LIBRA R.Y OF THE UNIVERS ITY Of 1LL1 NOIS 546 1951 /SZ rJ Return this book on or before the Latest Date stamped below. University of Illinois Library l.lul — H41 Digitized by the Internet Archive in 2012 with funding from University of Illinois Urbana-Champaign http://archive.org/details/inorganicsemi195152univ INORGANIC SEMINARS 1951 - 1952 TABLE OF CONTENTS 1951 - 1952 Page TETRANITROGEN TETRASULFIDE (N 4 S 4 ) 1 P, Klppur THE HALOGENS AND INTEBHALOGENS A3 SOLVENTS 5 Niels C. Nielsen 9 CYANATE ADDITION REACTIONS 12 James W. Currier STEREOCHEMISTRY OF SOKE BORON COMPOUNDS 18 R. 0.. Kerr Oi ORGANOMETALLIC COMPOUNDS GROUP III 23 . John $ . Walker VITAMIN B xa - PART I 27 James M, ^ulnn VITAMIN B 13 -_PART II 32 Shelcion E. rrey MOLECULAR ADDITION COMPOUNDS 0* STANNIC CHLORIDE"" 36 Win. 0, Smith RhRE EARTH SEPARATIONS UTILIZING COMPLEXING AGENTS 41 Robert H. Marshall THE ART OF ELECTROPLATING 44 Ernest H. Lyons, Jr. FERROELECTRIC CRYSTALS 52 Laurence F. Dempsey OXIDATION STATES OF THORIUM 58 Philip A. Horrigan PURIFICATION OF HYDROCARBONS BY MEANS OF INORGANIC REAGENTS 61 J, P, Freeman PROCESS DEVELOPMENT OF INORGANIC ChEMICALS 67 Roger W. Sanftner ADDITION PRODUCTS OF BORON TRIFLUORIDE WITH SALTS Or OXY-ACIDS 70 Paul G. Gordon THE STRUCTURES OF THE IRON C^RBONYLS 73 Donn D. Par sow DISPOSAL OF RADIOACTIVE WASTES 79 S. J.. Bodnar . TABLE OF CONTENTS Page 2 Page BORIDES 83 Walter E. Thatcher ThE STEREO CREhlSTRY OF COkPLa/. INORGANIC C0foPOUi\iD3 CONTAINING ORGANIC hOLECULES. THE PARTIAL RESOLUTION OF RACEkIC MIXTURES Of SOLE ORGANIC ACIDS BY MEANS OF DIFFERENT STABILITIES OF ISOkERS OF COMPLEX IONS AND THE PRINCIPLE 0¥ PREFERENTIAL COORDINATION 88 Allan D. Gott THEORY OF OV^RPOTENTIAL IN ELECTRODEPOSITION 94 Ernest H. Lyon?* Jr. SUPPLEMENTARY REMARKS ON OVERPOTENTI ALS Ernest H, Lyons Jr. 100a THE "HALF-BOND" AND ITS APPLICATION TO THE STRUCTURE OF ELECTRON DEFICIENT COMPOUNDS Niels C, Nielsen 101 ROLL CALL (Development in Technetium Chemistry) Therald Moeller 110 ROLL CALL (The I mine Radical) Melvin Tecotzky 111 ROLL CALL (First Isolation of Curium) Dale Woerner 113 SEPARATION OF LANTHANONS BY ION EXCHANGE Phillip A. Horrlgan 114 SOME RECENT ADVANCES IN THE CHEMISTRY' OF THE HYDRIDES Harold M. Foster 117 ROLL CALL (Cyanide Complexes of Cobalt (II) ) Ernest H. Lyons, Jr« 125 ROLL CALL (A Review of the Russian Concept of Chemical Structural Theory) . Niels C # Nielsen 126 ROLL CALL (Electrodeposition of Cobalt - Tungsten *- Molybdenum Alloys) John C, Bailar, Jr, 129 COORDINATION COMPOUNDS CONTAINING GROUP V HALIDES . Robert Marshall 130 VALENCE INDUCTIVITY Stanley Kirschner I35 SOME MOLECULAR ADDITION COMPOUNDS OF TRIMETHYLiMINE OXIDE AND TRIMETHYLOPHOSPHINE OXIDE William C. Smith I39 TABLE OF CONTENTS Page 3 Page SOLVENT EXTRACTION AND ITS APPLICATIONS TO INORGANIC ANALYSIS Lewis I. Krimen 143 ALKALI METAL PHOSPHIDES Paul G. Gordon 151 PREPARATION -AND PROPERTIES OP SOME BRANCHED POLYSILOXANES Richard A. Rowe 157 THE REDUCTION OF COMPLEX CYANIDES WITH ALKALI METALS IN LIQUID AMMONIA Robert N f Hammer 163 STRUCTURE OF THE PLATINUM OLEFIN COMPLEXES James W, Currier 167 THESIS REPORT Robert F. Vance 171 THESIS REPORT Fred L, Pundsack 174 THESIS REPORT Earle Scott 177 THESIS REPORT Ralph Gher 181 ***** ' TETRANITBOGEN TETRASULFIDE (N 4 S4 ) P. Kippur September 25, 196L Standard inorganic textbooks list three sulfides of nitrogen, namely, NS 3 , nitrogen disulfide, N 4 S4 tetranltrogen tetrasulfide and N 3 S S , dlnitrogen pentasulfide. The compound N 3 S4, dinltrogen tetra- sulfide, has been isolated recently and its absorption spectra found to be Identical with that of nitrogen disulfide and of di- nltrogen pentasulfide wliich would indicate that the latter are actually dinltrogen tetrasulfide (l). Tetranltrogen tetrooulfide was first prepared by Gregory in 1835 (2). Although subsequent investigations have contributed a great deal to our present knowledge of tetranltrogen tetrasulfide, the exact nature of this compound with respect to many of its pro- perties and reactions is still undetermined. Physical Properties Tetranltrogen tetrasulfide is an orange-red crystalline mater- ial with a melting point of 179°C. It is not wet by water, but it is soluble in such solvents as carbon disulfide, benzene, chloroform and liquid ammonia. Tetranltrogen tetrasulfide and most of its derivatives, with the exception of cyclotetrathlatotrimine (N4S4IO, are sensitive to heat and shock; investigations have been carried out with respect to its possible use as a priming agent (3) (4) (5) (6) (7) (8) (9) (10 ). It has been found to be inferior to such materials as mercury (jl) fulminate and-is therefore not utilized for this 'purpose. Structure The structure of tetranltrogen tetrasulfide, which is in agreement with most of the available data, may bo represented as an eight-member ed puckered ring with alternating Sulfur and nitrogen atoms. (ll)(l2)(l3). Preparatio n There are two general modes of preparation: 1. The reaction of either sulfur mono chloride or sulfur di chloride with gaseous ammonia (I4)(l5)(l6)(l7)(l8)(l9) (20) (21) (22) (23) (24) (25) (26) (27) (28) (29), These reactions ^5<0"uu^ally carried out in a .non-aqueous nolvent (i,o CCJI4- C e K e ), and the by-products are uulfur, imlnosulfur (S 7 NH), and ammonium culflde and/or poly sulfide. 2* The reaction of sulfur and liquid o.mmonla (30)(3l). 10 S + 16 NH a (liq.) ^ £ N4S4, + 6(NH4 ) a S This reaction is a balanced one and the equilibrium may be shifted to the right 'by the addition of silver iodide which precipitates the sulfide ion. ) -2- Reactions Tetranitrogen tetrasulfide reaots with the ohlorides of Tl(lV), Sb.(V), Mo(V), Wlvi) and Se(l) in solvents, auoh as, chloroform and oarbon tetrachloride, to produoo addition oompounds (32) (33). The reaction' of tetranitrogen tetranulfide and lead (il) , iodide in liquid ammonia producoo the compoundg Pb(N3) 3 NH8 in con-' centrated solution and PbN a S, N*S*»3NH 3 in dilute solution (l6)(34l With meroury (II) iodide only the oompound HgN a S»NH 3 is formed, (16; Treatment of tetranitrogen tetrasulfide with ohlorine in non- aqueous media produces trithiazyl trichloride (NS) 3 Cl a # (34)(35)(36) (37), The corresponding bromine oompound has also been prepared ("8). These compounds were first reported to be tetrameric, but were later shown' to be trimerlo (34), Thiotrithiazyl chloride (NS) 8 SC1 is produced when tetranitrogen tetrasulfide reaots with either sulfur monochloride or thionyl chloride in a non-aqueous solvent (33) (39) (35) (40). The corres- ponding 'bromide is produced in a similar manner (33) (35), The iodide has also been prepared (35) (41), The 3 6* compounds behave as though the thiotrithiazyl group (NS) 3 S is a monovalent cation; treatment of thiotrithiazyl chloride with nitric acid, sulfuric add and thiocyanate ion yields the corresponding nitrate, bisulfate and thiocyanate (35), Further evidence for the lonio character of these materials is th6ir insolubility in most organio solvents (39). # Tetranitrogen tetrasulfide may be reduced in benzene solution to cyclotetrr.thiatetrlmlne (NSH) 4 upon treatment with an alcoholio solution of tin (II) chloride at 60 °C. (33). This material is un- usual as it is the only member of this group of compounds that is not sensitive to heat or Ohock (33) (42). In- strongly alkaline solution, tetranitrogen tetrasulfide undergoes hydrolysis to produce ammonia, thlosulfate and sulfite (42). However, in neutral or weakly alkaline solution trithionate, thlosulfate and ammonia are formed (12). Tetranitrogen tetrasulfide undergoes ammonalysis in liquid ammonia with the formation of ammonosulfurous and ammonothio sulfuric acids. This is evidenced by the formation of Pb(NS) a and HgN a 3 upon the addition of lead(ll) or meroury(Il) iodide to the above solution (16) (43). Uses 1. Insecticide (18)^4) (45) (46) (47) (48) (49) (50 ) (51 2. Fungicide (18) (44) (52) (53) (54) ' 3. Ignition promoter for diesel fuels (55) (56) 4. Accelerator in the vulcanization of rubter (57) 5. Indicator in the titration of aoldg in non-aqueous solvents (58) (59). -3- The utilization of tetranitrogen tetrasulfide as an inseotioido and fungicide is by far its most important praotloal application. Bibliography 1. G-oehring and Kaloumenos, Z. anorg. Chem., 263, 137-44 (1950 ). 2. Gregory, J. de Pharm., 21, 315-17 (1835). 3. Berthelot and Vleille, Inn. Chim. Phys.. (5) 27, 2«2 (1882). Ibid., Bull. Soc. Chim. ,.(2) 37, 388 (1882). 4. Ibid., Compt. Rend., 92, 1307-09 (1881). ' Ibid., J. B. (Llebig), 1114 (1881). Ibid., Ber., 14, 1558 (1881 ). 5. Hoitsema, Z. physik. Chem., 21, 136-48 (1896). 6. Koettnitz. Z. Elektroohem., 34, 768-83 (1928). 1152-66 7. Muraour Bull. Soc, Chim., 51, ' (l932). 8. Ibid., Mem. Artillerle France, 18, 895-7 (1939). 9. Wflhler and Matter, Z.f.d.ges. Schiess u. Sprengstoffwesen, 2, 203-6, 244-7, 265-69 (1907). 10. Wlhler, Z, angew. Chem,, 24, 2089-99 (l9ll). 11. Lu and Donohue, J. Am. Chem. Soc, 66, 818-27 (1944). 12. Goehrlng Ber., 80, 110-22 (1947). 13. Arnold, Kugill and Hutson, J. Chem. Soc. 1645-49 (1936). 14. Voznesenskil, J. Russ. Phys. Chem, Soc, 59, 221-32 (1927), 15. Schenck, Ann., 290, 171-85 (1896). 16. Ruff and G-eisel, Ber., 37, 1573 (1904). 17. Arnold and Perry, (to Imp. Chem. Ind. Ltd.) U.S. Patent 2,382,845, Aug. 14, 1945; C.A. 185 (1946). 18. Arnold, (to Imp, Chem. Ind. Ltd.) U.S. Patent 2,372,046, Mar. 20, 1945; C.A. 3862 (1946). ' 19. Carl, U.S. Patent 2,337,798, Dec 28, 1943; C.A. 3428 (1944). 20. Van Valkenburgh and Bailar, J. Am. Chem. Soc, 47 2134-37 (1925). 21. Macbeth and Graham, Proc. Roy. Irish Acad., 36B, 31-40 (1923). 22. Burt and Usher, Proc. Roy. Soc. London, Series A, 85, 82-98' (1911).