; in the most severe experiments the keeping with Kellner’s findings as to the productive concentration continued to increase after actual value of digested fibre. The occurrence of cellobiose bleeding had ceased. The increased lactic acid con and dextrose in the fermentation of cellulose by tent of the blood resulting from injection of sodium bacteria, as shown by Pringsheim (A., 1912, ii, 587), lactate decreased at first rapidly, by diffusion, and is quoted in support of this view. then more slowly as it was utilised by the tissues. C. T. Gimingham. There was simultaneously a fall in the inorganic Specific dynamic action of foodstufis. VI. phosphate and a rise in the sugar content of the Specific dynamic action and carbohydrate blood, from which it is concluded that the utilisation exchange. I. A b e l i n and B. K o b o r i (Biochem. Z., of the lactic acid consisted in its synthesis into 1927,1 8 6 , 3—27).—Repeated injections of phloridzin lactacidogen and glycogen. C. R. Harington. increase considerably the specific dynamic action of meat, the increased requirement of sugar possibly Production of lactic acid in frog’s muscle in inducing an increased synthesis from protein by a vivo. C. E. W o o d r o w and V. B. W igglesworth series of exothermic reactions (cf. A ., 1925, i, 332; (Biochem. J., 1927, 2 1 , 812—814).—When placed in this vol., 276). P. W. Clutterbuck. a bath at 38° the frog is at first violently active but becomes stiff and motionless in about 1 min. In this Relation of the intestinal wall and of the liver state the muscles of the hind legs show an average to the formation of glycogen. A. Y. K h a r i t content of lactic acid of 0-125%. The muscles of a (Arkh. Biol. Nauk, 1926, 26, 255—258).—Glycogen is pithed frog under similar conditions contain little not synthesised from lower carbohydrates by the more lactic acid (0-043%) than the normal resting intestinal wall of dogs. The glycogen content of minimum (0-03%). On removal to the ordinary blood of the portal vein was equal to or less than that temperature the high lactic acid content of muscle of the hepatic vein, or of peripheral blood. does not regain the normal level until ^ to 1 hr. later. Chemical Abstracts. S. S. Z i l v a . Dextrose metabolism of kidney tissue in Digestion in the cockroach. I. Hydrogen-ion titr o . I. J, T. Irving (Biochem. J ., 1927, 2 1 , concentration in the alimentary canal. II. The «SO 886),—Kidney tissue in vitro utilises dextrose digestion of carbohydrates. V. B. W igglesworth aerobically at a rate which is probably linear. In a (Biochem. J., 1927, 2 1 , 791—796, 797—811).—I. In vacuum or in the presence of potassium cyanide the wild cockroaches (Blatella germánico) the average pK utilisation of dextrose is markedly inhibited, or stopped of the saliva is 6-9, of the crop contents 5-2, and of completely. The integrity of the kidney cell is the stomach 6-2. The acid in the crop is produced by essential for the utilisation of dextrose. It is probable bacterial and yeast fermentation from the carbohydrate that an active surface is involved. S. S. Z i l v a . ingested by the insect, the acid production being more Metabolism of lactose. I. Fate of intra intense with sucrose and dextrose than with starch, venously administered galactose in the rabbit. maltose, and lactose. After protein food the average • Effect of dextrose and galactose on fate of pn in the crop is 6-3; after carbohydrate food it is 4-8. galactose in the rabbit. R. C. Corley (J. Biol. A colorimetric method for the determination of pa „ r?1’. 19?7, 74, 1—18, 19—31).—I. After intraven- in about 0-002 c.c. is described. It is based on the us injection of 0-5—2-0 g. of galactose into rabbits use of waxed plates and pipettes in the manipulation ji e taken for the substance to disappear from of the fluid. e blood was proportional to the dose; larger doses II. The salivary glands of the cockroach secrete an 2 aP?earec* approximately the same time as the amylase and in B. germanica (although not in Peri- g- rae. The rate of disappearance was increased planeta americana) an invertase. Extracts of the crop 898 BRITISH CHEMICAL ABSTRACTS.— A. when thoroughly freed from food contents do not con intense after the “ blockade ” than before. It is tain enzymes acting on carbohydrates. The stomach concluded that the retieulo-endothclial systems of and hepatic cajca secrete invertase, maltase, and small the spleen, liver, and b one-marrow are concerned in the quantities of lactase. The ratio of amyloclastic to removal of neutral fat and cholesterol from the blood saccharogenic activity is similar to that of human and in the metabolic changes of these substances. ptyalin. The ;pH-activity curves for these two enzymes V . The administration p e r o s of large amounts of have been compared. Under the same conditions olive oil or olive oil-(-cholesterol usually, but not cockroach amylase is more resistant to acid (optimum always, causes a greater cholesterolremia in splenec- pn 5-9). This is due in part at least to some associated tomiscd dogs than in the normal animal. Similarly factor which is not destroyed by heating at 100° for the intravenous injection of an emulsion of olive oil 5 min. Cockroach invertase is partly inhibited by leads to a rise in the blood neutral fat after splenec 1% sodium chloride, 20% glycerol, or O-OOOliV-silver tomy, whereas no increase occurs before the operation. nitrate, and completely inhibited by - O-OOlJV-silver The characteristic results obtained after splcnectomy nitrate. The ^-activity curve for cockroach invertase are due to the absence of the spleen, which is concerned shows an optimal range from 5-0 to 6-2, which is with the elimination of neutral fat, and to a disturb intermediate between the ranges for yeast invertase ance in the elimination or splitting of neutral fat in and human jejunal invertase. Cockroach maltase is the liver. A. W o r m a ll. partly inhibited by 1% sodium chloride and com Nutritive value of fats and lipins. K . T aka- pletely inhibited by 10% glycerol. It is adsorbed h a s h i (Sci. Papers Inst. Phys. Chem. Res. Tokyo, 1927, by powdered sand, but can be extracted from this with 5, 103—132).—From feeding experiments with rats phosphate buffer pn 6-8. The ^n-aetivity curves using a basal diet of flesh, starch, lactose, mineral show an optimal range from 5-0 to 6-2 which is more salts, and oryzanin, it is concluded that 1% of acid than the range in the maltase of either yeast or cholesterol, lecithin, kephalin, or protagon does not human jejunum. Cockroach lactase is completely supply the nccessary growth factor. Normal growth inhibited by 10% glycerol and shows an optimal zone is not procured when 5, 10, or 20% of the following of ps from 5-0 to 6-4. S. S. Z i l v a . synthetic fats are added to a fat-free basal diet defi cient in vitamiiwi : triacetin, tributyrin, trivalerin, Effect of alkalosis on the excretion of chloride tricaproin, tricaprylin, tricaprin, trilaurin, trimyristin, and on carbohydrate metabolism. M. W. G o l d - tripahnitin, tristearin, triarachin, tricerotin, triolein, b l a t t (Biochem. J., 1927, 21, 991— 1004).—The trilinolein. The nutritive value of these synthetic maximum concentration of hydrogen carbonate present fats increases from eerotin to caprin, and then decreases in the urine of a normal human subject after the from caprin to acetin, with the exception of tributyrin ingestion of 30 g. of sodium hydrogen carbonate is and trivalerin, which are definitely toxic. Using a 3-2%. The rise in the excretion of the carbonate fat-free basal diet not deficient in vitamin-A or -is is accompanied by a marked fall in chloride excretion. and 10% of a single synthetic fat (stearin, palmitm, This fall is not recorded in the blood, the plasma, or laurin, and olein) fairly good growth is secured; the the stomach. Alkalosis is accompanied by a definite replacement of the fat- by an equal amount of the cor diminution in carbohydrate tolerance and sometimes responding acid fails to produce satisfactory growth. by a ketosis. This ketosis is not a “ washing-out ” Good growth of rats was secured on a fat-free diet effect, i.e., elimination of the ketonic acids hi associ of flesh, starch, salts, and vitamins-^, and -B and also ation with the excreted alkali, but is due to defective on a carbohydrate-free diet of protein, butter-fat, carbohydrate utilisation. The ketosis of starvation salts, and vitamins-/! and -B. E. A. L u s t. is much increased in alkalosis and the maximum excretion of ketonic acids does not necessarily coincide Is the metabolism of sterols related to that of with the maximum output of alkali in the urine. The fats ? E. F. T e r r o i n e , R. B o n n e t , G. K o p p , ana ketolytic action of dextrose in starvation is markedly J. V e c h o t (Bull. Soc. Chim. biol., 1927,9,678—691). diminished by ingestion of alkali and so is also the When the total f a t of animals has been increase action of insulin. From experiments in rats it is by rich nutrition, there is no increase in cholestero, found that the deposition of glycogen in the liver and in bacteria rich in f a t , whether n a tu ral!} or as and muscle is diminished by alkalosis. a result of culture on media containing much dextrose, S. S. Z i l v a . there is no parallelism between their conten Fat and lipin metabolism. IV. Role of the of fatty acids and of sterols. Such facts sugge^ reticulo-endothelial system. V. Role of the independence of the metabolism of fats and of stero • spleen. S. L e i t e s (Biochem. Z ., 1927, 186, 391— On the other hand the germination of certain see 412, 430— 450).—IV. Experiments have been carried is accompanied by a decrease in fatty a cid s a a out to determine the effect of “ blocking ” the reticulo increase' in phytosterol, whilst Aspergillus mge endothelial systems by intravenous injection of richer hi sterols when cultivated on fatty ma e colloidal silver, colloidal iron, or Indian ink on the fat, than when grown on dextrose or peptone. cholesterol, and lipin of the blood. Simple blocking W. O. K e r m a c k . with the colloidal solution causes a conversion of the Effect of irradiation on fat metabolism. ■ first type of lipmmia into the second type (cf. this K u l t j u g i n (Biochem. Z., 1927, 186, 36—-4 -)- vol., 695) and splenectomy has a similar effect. The effect of irradiation on the weight, the total m '■ » • lipsemia and cliolesterolajmia, resulting from the inorganic phosphorus, calcium, potassiiini» c, administration per o s of large amounts of olive oil, magnesium contents of the urine and on the o- lecithin, oleic acid, or olive oil-j-cholesterol, are less cholesterol, inorganic phosphorus, organic phosp BIOCHEMISTRY. 899 calcium, potassium, and magnesium of the blood of decrease, after which the continued intake of potassium rabbits is tabulated. In blood, the total fat is greatly has little or no effect on the excretion. The converse increased, and the cholesterol and inorganic phos takes placc on withdrawing the salt. Observations phorus to a less degree. P. W. Clutterbuck. on the sodium excretion do not support the theory Relationship between amino-acids and bile of sodium impoverishment consequent on increased acids in fat digestion in the intestine. R . K a r a - potassium intake put forward by Bunge as the result saw a (J. Biochem. [Japan], 1927, 7, 117— 127). of experiments on himself. S. S. Zilva. Chemical Abstracts. Minimum mineral requirements in cattle. A. Effect of bile acids on the protein and purine T i i e i l e r , H. H. G r e e n , and P. J. d u T o i t (J. Agric. metabolism and the significance of choleic acid. Sci., 1927, 17, 291—314).—Experiments with regard R. K a r a s a w a (J. Biochem. [Japan], 1927, 7, 145— to the minimum requirements of growing cattle for 519).—Injection of bile acids into rabbits inhibits the calcium, phosphorus, sodium, potassium, and chlorine protein metabolism and stimulates the purine meta are recorded. Special attention was given to phos bolism. The effect of cholic and deoxycholic acids phorus deficiency, and “ aphosphorosis,” or clinically is much greater in this respect than that of stearin- recognisable phosphorus deficiency disease, was choleic acid. The degenerative changes in cells experimentally produced, and shown to be identical during stasis icterus are ascribed to the toxic action with the naturally occurring South African disease, of the bile acids which strongly stimulate the purine “ Styfsiekto.” Minimum requirements for growth metabolism. Choleic acid influences the protein and are higher for phosphorus than for calcium, and a purine metabolism to a much smaller degree than ratio as high as 3P20 5: ICaO is not necessarily dis deoxycholic acid in post mortem autolysis. The advantageous. Requirements for sodium and chlorine formation of choleic acid from the deoxycholic acid are low. No evidence was obtained that excess of present in the liver is regarded as a process of detoxic basic over acidic constituents was necessary. The ation of the latter. Chemical Abstracts. composition of the milk of animals suffering from aphosphorosis need not necessarily be abnormal, but Fate of heterocyclic compounds in the animal the inorganic phosphorus of the blood may drop to a body. N. J. Novello (J. Biol. Chem., 1927, 74, quarter of the normal, the calcium of the blood 33—36).—After administration to rabbits, pyridine remaining unaffected. C. T. Gimingham. was excreted entirely unchanged; glyoxaline was for the most part unchanged but gave rise to a small Influence of concentration on the loss in weight increase in uric acid excretion; pyrrole was eliminated of young fasting eels in sodium chloride solution. unchanged to the extent of 40—50%, the remainder U. D’A n c o n a (Atti R. Accad. Lincei, 1927, [vi], 5 , being accounted for by an increase in the carbamide 693—696).—Data are cited for the weight of young excretion. C. R. Harington. eels under normal conditions of growth and for the following characteristics of young fasting eels in Effect of composition of diet on the urinary pure water, and in 0-5, 1-0, 3-0, and 5-0% sodium C: N ratio with special reference to amino- chloride solutions : mean length, mean weight, mean acids. A. B i c k e l and I. R e m e s o v (Biochem. Z., dry weight, and mean ash. The percentage loss in 1927, 1 8 6 , 54—63).—When a portion of the normal mean weight diminishes from 15-61 in pure water to protein of a dog’s diet is replaced by an amount of 11-21 in 1% sodium chloride solution, and then rises amino-acids equivalent in nitrogen content, the to 28-81 in 5% sodium chloride solution; the ratio of absorption in the intestine of nitrogen and carbon is dry to total weight shows a minimum at 0-5% sodium more complete and the urinary C : N ratio increases. chloride solution, a maximum at 1% ; the ratio of The amount of protein metabolised is not increased ash to total weight shows a minimum at 6% sodium and the excess of nitrogen is retained. chloride solution. R. W . L i j n t . P. W. Clutterbuck. Influence of administration of active iron oxide Diurnal variation of the gaseous constituents on metabolism with special reference to nitro of river waters. R. W. Butcher, P. T. K. P e n t e - gen equilibrium and the behaviour of the l o w , and J. W . A. W o o d l e y (Biochem. J., 1927, 21, 945—957).—In the water of the rivers Lark and binary quotient. I. R e m e s o v (Biochem. Z., Itchen the dissolved oxygen and the pn are at maxi 191.7, 1 8 6 , 64—86).—Administration of “ active ” won oxide to dogs usually produces a retention of mum during the day, whilst ammoniacal nitrogen is nitrogen due to decreased oxidation of protein together at a minimum. The reverse is observed at night, with a better utilisation of the food in the intestine. since in the process of diurnal photosynthesis the plants liberate oxygen which removes the ammonia e oxide also appears to modify the oxidation of lats and carbohydrates (cf., A., 1926, 1057). produced by the decay of organic matter. At night, on the other hand, not only is there a cessation in the - P. W. Clutterbuck. production of oxygen, but also any residue of this gas influence of variations in the sodium : potass ium ratio on the nitrogen and mineral metabol- is being utilised in the nocturnal respiration of river organisms. S. S. Z i l v a . m of the growing pig. II. M. B. R i c h a r d s , W. 971—qs- and A‘ D' Husband (Biochem. J., 1927, 21, Blood-fat and exercise. J. W . T. P a t t e r s o n rat' * addition of potassium citrate to a (Biochem. J., 1927, 21, 958—966).—I here is a lon cereal grain fed to growing pigs decreases remarkable constancy of the fasting blood-fat content ^ / ss™ ° n and retention of nitrogen, phosphorus, for the same individual, but after severe exercise there calcium. There is an immediate increase in the is a definite increase. If, however, the individual rJ excretion of chlorine followed at once by a receives 100 g. of dextrose per os prior to the muscular 900 BRITISH CHEMICAL ABSTRACTS.----A. exertion this increase is not observed. The blood- panying the fall in blood-sugar. If a poisonous dose cholesterol content is unaffected by the exercise. of “ synthalin ” is given, the inorganic phosphorus S . S. Z i l v a . rises sharply. Lactic acid increases in the blood of Effect of cooling on muscle. I. Biochemistry sheep after “ synthalin” administration. The toxic of frozen fish. II. Creatine and creatinine in symptoms which often develop are reminiscent of albino-rat muscle. H. A k a t s u k a (J. Biochem. guanidine poisoning. H. D. K a y . [Japan], 1927, 7 , 27—39, 41—51).—I. When carp is Intoxication with com m ercial methyl chloride. frozen at —1° to —3°, or —10° to —13°, no change in H. M. B a k e r (J . Amer. Med. Assoc., 1927, 8, 1137— the total or residual nitrogen content of the muscles 1138)—Commercial methyl chloride, which may be takes place; freezing at —24° for 20 mm. decreases absorbed by respiration in toxic amounts, is cumul the creatine content by 19%. ative in action. It may be detected in the urine as II. Freezing at —3° to —20° for 2 hrs. causes a ammonium formate before symptoms of intoxication slight mcrease, and for 6 hrs. a diminution of 8% in develop. A. A. E l d e id g e . muscle creatine. In moderate curare paralysis the diminution is 7%. Freezing curarised albino-rat Toxic effects of ethylene dibromide. B. G. H. muscle for 6 hrs. causes a decrease of 22—23%. T h o m a s and W. P. Y a n t (U.S. Pub. Health Rep., 1927, C h e m i c a l A b s t r a c t s . 4 2 , 370—375).—Ethylene dibromide (0-25 c.c.) applied Effect of increased calcium intake on dystro to the abdomen of rats or inhaled (0-8% for 30 min., phic renal calcification in rabbits. I. R e m e s o v 0-4% for 60 min., or 0-2% for 150 min.) causes (Biochem. Z., 1927, 1 8 7 , 51—56).—Administration death within 24 hrs. C h e m i c a l A b s t r a c t s . of calcium salts by any route caused an increase in Toxicity of phenylarsinic acids for Balan the calcium content of the kidneys of normal rabbits. tidium coli, M alm., in cultures in relation to When one kidney was ligated the process of calcific their chemical constitution. A. S. Co r b e t and ation was accelerated by intravenous or subcutaneous, A. P. J a m e s o n (Biochem. J ., 1927 , 2 1 , 986—990).— but not by oral, administration of calcium salts. The toxicitics of the sodium salts of a number of these C . R . H a r i n g t o n . acids are tabulated. Amino- and hydroxy-phenyl- Physico-chemical basis of the action of the arsinates aro toxic in dilutions above 1/20,000, sodium phenol-camphor medicaments. F. M ü l l e r , P . 3-hydroxy-l : 4- benzisooxazine-6-arsinate, sodium G ü n t h e r , and M . P e i s e r (Arch. exp. Path. Pharm., JV-glycineamidophenylarsinate, sodium 5-acetamido- 1927, 1 2 4 , 41—58).—The m. p., d, and nu of 4-hydroxyphenylarsinatc in dilutions below 1/10000, mixtures of phenol and camphor in varying pro whilst sodium 5-acetamido-2-hydroxyphenylarsmate portions have been determined. It is concluded that and sodium 8-acetamido-3-hydroxy-l : 4-benztso- the phenol-camphor mixture used medicinally is a oxazine-6-arshiate are not toxic in dilutions of 1/500 very loose molecular compound which is readily and only very slightly so in 1% dilutions. dissociated in contact with water, giving rise to an S. S. ZlLVA. aqueous phase containing phenol in approximately Differential analysis of heart poisons. V. constant (1*3%) concentration, the camphor being Action of magnesium, strontium, and barium precipitated in a very finely-divided condition. chlorides on stimulus formation in the heart of W. 0. K e r m a c k . cold-blooded animals. B. K i s c h (Arch. exp. “ Sympathol,” a new adrenaline-like sub Path. Pharm., 1927, 1 2 4 , 210—230).—A pharma stance. Constitution and pharmacodynamical cological investigation of the action of the abo\e action. F. L a s c h (Arch. exp. Path. Pharm., 1927, salts on stimulus formation in the shark’s heart. 1 2 4 , 231—244).—“ Sympathol ” (methyl-a-hydroxy- W. 0. K e k m a c k . ß-p-hydroxyphenj’lethylamine hydrochloride), m . p. Purgative action of hydroxyanthraquinones. 154°, has pharmacological properties resembling those H. F ü h n e r and J . d e D io s F e r n a n d e z (Arch. exp. of adrenaline, although there are quantitative and Path. Pharm., 1927, 1 2 4 , 185— 191).—The purgative qualitative differences. W. 0. K e r m a c k . action has been determined, on white mice, of seven dihydroxy- and four trihydroxy-anthraquinones as we Action of ‘ ‘ synthalin ’ ’ in the animal organism. as of 1 : 8-dihydroxy-3-methylanthraquinono (ehryso- P. E. S i m o l a (Z. physiol. Chem., 1927, 168, 274— phanol, chrysophanic acid) and 1:6: 8-trihydroxy-o- 293).—It has been claimed (Northmann and Wagner, methylanthraquinono (rhcumcmodiri). 5 2 , Deut. med. Woch., 1926, 2067) that “ synthalin,” W. O. K e r m a c k . a synthetic guanidine derivative, is of great value as a Toxicity of zinc. V . G. H e l l e r and A. D- substitute for insulin in the treatment of diabetes, B u r k e (J . Biol. Chem., 1927, 7 4 , 85—93).—Addition particularly since it may be effectively given by the of metallic zinc, zinc oxide, or soluble zinc salts to e mouth. The result of the administration of this diet of rats in amounts up to 0-5% caused no Pat“0' substance on the concentration of reducing substance, logical symptoms and no significant increase ui lactic acid, and inorganic phosphorus in the blood of zinc content of the viscera. Contamination of jooc goats and of rabbits has been investigated. “ Synth with zinc from zinc containers appears, there ore, alin ” administered either by the mouth or subcutane- not to be a clanger. C. R. H a r i n g t o n . ously differs from insulin in its effect on the blood-sugar, hypoglycemia being far less marked (hi some cases Mechanism of enzyme action. F. F. & obd scarcely perceptible), coming on after some hours, and (Nature, 1927, 120, S2—83).—Certain chemical com lasting longer. In most, but not all cases there is a pounds are capable of forming an adsorption fall in the inorganic phosphorus of the blood accom- on the. surface of enzymes which acts as protec BIOCHEMISTRY. 901 So-called “ activators are really protectors, pro gallodeoxycholic, deoxycholic, and hyodeoxycholic tecting the enzyme from the damaging effect of acids. Chemical Abstracts. intermediate or final products of the reactions concerned. A. A. E l d r i d g e . Enzyme action. XLV. Lipase action of the whole trout at different ages. K. G. F a l k , H. M. Conditions of autolytic ammonia formation in N o y e s , and I. Lorberblatt. XLVT. Ester-hydro tissues. III. Relation of tissue ammonia to lysing actions of whole trout preparations under purine metabolism. P. G y o r g y and H. R o t h l e r various conditions. H. M. Noyes, I. Lorber (Biochem. Z., 1927, 187, 194—219).—Extracts of b l a t t , and K. G. F a l k (J. Gen. Physiol., 1927, 1 0 , liver, kidney, muscle, and thymus (but not blood) are 837—844, 845—851; cf. A ., 1925, i, 1360; this vol., able to eliminate ammonia from sodium nucleate 227).—The ester-hydrolysing actions of extracts and and from adenosine; the course of the reaction is total solids of trout eggs and whole trout of various similar to the liberation of ammonia which takes ages have been ascertained, ten different esters being place in the tissues alone as the result of autolysis. used as substrates. The type of diagram which The optimum pa for the reaction is 5-2—5-5 except represented the relative ester-liydrolysing powers in the case of muscle, for which it is 7-0—8-0. The varied from that characteristic of immature eggs to experiments indicate a relationship between form that given by the adult fish after they had eaten ation of ammonia in tissues and purine metabolism. for a few weeks, and henceforward it remained con C. R. Harington. stant for 4—5 years. The influence of the hydrogen- Nucleosidases. I. H. von Euler and E . ion concentration on the activity of the enzymes has B ru n iu s (Ber., 1927, 6 0 , [B], 1584—1591).—Nucleo been investigated, and also the effect of using various sidase is obtained by extraction of pig kidney with solvents such as glycerol or sodium chloride solutions water and purified to some extent by dialysis or, instead of water for the preparation of the extracts. preferably, by isoelectric precipitation combined with W. O. K e r m a c k . dialysis. Kaolin is unsuitable as adsorbent, whereas Amount of light emitted by mixtures of aluminium hydroxide B at pa 5—6 effects 75% Cypridina luciferin and luciferase. K . P. adsorption; subsequent elution is difficult. Pre S t e v e n s (J. Gen. Physiol., 1927, 1 0 , 859—873).—A cipitation with alcohol and colloidal ferric hydroxide photometric method is described for the determin effects adsorption of the enzyme, which is not recovered ation of the amount of light produced per c.c. of the by means of phosphate or alkali. The best puri luciferin solution containing luciferase and from the fication is effected by combination of precipitation results the amount of light emitted by 1 g. of dried with acetone and isoelectric precipitation. Activity Cypridina powder has been calculated. This amount is measured by using adenosine as substrate, the varies slightly with the concentration of luciferin liberated ribose being determined. The enzymic and also markedly with the nature of the medium, action of nucleosidase is restricted by nucleic and being maximal in neutral sea-water and minimal wie acids but appears to be unaffected by arabinose. in distilled water saturated with hydrogen. It also Apparently the amino-group of adenosine and the decreases slightly as the concentration of luciferase primary alcoholic group of ribose are not essential is increased. W. O. K e r m a c k . for the specific union of adenosine and the nucleosidase. Quanta of light produced and the molecules of H . W r e n . oxygen utilised during Cypridina luminescence. Phosphoric and lactic acid production in E. N . H a r v e y (J. Gen. Physiol., 1927, 1 0 , 875— pulped glands. F. K r a u s e (Z. physiol. Chem., 881).—From measurements of the oxygen absorbed 1927, 168, 216—232).—If pulped glands (liver, during the oxidation of luciferin with production of pancreas, salivary gland) are incubated in sodium light, it is found that lM x lO -5 g. of oxygen is hydrogen carbonate solutions at 42°, phosphoric and utilised for each lumen of light produced or that lactic acids are produced. As a rule there is a greater 88 mols. of oxygen correspond with the emission of molecular quantity of the former acid. In presence one quantum of light of 4800 A. (the wave-length of of sodium fluoride, although acid production is maximum intensity). This result may be too high, checked, there is no synthesis of phosphoric ester, and and it is probable that for each quantum of light it is concluded that a substance similar to lactacidogen produced about 50 mols. of oxygen are absorbed and is not present in these glands. Nucleic acid, present 100 mols. of luciferin oxidised. Of the energy m considerable quantities in the fresh tissues, is produced, 1% is converted into light. believed to be the source of both the phosphoric and * W . 0 . K e r m a c k . the lactic acid. H . D . K a y . Efiect of cyanide on the Schardinger enzyme. Behaviour of bile acids in the digestion of M. D i x o n (Biochem. J., 1927, 840—843).—Inhibition protein. R. K a r a s a w a and M. S h o d a (J. Biochem. of the aerobic oxidation of aldehyde by the Schar [Japan], 1927, 7, 129—143).—Bile acids exert no dinger enzyme is produced only by concentrations noticeable effect on protein hydrolysis. They have a of cyanide greater than M/200. It is due to an actual ejiressing effect on the tryptic digestion of protein, destruction of the enzyme itself, and not to the .I l™> however, is lessened wrhen the bile acids are in inactivation of the iron, which acts catalytically on alf state. The protein digestion by erepsin is molecular oxygen in accordance with Warburg’s ac'°l to a variable degree by different bile theory (cf. Szent-Gyorgyi, A ., 1926, 867). !.s' ihus, cholic acid has the strongest depressing S- S..ZlLVA. °n the peptide cleavage, whilst the other Hydrolysis of sucrose by invertase in very ac exert a diminishing effect in the order: concentrated solutions. C . D. I n g e r s o l l (Bull. 902 BRITISH CHEMICAL ABSTRACTS.----A. Soc. Chiin. biol., 1927, 9, 838—840).—Polemical this system, the fermentation of pyruvic acid in their against Achalme (A., 1926, 977). W. 0. K e r m a c k . presence proceeding almost as rapidly as in the Alcoholic fermentation. XIII. Non-exist (unbuffered) dextrose controls. H. D. K a y . ence of cell-free fermentation. S . K o s t y t s c h e v , Fermentation of sugar and pyruvic acid. A. G. M e d v e d e v , and H. K a r d o -S y s o j e v a (Z. physiol. L e b e d e v (Biochem. Z., 1927, 186, 376—377).— Chem., 1927,168, 244—266).—Alcoholic fermentation Mainly deals with priority questions. The author by dried yeast or by extracts of dried yeast is due, cannot support the statement (Hagglund and not to so-called “ cell-free fermentation ” but to the Augustson, A., 1926, 543; Hagglund and Alilbom, presence of relatively small numbers of surviving this vol., 379) that on occasions the zymase may still cells, the activity of which is extraordinarily stimulated be active, even when the carboxylase is inactive. by unknown substances derived from the killed cells. A. W o r m a l l . The fermentative activity of such preparations is a Fermentation of pyruvic acid. C. N eu berg function of the number of living cells present. These and E . S im o n (Biochem. Z., 1927, 187, 220—253).— findings explain many anomalies in current view's on The theory of the intermediary part played by pyruvic “ cell-free fermentation.” H. D. K a y . acid hi alcoholic fermentation is supported by the fact that, under the appropriate conditions, all Fermentation of glycogen and starch by malt- preparations of yeast can ferment pyruvic acid more ase-free yeast. A. G o t t s c h a l ic (Z. physiol. Chem., rapidly than dextrose. The failure of other workers 1927, 168, 267—273).—Dried, washed S. Ludwigii, to secure this result is due to neglect of such con which does not attack maltose, will nevertheless siderations as the effect of pn, the difference of per ferment glycogen readily, and soluble starch less meability of the yeast-cell towards dextrose and readily, if relatively large amounts of co-zymase are pyruvic acid, and the toxicity of high concentrations present (boiled extract of fresh bottom yeast used). of the latter towards yeast. C. R. II a r in g t o x . Dextrose appears to be produced by such yeast preparations from both these substances without the Purification of co-zymase. A. L . R a y m o n d and intermediate formation of maltose. The production H. M. W i n e g a r d e n (J. Biol. Chem., 1927, 74, 175— of phosphoric esters, which is dependent on the 188).—Solutions of co-zymase were prepared by presence of co-zymase, is an essential step in the extracting yeast with hot water; electrodialysis, fermentation of glycogen by S. Ludwigii. precipitation with alcohol, cadmium hydroxide, or H. D. K a y . ferric hydroxide, caused no purification. Treatment Influence of different carbohydrate phosphoric with lead acetate gave variable results and the esters on the fermentation of dextrose. P. experiments of von Euler and Myrback (A., 1924, i, M a y e r (Biochcm. Z., 1927, 186, 313—316).—All 918) could not be repeated. By precipitation of the the known carbohydrate monophosphoric esters co-zymase with excess of mercuric chloride or nitrate accelerate the commencement of fermentation, those or silver nitrate and recovery by decomposition of of Neuberg and of Robison having the greatest effect. the precipitates with hydrogen sulphide, a 4- or P. W . C l u t t e r b u c k . 5-fold increase in activity was obtained, which was, Graded phytochemical reduction. G. N a g e l - however, accompanied by considerable loss of material. s c h m i d t (Biochem. Z., 1927, 186, 317—321).—Di- Preliminary treatment of the crude extract with lead acetyl added to a fermenting sugar solution is con acetate, followed by adsorption of the co-zymase in verted fairly rapidly into acetylmethylcarbinol, which the filtrate on aluminium hydroxide at pn 10, and is then much more slowly reduced to ¡3y-butylene glycol. recovery from the adsórbate with hydrochloric acid P. W. C l u t t e r b u c k . at 2>n 6-0, gave a 9-fold purification and better yields. Fermentation of a-ketobutyric and oxalacetic C. R. Haringtox. acids. VII. Dependence of alcoholic ferment Co-zymase. XII. Molecular weight of co v o n E u l e r , Iv . M y r b a c k , ation on p a. E. H a g g l u n d and A. R i n g b o m (Bio zymase. H. and R. chcm. Z., 1927, 187, 117— 119).—The velocity of N il s s o n (Z. physiol. Chem., 1927, 168, 177—187).-- fermentation of a-ketobutyric acid by yeast is greatest From observations on the fate of free diffusion of at ps 4-3, and that of oxalacetic acid at pK 4-6; neither co-zymase in an apparatus adapted by Euler (Wied- acid is fermented at all below j)a 3-0 or above pH 8-0. Aim., 1897, 63, 273) and by Oholm (A., 1910, ii, 273) The pa range of activity of carboxylase appears there for the determinations of the mol. wt. of dissolved fore not to be dependent on the substrate. substances, that of co-zymase has been found to be 4S6¿6. This mol. wt. is constant for very different C . R . H a RINGTON. Yeast fermentation. III. Pyruvic acid. H. degrees of purity of co-zymase, and does not change with the acidity of the diffusing solution. The con H a e h n and M. G l a u b i t z (Z. physiol. Chem., 1927, 168, 233—243).—Sodium pyruvate in presence of centration of co-zymase was determined by its eneet excess of yeast only gives rise to minimal quantities on carbon dioxide production in co-zymase-free v«la of carbon dioxide. 1% pyruvic acid rapidly kills under standard conditions. Li the same apparatus yeast-cells. If, however, disodium hydrogen phos sucrose gave a mol. wt. of 336¿S . H. D. K a y . ^ phate is added in increasing quantities to 1% pyruvic Extraction of maltase from yeast. "V. K acid, increasing speeds of fermentation are observed I v r i e b l e , E. L. Skau, and E. W. L o v e r in g (J. Amer. when yeast is added. The proportion of yeast-cells Chem. Soc., 1927, 49, 1728—1735).—The rate ot which survive the process rises with increase in the extraction of maltase from dried yeast increases wi added phosphate. Lysine hydrochloride-j-sodium rise in temperature, but stronger^ extracts can D hydroxide, and glycine both act as good buffers for obtained at lower temperatures (15°) as the rate BIOCHEMISTRY. 903 destruction of the maltase is less. The maximum of surface tension between the medium and air or activity is obtained when the extracting medium is the medium and benzene. The type of growth neutral, but this effect is less marked with fresh than (film or deposit) is correlated with change in interfacial with dried yeast. The rate of extraction of maltase tension of the medium against benzene. from fresh yeast is less than that from dried yeast, S. S. Z i l v a . but maltase is best extracted from fresh yeast at 30°. Mechanism of the action of fatty acids and F. particularly of G. the W unsaturatedi l l s o n . acids and of their Unsaponifiable m atter of yeast-fat. C. G. soaps on bacteria and toxins. P . S e d a l l i a n and Da u b n e y and I. S. M a c l e a n (Biochem. J., 1927, 21, L. V e l l u z (Bull. Soc. Chim. biol., 1927, 9, 825— 869; cf. this vol., 373).—The iodine values of the 837).—From experiments on the neutralisation of unsaponifiable matter vary widely according to the tetanus toxin by various fatty acids and soaps, it is particular sample of yeast and according to the concluded that the formation of cryptotoxins is method used for the preparation of the fraction. After dependent on the adsorption of these acids on the removal of the sterol precipitable by digitonin an toxin-micelles in such a way as to inhibit their action oil may be obtained giving a very high iodine value, on the animal organism. W. O. K e r m a c k . the degree of unsaturation being very largely in Quantitative dismutation of methylglyoxal fluenced by the method of saponification and by the to lactic acid by Bacillus Delbriicki and by subsequent treatment of the material. S. S. Z i l v a . Bacterium lactis aiirogencs. Irregular be Iodine as a biogenic element. XI. Action of haviour of phenylglyoxal in this reaction. C. iodine on yeast. K. S c h a r r e r and W. S c h w a r t z N e t jb e r g and E . S im o n (Biochem. Z ., 1927,186, 331— (Biochem. Z., 1927, 187, 159— 179).—Iodine in small 336).—B. Delbriicki and B. lactis aerogenes convert concentrations has a slight stimulating effect on the methylglyoxal quantitatively into r-lactic acid but, growth of yeast, the iodine being taken up to some although both convert phenylglyoxal quantitatively extent by the yeast-cells; it does not appear, how into mandelic acid, the former gives rise to a product ever, to be of great significance in yeast metabolism. containing 82% of the d-acid whilst the latter gives a C. R. H a r i n g t o n . product containing 10% excess of the ¿-acid. Necessity of carbon dioxide for the growth of P. W. C l u t t e r b u c k . bacteria, yeasts, and moulds. G. E. R o c k w e l l Vitamins and tubercle bacilli. I, II. N. and J. H . H i g h b e r g e r (J. Infect. Dis., 1927, 40, U y e i (J. Infect. Dis., 1927, 40, 425, 433).—Growth- 438).—Experiments indicate that bacteria, yeasts, and stimulating substances could not be found in tubercle moulds require carbon dioxide as a source of carbon. bacilli or their metabolic products. Substances rich C h e m i c a l A b s t r a c t s . in vitamin-!? stimulate the growth of tubercle bacilli Physico-chemical antagonisms of bacteria. in Long’s medium. C h e m i c a l A b s t r a c t s . C. Aenatjdi, W. K o p a c z e w s k i , and M . R o s n o w s k i Influence of thyroid on the stimulation of (Compt. rend., 1927, 185, 153—156).—The antagon autonomic nerves and on the action of adrenaline. ism between different species of bacteria present W. F e l d b e r g and E . S c h l if (Arch. exp. Path. together in a culture medium is explainable by Pharm., 1927, 124, 94— 101).—Thyroxine and other variations in certain physical properties of the thyroid preparations have no immediate action in medium. T. H. P o p e . increasing the effect of adrenaline in raising the blood- Relation of the growth of certain micro pressure. Likewise they do not intensify the action organisms to the composition of the medium, of vagus stimulation in lowering the blood-pressure b The synthetic culture medium. II. The nor the effect of stimulating the cervical-sympathetic effect of changes of surface-tension on growth. in dilating the pupil. W. O. K e r m a c k . V. R e a d e r (Biochem. J., 1927, 21, 901—907, 90S— Fat metabolism. I. A. Low and R. P f e i l e r 912).—I. Traces of manganese or iron do not increase (Biochem. Z ., 1927, 187, 114— 116).—Injection of the rate or amount of growth of Streptothrix corallinus, 0-4 mg. of adrenaline into rabbits causes a slight a white Streptothrix, and Sarcina aurantiaca. No decrease in the light petroleum-soluble and a marked appreciable variation hi the growth of these organisms increase in the alcohol-soluble fraction of the blood- takes place when the medium contains dextrose within lipins. C. R. H a r i n g t o n . be range 0-06—2%. Glycerol, mannitol, arabinose, Determination of adrenaline. L. C. B a k e r and sodium lactate, sodium citrate, sodium pyruvate, or G. F. M a r r i a n (Biochem. J., 1927, 21,1005— 1009).— g ycogen may replace dextrose as a source of carbon A modification of Folin, Cannon, and Denis’ method vi bout loss of efficiency in the medium. The sub- (A., 1913, ii, 163). Comparisons arc made in a s ltution. by lsevulose, rhamnose, sodium acetate, Lovibond colorimeter and a calibration curve is if propionate diminishes the growth, whilst utilised, the working temperature bemg 20°. In the e butvrate, oxalate, succinate, or tartrate cannot extraction by the Folin, Cannon, and Denis ;method as a source of carbon at all. Of the amino-acids there is small but definite oxidation of adrenaline. C,Ule’ asparagine, alanine, and possibly cystine This can be avoided by using trichloroacetic acid as but" SU % ^le carf)0n requirements of the medium the extracting agent. S. S. Z i l v a . onone °f the amino-acids tried acted as efficiently Trmr™omum salts in providing nitrogen, Efiect of insulin on the sugar excretion thres medium 6 a“ 0Unt Sro"'th of Streptothrix in synthetic hold and its after-efiect on sugar assimilation. connon* C? am’ng additions of broth or antineuritic G. E d a (J. Biochem. [Japan], 1927, 7, 53—77).— rates (torulin) is not related to the change After the first insulin injection the threshold of sugar 904 BRITISH CHEMICAL ABSTRACTS.— A. excretion is often lowered; after several consecutive 21, 940—944).—The minimum quantity of cod-liver days’ injections it usually rises (e.g. 0-04%), but the oil required for rearing chicks is 0-5% of the diet. effect is variable. Long-continued insulin injections There are indications that a higher percentage is diminish the assimilability of sugar, but the effect necessary for hens in order to ensure the production rapidly disappears when the injections are discon of fertile and hatching eggs. S. S. Z i l v a . tinued. C h e m i c a l A b s t r a c t s . Antineuritic yeast concentrates. II. Use of Insulin and glycogen formation. K. P o g a n y norite charcoal in the concentration of torulin. (Biochem. Z., 1927, 187, 72—77).—In mice weighing H. W. Iv x n n e r s l e y and R. A. P e t e r s (Biochem. J., 17—25 g., doses of 0-004—0-006 unit of insulin have 1927, 21, 777—790).—The aqueous extract from yeast no effect on the total glycogen content; 0-01—0-02 is precipitated with neutral lead acetate. By treating unit causes an increase, whilst larger doses cause more the filtrate with baryta gum impurities are further or less complete disappearance of the glycogen. removed. After removing the baryta from the C. R. H a r i n g t o n . solution with sulphuric acid more impurities are Variations in the serum-calcium of rabbits. precipitated with mercuric sulphate. The solution K . C u l h a n e (Biochem. J ., 1927, 21, 1015— 1023).— is then adsorbed with norite at pn 7-0 twice and the The administration of insulin whether pure or crude active principle extracted from the adsorbent by causes no rise in the serum-calcium of rabbits, nor extraction with 0-lAr-hydrochlorie acid and with 50% can such a rise be recorded during insulin convulsions alcohol. The highest yield obtained by this method (cf. Davies, Dickens, and Dodds, A., 1926, 980). An from 14 lb. of yeast was 4400 doses of about 1 mg. immediate rise in the serum-calcium occursindependent The treatment with mercuric sulphate can be avoided of insulin administration in rabbits fed with cabbage if the solution is brought to pa 2-5 after treatment except when the initial value is exceptionally high. with baryta, and after removal of the reagent S. S. Z i l v a . the solution is adsorbed with norite. At this ps Vitamin-yl formation in the etiolated wheat the adsorbent removes impurities. By bringing the shoot. T. M o o r e (Biochem. J., 1927, 21, 870— solution to pn 7 after this purification, the fractionation S74).—Fresh etiolated wheat shoots, 10 days old, can be continued as before; the yield, however, is not fed to rats receiving a diet deficient in vitamin-./! as good as that obtained by the first method. Adsorp but adequate in vitamin-D at the rate of thirty shoots tion on norite charcoal is not a property of torulin of per day, prevent death and restore growth. Seeds activity 1-0 mg. per daily dose and is therefore due to fed at the same rate are ineffective. The condition to a co-adsorbent in the earlier stages. of the animals after a few months is, however, not S. S. Z i l v a . as good as that of animals subsisting on a liberal diet Tem porary spontaneous disappearance of (cf. Wilson, J. Biol. Chem., 1922, 51, 455; Coward, typical * * beri-beri ’ ’ symptoms in pigeons fed on this vol., 595). S. S. Z i l v a . diets deficient in vitamin-jS. S. K. K on (Bio Vitamin-yl and greenness in plant tissue. I. chem J., 1927, 834—836).—The occurrence of tem Relative vitamin-/l content of head and leaf porary spontaneous cures in a large percentage of pigeons fed on a vitamin-5-deficient but otherwiso lettuce. M . D y e , O. C. M e d l o c k , and J. W. C r i s t (J. Biol. Chem., 1927, 74, 95— 106).—The vitamin-^4 complete synthetic ration is fully confirmed (cf. Kon content of the leaves of lettuces of various modes of and Drummond, this vol., 702). S. S. Zilva. cultivation was approximately proportional to their Effect of administration of glycine t o pigeons chlorophyll content. C. R . H a r l n g t o n . on a diet deficient in vitamin-1?. S. K . K o n (Bio Detection of the antirachitic factor in grasses chem. J., 1927, 21, 837— 839).—Administration ot grown in the dark and under glass. W. V o l t z glycine has no beneficial effects on pigeons fed on and W. K i r s c h (Biochem. Z., 1927,186, 255—263).— diets deficient in vitamin-5. Bad effects were Grass seeds (Lolium perenne) do not contain the observed on the administration of the amino-acid an antirachitic factor, but the germinating plants do, these are attributed to the high molecular concen even when grown under glass or in complete darkness. tration of the solution given. Collazo’s opinion (i •> This is opposed to the view that the antirachitic 1923, i, 506) that carbohydrates when admnusterea vitamin is formed only by irradiation of a provitamin. to vitamin-¿-deficient pigeons are toxic per se is no Z il v a . P. W. C lutterbttck . corroborated. S. S. Vitamins-/1 and -D of spinach. S. G. W i l l i - Different behaviour of pigeons and hens on m o t t and F. W o k e s (Biochem. J., 1927, 21, 887— supplying their vitamin-jB requirements y S94).—A stable acetone-etlier extract of dried spring fresh green plants. A. S c h e u n e r t and spinach was prepared which in daily doses of 25 mg. S c h i e b l i c h (Biochem. Z., 1927, 186, 222—--¿8). secured complete freedom from xerophthalmia and Pigeons require a much greater amount of gre<- induced satisfactory although slightly subnormal material e.g., sugar-beet leaves, grass, lucerne, growth in rats. A dose of this order, however, did certain acid fodders, than do hens, in order to sa not show any significant antirachitic protection. The their requirements of the antineuritic factor, extract is practically free from mineral matter and this large amount cannot be administered satisfac or y, oxidising enzymes. S. S. Z i l v a . pigeons are unsuitable for testing plant materia an Nutrition. VII. Fat-soluble vitamin require must not be c o n c lu d e d from n e g a t i v e experimen s _ _ ments of chickens. R. H. A. P l i m m e r , J. L. pigeons that such material is lacking in the antineu R o s e d a l e , and W. H. R a y m o n d (Biochem. J., 1927, factor. P. W. Clutterbttck . BIOCHEMISTRY. 905 Nutrition. VI. Balance of food by vitamin-jB. in the fresh condition, is rich in vitamin-C, 1 g. per R. H. A. P l u m m e r , J. L. R o s e d a l e , and W. H. diem being sufficient to protect guinea-pigs against Ra ym o n d (Biochem. J., 1927, 21, 913—939).—Pro scurvy. In scurvy there was observed a decrease in tein, fat, and carbohydrate in the diet need balancing the weight of the thymus and an increase in that of the by vitamin-!?, which must not fall below a certain adrenals. C. R. H a r i n g t o n . ratio to the calorie content. Chickens require more of the vitamin than pigeons, and pigeons more than Dietary requirements for reproduction. VIII. rats, per unit calorie, the requirement of young Reproduction-deficient diet. IX. Cod-liver oil animals being higher than that of adults. As tested versus wheat oil as sources of vitamin-JS. X. on pigeons “ marmite ” is about half as potent as Vitamin-J3 requirements for lactation. XI. dried yeast; samples of yeast extract vary consider Potency of butter-fat in vitamin-J3. B. S u r e ably in potency. Various pathological changes are (J. Biol. Chem., 1927, 74, 37-^4, 45—53, 55—69, produced by the consumption of diets containing too 71—84).—VIII. In contradiction to the results of little vitamin-B. The composite nature of vitamin-B Anderegg and Nelson (B., 1925, 520), the fact is con has not been taken into consideration in this research. firmed that on a diet of dried skimmed milk, cod-liver oil, and yeast, rats are sterile; addition to such a diet S . S . Z i l v a . Relation of protein intake to requirement and of 0-035% of the unsaponifiable matter from cotton seed oil secures a normal reproductive cycle. determination of vitamin-Ii. H. C. S h e r m a n and IX. Normal reproduction could not be obtained by 0. H. M. G l o y (J. Biol. Chem., 1927, 74, 117—122).— Neither the time of survival of rats after deprivation increasing the proportion of cod-liver oil in the above- of vitamin-B nor their maintenance requirements of mentioned basal diet, although the oil was rich in this vitamin were altered by changing the protein vitamins-.4 and -D ; large increases in the amount of content of the basal diet from 12 to 54%. oil caused toxic effects. X. The vitamin-JS requirements of rats are much C. R. H a r i n g t o n . increased during lactation. Preparations rich in Determination of vitamin-B. H . C. S h e r m a n vitamin-B were made by extracting wheat embryo and E. H . M a c A r t h u r (J. Biol. Chem., 1927, 74, 107—115).—In quantitative tests for vitamin-5 with 25% alcohol in the cold; such an extract pre carried out on young rats, the amount of vitamin- pared from 6 g. of wheat embryo formed a sufficient containing food should be adjusted until, in daily supply of vitamin-jB for the lactating rat. combination with the basal diet, it induces a Wheat-germ oil in amounts up to 5% of the diet was preliminary gain in weight followed by a slight fall non-toxic. and subsequently a steady period of some weeks. XI. Addition of 10% of butter-fat is required to Preliminary removal of vitamin-2? from the diet is of convert the basal diet into one sufficient for normal reproduction; butter-fat therefore contains much no advantage in testing for this factor. A t the same age, larger animals respond less readily than smaller less vitamin-2? than does wheat oil. ones to vitamin-B, whilst, under the same conditions C. R. H a r i n g t o n . of age and weight, females require larger amounts of Liberation of oxygen from fleshy-leaved plants in the absence of carbon dioxide. A. M a y e r the vitamin than males. C. R. H a r i n g t o n . (Landw. Versuchs-Stat., 1927, 105, 261—266).—A Content of glutathione in certain tissues, and discussion of the trend of modern research in this in the blood of the pigeon under normal con connexion, in comparison with the author’s earlier ditions, when underfed, and when deprived of views. A. G . P o l l a r d . vitamin-B. L. R a n d o i n and R . F a b r e (Compt. Special form of biological oxidation [of oxalic rend., 1927, 185, 151— 153).—-With the normal acid in presence of a moss]. J. H o u g e t , A. adult pigeon, the skeletal muscles contain, per 100 g. M a y e r , and L. P l a n t e f o l (Compt. rend., 1927, 185, <» fresh tissue, 0-017—0-032 g. (average 0-026 g.) 304—306).—Hypnum triquetrum suspended in dilute of glutathione; the heart, 0-030 g .; the liver, 0-140 g .; oxalic acid solution through which oxygen is passed and the blood, 0-061 g., with comparatively large causes at 25° complete oxidation in a few hours. The individual variations. Malnutrition causes a general action is not influenced by rise of temperature; it lowering of the content of glutathione, the average proceeds best at an acid concentration of 0-04—0-022V7, w the skeletal muscles being 0-0143 g. Deprivation and ceases if the acid is neutralised. The activity of of vitamin-# produces no marked change at first, but the moss is destroyed only by vigorous treatment; n.nfo? Bering of the proportion of glutathione to e.g., with water at a temperature above 96°, chlorine, «J ” 8- and, at the critical period, to 0-0139— osmic acid, picric acid, hydrogen peroxide, hypo WJ9 g. per 100 g. of skeletal muscle; with the sulphites, acid sulphites, iodides, ferro- and ferri-cyan- ? ^ the blood, the diminution is far less, and ides, and phenylhydrazine hydrochloride. Urethane, 1 the liver there is a tendency to increase. In- ohenyluretliane, and hydroc3Tanic acid have no action. skTf f 1 va^uc the ratio n' : n in the case of r E. W . W i g n a l l . witu , , musc\e ’s pronounced when vitamin-jB is Respiration and fermentation in green plants. st-m alllc'' indicates an increase in reducing sub- L. G e n e v o i s (Biochem. Z., 1927, 186, 461—473).— 2rni°eS er ^an those containing the sulphydryl The respiratory and fermentative activities of six T. H. P o p e . different types of alga;—Chlorella pyrenoidea (Chick), content of green grass ; weight of Scenedesmus Basiliensis (Ckodat), Codastrum Pro- 1927 187^1 <«°UrV?r‘ Brouwer (Biochem. Z., boscideum, Hcematococcus pluvialis, Stichococcus . 183 193).—A t all seasons Lolium perenne, bacillaris, Pseudendoclonium Basiliense (Visch)—have 906 BRITISH CHEMICAL ABSTRACTS.----A. been, studied and compared with fermentation by investigated witli regard to the liydrogen-ion con yeast (cf. Meyerhof, A., 1926, 95). Respiration of centration of the culture medium, and to the rate of Chlorella, in the presence of air, is increased by the acid formation by the mould. The accumulation of addition of dextrose, laevulose, mannose, or galactose, kojic acid in the culture medium (determined by the respiratory quotients in all cases being unity. colorimetric titration with ferric chloride) increased Lactic acid and pyruvic acid have no influence, but the j)a but slightly; the observed increase is there acetaldehyde increases respiration up to threefold, fore due to the removal of the cations of the medium with R.Q. 1-26; the acetaldehyde is probably syn by the mould. When ammonium nitrate is used as thesised to fatty acids. Propaldehyde and valer- the source of nitrogen the ammonium ions are con aldehyde have less effect than acetaldehyde, whilst sumed more rapidly than the nitrate ions; at a certain formaldehyde completely inhibits respiration. Sodium pB (3-4) the latter begin to be consumed with a corre butyrate, and to a less extent the acetate and valerate, sponding reduction in acidity. Growth can take increase respiration and cause a fall in R.Q. to 0-S, place in cultures of this mould between the limits of indicating that the acid is oxidised. Soluble aniino- j)n 2’1 and S-6, and is a maximum at 3-5 and 7-0. At acids give a smaller but still definite increase in the minimum, pa 5-5, the formation of kojic acid is respiration. Lactose and sucrose have no effect but maximal. Free organic acids inhibit the growth of two hexosemonophosphoric acid preparations caused the organism, although their salts accelerate growth: an increase in respiration up to threefold. The other oxalic, citric, and kojic acids are most active, then algae give results agreeing in general with those for follow tartaric, lactic, acetic, and formic acids. The Chlorella. No fermentation by Chlorella occurs in a kojic acid formation is rapidly diminished by the sodium hydrogen carbonate-Ringer solution in the addition of oxalic, citric, formic, hydrochloric, and absence of oxygen, but fermentation is induced by the nitric acids, whilst sulphuric acid produces a slight addition of dextrose, laevulose, mannose, or galactose. increase; the production is also increased by the The other algae behave like Chlorella in the ferment addition of tartaric acid at a low. ps, and by the ation experiments. Algae differ from yeast-cells to addition of phosphoric, lactic, and pyruvic acids in a some extent in their sensitivity to potassium cyanide, medium with a pn corresponding with the so-called for respiration in the salt solution is inhibited by small isoelectric point of plasma protein, 5—6. amounts of cyanide only in the case of Scenedesmu-s. E. A. Lunt. In all cases, respiration in the presence of dextrose, Influence of temperature on the nature of the sodium butyrate, acetaldehyde, etc. is inhibited by fat formed by living' organisms. L. K. P e a r so n cyanide. Similar amounts of cyanide cause no and H. S . R a p e r (Biochem. J., 1927, 21, S75—879). inhibition of fermentation, but respiration and fer The iodine value of the fatty acids produced by mentation are equally sensitive to narcotics such as Aspergillus niger and Rhizopus nigricans varies with phenylurethane. It is concluded that the “ intra the temperature at which these organisms are grown. molecular ” respiration of algae is essentially similar At higher temperatures the fatty acids produced are to yeast fermentation and fission processes in animal more saturated. S. S. Z il s a . cells. One difference, however, is that in a sugar Influence of Turkestan climate on the chemical solution part of the respiratory process is insensitive processes of plants. S . L. I v a n o v (Bull. Univ. to cyanide and this respiration is approximately equal Asie Centrale, 1926, No. 12, 21—25).—A warm to that in a salt solution, which is itself insensitive to climate lowers, and a cold climate raises, the quantrtv cyanide. A. W o r m a l l . of unsaturated acid (particularly linolenic) in the oi of seeds. C h e m ic a l A b str a c ts. Growth of moulds on cobaltammine salts. K. K in o s h it a (Acta Phytochim., 1927, 3 , 31—50).— Nitrogen content of aspergillin. A. ^ .FEL Cultures of Aspergillus niger, A. oryzee, and Peni- and K. W a l t e r (Biochem. Z., 1927,186,474—4/ 7). cillium glaucum have been made using various The fractions of the black spore pigment of Aspergi u cobaltammine salts as the source of nitrogen; the niger contain different amounts of nitrogen, 1(j nitrogen content in each case was adjusted to a alcohol-soluble fraction giving a value of 3’3 /0 am constant value. In all cases growth was very much the alkali-soluble fraction about 4-6%. -¡No co11^ less than for the control experiments in which ammon elusions can be reached as to whether these differences ium and potassium nitrates were used. In the few are due to chemical changes or to the presence o salts which produced appreciable growth the mycel impurities. Large variations in the n itro g e n supp ium contained a high percentage of cobalt. During in the medium do not, however, appreciably altei i growth under these conditions A. oryzee converts 33% amounts of these fractions or their nitrogen con en ■, of the sucrose of the culture solution into kojic acid; and it is concluded that the formation of aspergi i A. niger under the same conditions produces large is due to uniform chemical processes. amounts of acid. It is concluded that these effects A. W o k m a l l are due to the lack of easily assimilated nitrogen, since Soluble enzymes secreted by liymenoniycei.es. A. niger when grown in a culture solution with only Tannin as antioxidant. L . L u t z (Compt. rei ■> small amounts of ammonium nitrate produces citric, 1927, 184, 1493— 1494).—Tannin p o s s e s s e s strong malic, succinic, tartaric, and oxalic acids. antioxygenic properties in the presence of t.ie i s E. A. L u n t . mycelium of hymenomycetes; in t h e presence Metabolism of Aspergillus ortjzm. I. H. 5 drops of a 1% ethereal aqueous solution o T a m iy a (Acta Phytochim., 1927, 3, 51— 173).— The reduction of methylene-blue is apparent after < conditions for the growth of A. oryzce have been with cultures of Stercum hirsutum, S. purpureutn, <■ BIOCHEMISTRY . 907 Polyporus versicolor, 'whilst in tannin-free controls enzyme present in the rootlets of germinating barley redaction is not perceptible until 8— 15 days have which is capable of deamidating asparagine. An passed. The coloration of guaiacol, a-naphthol, and active preparation of this enzyme can be obtained from K-naphthylamine hydrochloride in presence of the the aqueous extract. It appears to be specific for same fungus is considerably retarded in the presence the naturally occurring ¿-asparagine. The simple of tannin. A parallel series of experiments with amides acetamide and propionamide are entirely gallic acid gave similar results. R. B r i g h t m a n . resistant to its action but ¿-glutamine is hydrolysed by Nature of the dye penetrating the vacuole of it. The optimum pu is about 7 and the optimum Valonia from solutions of methylene-blue. M. temperature about 37°. Pig erepsin also deamidates Irw in (J. Gen. Physiol., 1927, 10, 927— 947).— asparagine. On the other hand the barley preparation Speetropliotometric observations demonstrate that hydrolyses glycylglycine. The enzyme is therefore the dye which penetrates into the vacuoles of un considered to be a plant erepsin (peptidase). injured cells of Valonia macrophysa, immersed in S. S. Z i l v a . methylene-blue solutions, is in reality the lower Volatile fatty acids formed by the acid ferment homologue, trimethylthionine (azure-5). Since this ation of foodstuffs. II. C. B r a h m , G. A n d r e s s e n , dye is a weaker base than methylene-blue, and there a n d R. P r i l l w i t z (Biochem. Z., 1927,186, 232—242). fore may exist as free base under the conditions of the — The separation and determination of the volatile experiment, the staining of cells by methylene-blue acids formed during acid fermentation of green maize solutions is not necessarily a contradiction of the view (A ., 1925, i, 623) are described. that the dye ions are unable to penetrate into the P. W. C l u t t e r b u c k . cells. If the cells are injured methylene-blue itself Early stages of microbiological decay and A . T h a y s e n * may be detected in the vacuoles. W. 0. K e r m a c k . humification of vegetable tissues. C. and W. E. B a k e s (Biochem. J., 1927, 21, 895—900). Subsidiary dyes in methylene-blue. W. C. —The humification of oat straw proceeds most Holmes (Stain Tech., 1927, 2 , 71—73).—All samples rapidly between the first and sixty-fourth day of of methylene-blue examined have been found to fermentation. The hemicelluloses (pentosans) of the contain azure-5 (trimethylthionine). Since the latter, raw material are at least partly responsible for the and not the former, is the dye which normally enters appearance of the carbohydrate fraction of the humus. the living cell, it is important to be able to detect it in The proportions of the carbohydrate and lignin samples of methylene-blue. The following qualitative fractions (B., 1926, 305) vary appreciably with the test has been devised : 0-1 g. of methylene-blue is progress of the humification. In three samples of dissolved in 25 c.c. of M /15-borate buffer solution bituminous coal no definite proof could be obtained (Clark). An equal volume of water is added and the of the presence of a carbohydrate fraction hi the solution is shaken with 25 c.c. of chloroform. The regenerated humus, although the percentage of halogen chloroform solution is then filtered twice through in the chlorine derivatives of these humus samples paper. If azure-5 is present the solution will appear was of the order characteristic of a mixture of carbo riolet in colour. The chloroform is then shaken with hydrate and lignin humus. The muscular tissues water (or water containing a trace of acetic acid) adhering to a mummified human vertebra of 200 «‘hen the azure-5 enters the water and may be identi B.C. had been converted into a humus with the pro fied spectrophotometrically. If methylene-violet is perties of a typical carbohydrate humus. present (only traces are usually found in methylene- S. S. Z i l v a . Mue) the chloroform will remain pink after repeated Nutrient solutions having stable pa values extraction with water. On shaking with hydro throughout the growing period of plants. R. Zin- chloric acid (pu 1) methylene-violet is removed from z a d z e (Landwr. Versuchs-Stat., 1927,105,267—332).— the chloroform quantitatively, giving a reddish- The preparation is described of a series of solutions nolet solution. H. W. D u d l e y . which can be used in water culture work, without Ketone-aldehyde mutase in wheat, rye, and repeated changing, the pB value remaining constant soya beans. L. K l a r (Biochem. Z., 1927, 186, within narrow limits during plant growth. The basis —330).—Wheat, rye, and soya beans contain the of these solutions is the use of ammonium nitrate e n z y m e . p. W . C lutterbuck. (physiologically acid), ferric sulphate (hydrolytically acid), and sparingly soluble phosphates with which Enzymic production of volatile products from the solutions are buffered. A. G. P o l l a r d . cotme under the influence of tobacco-leaf j ufnC-S' F o d o r and A. Reifenberg (Biochem. Absorption of ions by citrus and walnut Tol ^65).—-Polemical againstFaitelowtz (this seedlings. A. R . C. H a a s and H. S. R e e d (Hil- fen-’ (. •' ^ c°tme is decomposed in tobacco gardia, 1926, 2, 67— 106).—Rough-lemon and grape entation even when sterility is observed. There fruit seedlings remove more potassium than calcium amf ?i Sm between the decomposition of nicotine from solutions containing equivalent amounts of the iolnr 'c.amoun^ of oxygen absorbed by moistened ions; with small potassium concentrations more thrrmJv, ves> even when the macerates are filtered calcium, magnesium, and phosphorus are absorbed, germicides ^°r°US canc^e or *n presence of and potassium is excreted from the roots. Citrus ' S. S. Z lL V A . seedlings absorb more cation than anion from solutions hiewj^10 ,^eamidation of asparagine in the of calcium salts. Chloride is most readily absorbed (Biochpm aiT G r o v e r and A. C. Chibnall from calcium chloride solution; the presence of I 1, J- 1927, 21, 857—8681.—There is an chloride reduces the absorption of nitrate. The 908 BRITISH CHEMICAL ABSTRACTS.— A. nature of the growth of citrus seedlings in water available for combination with phosphoric acid. There cultures depends on the original pa, maintained pn, is a pronounced retention of phosphorus by wheat and the nature of the acid or alkali employed. starch when the latter is washed repeatedly with Walnut seedlings (ash of kernel contains 60% P) dilute acids, leading to the conclusion that this firmly- rapidly absorb all the phosphorus from a complete bound phosphorus is not combined with metals. The nutrient solution. The amount of magnesium comparison of mineral constituents of wheat and absorbed is independent of the potassium concen potato starch and experiments involving electro tration. Except with the nitrate, walnut seedlings dialysis, heating of the starch with water under press removed more cation than anion from solutions of ure, and peptisation with ultra-violet light fail to calcium salts. C h e m i c a l A b s t r a c t s . account for the peculiar electro-chemical and other properties of wheat starch. The nitrogen present in Influence of sodium carbonate and of calcium this starch, however, shows a resistance similar to chloride on the acidity of the sap of the maize that of the phosphorus in all these processes, and it plant (Zea Mais). S. K a r a s i e w i c z (Bull. Soc. is concluded that a salt-like compound of protein and Chim. biol., 1927, 9, 841—S50).—Details are given of amylophosphoric acid is present. On this assumption the procedure and methods of analysis used in experi many of the peculiarities of wheat starch can be ments on the effect of calcium and of the reaction of explained. A. W o r m a ll . the medium on the acidity of the sap of Zea Mais. Colloidal properties of peat. A. V. D um anski W. 0. K e r m a c k . (Zapiski Voronezhskii sel’skokhozyaist. Inst. [Russia], Physical and chemical changes during the 1926, 5, 61—80).—A peat of high lime content (46% ripening of grapes. P. R. v .d . R. C o p e m a n and of the ash), but not one of low lime content (10% of * 6 . P r a t e r (Dep. Agric. Union S. Afr. Sci. Bull., 1926, the ash), readily formed a suspension with water. 50,1—54).—The sugar content of the berries increases The particles are charged electronegatively and move rapidly during ripening, but only slowly or not at all in an electric field with a velocity of 0-000024 cm. at maturity; changes in the total solids other than (per sec. ?) for a P.D. of 1 volt between electrodes sugar after the commencement of ripening are small. 1 cm. apart. Neutral and acid salts and acids At maturity there is a definite relation between the coagulate peat hydrosol; alkali hydroxides and total solids and the sugar, the value being 0-6—0-7, carbonates peptise it. The coagulating power of according to the variety. The percentage of acid salts is in the order sodium (1), magnesium (14), decreased to 0-45—0-63 at maturity, and the ratio of aluminium (2700). Coagulation is also effected by acid to sugar decreased to 0-35—0-50. A connexion freezing. C h e m ic a l A b st r a c t s . between the nitrogen content and the texture, but not the ripening, of the berries was indicated. The mineral Determination of carbamide by gasometric content increased during ripening and was constant measurement of the carbon dioxide formed by at maturity. The percentage of total solids in the action of urease. D. D. Van Sl y k e (J. Biol. Chem., 1927, 73, 695—723).—Preformed carbon seed continued to increase after maturity; the ash dioxide and hydrogen carbonate are removed from content of the seed was maximal at the period of the solution containing carbamide by acidification rapid absorption of inorganic salts, and thereafter and agitation under diminished pressure ; the solution is decreased on account of the increase in ligneous and neutralised and treated with urease, and the ammonium cellulose constituents as the seed set and hardened. carbonate formed is determined in the apparatus o C h e m i c a l A b s t r a c t s . Van Slyke and Neill (A., 1924, ii, 872). Details are Nitrogen and carbohydrate composition of the given of the application of the method to the determin developing flowers and young fruits of the apple. ation of carbamide in quantities of material varving F. S. H o w l e t t (Cornell Univ. Agric. Exp. Sta. Mem., 1926, 99, 1—79).—At the opening of the fruit-buds from 0-2 c.c. of blood to 2 c.c. of urine. C. R. H a r in g t o n . the flowers are low in free reducing substances, total Cobalt thiocyanate as a m icrochem ical re sugars, and acid-hydrolysable fraction, but all types of agent. J. G r e g e r (Biochem. Z., 1927, 185, 43 carbohydrate material increase as the flowers progress 441).—A concentrated aqueous solution of co a towards full bloom. The nitrogen content of the thiocyanate has the property of dissolving; s arc flowers decreases up to full bloom. The limiting granules and of staining variously other consti uen » factor in normal flower development is lack of a of plant-tissue ; it is therefore a valuable reagen suitable, adequate supply of nitrogen. The nitrogen the microscopical examination of vegetable o content of the fruit is nearly constant. products. C. R- H a r in g t o n . C h e m i c a l A b s t r a c t s . Plant colloids. XVIII. Wheat starch. M. Pentose metabolism. II. Micro-deterinni S a m e c [with L. G u z e l j , J. K a v c i c , and L. K l i n c ] ation of pentoses and pentosans. G. E. X (Biochem. Z., 1927, 186, 337—359).—The ash of b u r g (J. Biol. Chem., 1927, 73, 599—606). potato starch contains a distinct excess of acid termination of pentoses by the furfuraldéhyde metnw constituents over bases and the silica is sufficient to is accelerated by the use of phosphoric acid ins e a _ neutralise all the calcium and magnesium, thus the hydrochloric acid formerly employed. Wit allowing the phosphoric acid to exert its acidic effect. of the colorimetric determination of furfuraldeny > The ash of wheat starch, however, has a much smaller its reaction with aniline in presence of acetic aci » excess of acid over base, and since the silica content is method is applicable to quantities of pentose relatively low, the calcium and magnesium are partly 0-1 to 1 mg C. R, Haringtok necessary thermo-chemical data are not ava a R-CH,.N02. The heats of activation of the above for consideration of conditions with regard to en®F§3; three nitro-compounds, calculated from the changes Aa£-Hexadicne-yS-diol, b. p. 98°/12 mm., / ORGANIC CHEMISTRY. 853 mm., ¿? l -006, nf, 1-4700, prepared by reduction of obtained by a similar method, in 65—69% yield, acraldehyde, is o x id is e d by permanganate to oxalic directly from ethyl y-phenoxypropylmalonate. Ethyl acid and converted through the ozonide into meso- S-bromovalerate has b. p. 94—97°/7 mm., b. p. 106— tartaric acid. It is hydrogenated in the presence of 110o/20 mm., <££ 1-3191, v% 1-4580 (cf. Cloves, A., spongy platinum to mesohexane-y8-diol, b. p. 91°/20 1902, i, 200). 8-Bromovaleryl chloride, b. p. 102— mm., m. p. 88°. 104°/15 mm., df 1-5010, n% 1-4879, was prepared. A^-Octadiene-Se-diol, b. p. 122°/9 mm., obtained Treatment of 8-bromovaleric acid with bromine and from crotonaldehyde after ozonisation (preferably phosphorus tribromide yields aS-dibromovaleric acid, of the corresponding diacetate), affords r-tartaric b. p. 150— 1520/5 mm., df 1-8629, nfi 1-5347 (acid acid. Hydrocinnamoin, as the diacetate, similarly chloride, b. p. 138— 145°/15 mm. ; ethyl ester, b. p. gives mesotartaric acid in 46% yield; meso-
ORGANIC CHEMISTRY, 869