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rattlesnake and two other species or classes. Rattle­ venom, 6 liters after an interval of 5 days, and 6 liters toms, and inversely with the size of the patient. More snake serum is prepared in Philadelphia. At the Pasteur after a second equal interval These 20 liters of blood is needed for a child than for an adult. Institute of Lille, which supplies all theFrench colonies, yield a little more than 10 liters of serum, which is If the case is far advanced and the patient is in a Calmette produces a polyvalent serum from mixed decanted into bottles, which are sealed and sterilized. critical state, there should be no hesitation about inject­ venoms of Colubridae and Viperidae. The former are The serum retains its activity for several years, but more ing 30 cubic centimeters into the veins, and repeating obtained in abundance from French Indo-China, but . certain preservation for a much longer period can be the dose if necessary. If the respiratory centers have there is often a shortage in viper venom. Hence Cal­ assured by desiccating the serum and sealing it in glass already been affected, it is advisable to practise artificial mette's serum is especially anti-neurotoxic, while its capsules, each containing one gramme (15.4 grains troy) respiration, in order to prolong the stage during which anti-hemorrhagic power varies greatly, according to the of the dried serum, which when required for use, is dis­ the organism can resist the venom until the serum can quantity of viper venom which the inoculated horses solved in 10 cubic centimeters (one third fluid ounce) of produce its effect. No matter how desperate the case have received. water that has been boiled and cooled. may appear, there should never be any hesitancy about The serum is prepared by the following method: A If the patient is treated promptly, before toxic symp­ employing the serum, which has effected cures absolutely horse is first injected with a mixture of venom and hypo­ toms have appeared, a hypodermic injection of 10 to 20 . unhoped for. chlorite of lime. The injection is repeated every three cubic centimeters (one third to two thirds fluid ounce) of Wherever the serum treatment is employed, the mor­ or four days, the proportion of hypochlorite being gradu­ serum usually suffices to prevent poisoning in an adult. tality among treated cases has become almost zero. In ally diminished to zero, and the operation being illter­ While awaiting the injection it is advantageous to ligature Sao Paulo, Brazil, of 275 cases treated with appropriate rupted if the animal loses flesh. After this treatment the limb, immediately above the bite, and to cauterize serums only one resulted fatally, .and in this case the has been continued about 16 months, the horse can with­ the wound with a red hot iron or a solution of potassium patient was at the point of death when the serum was stand the hypodermic injection of 2 grammes (30 grains permanganate or hypochlorite of lime. If the bite has applied. In India and some other countries, unfor­ troy) of dry cobra venom, which is about 80 times the been inflicted by a large or very venomous serpent, 30 tunately, the natives rebel against the new treatment, normally mortal dose, and is in condition to furnish an cubic centimeters (1 fluid ounce) of serum should be in­ and many deaths are still caused by venomous serpents. efficacious serum. The animal is then bled, 8 liters of jected at once. The quantity of serum required varies -Translated for the SCIENTIFIC AMERICAN SUPPLEMENT blood being drawn 12 days after the last injection of directly with the time lost and the gravity of the symp- from La Nature. * The Industrial Synthesis of Sodium Cyanide

Probable That the Supply Will Exceed the Demand Through a New De\Telopment

By Charles Gra vier

OF the three industrial forms of combined nitrogen­ and hydrogen, so that the final result is given by the By a modified process, in which the employment of cyanides, ammonia and nitric acid-the cyanides occupy equation: cyanide as a reagent is avoided, the sodium amide is the lowest place in industrial statistics. While Chile 2NaCN +4H20=2NHa+Na2COa+CO+H2 converted first into sodium cyanamide, and then, at 800 annually produces .2,500,000 tons of sodium nitrate, and Many chemists are now endeavoring to effect the in­ deg. Cent. (1,472 deg. Fahr.), into sodium cyanide, by 1,000,000 tons of ammonium sulphate are furnished by dustrial systhesis of ammonia by way of the cyanides. direct combination with carbon. gas works and coke ovens, the annual production of To me this method appears illogical, because hydro­ 2NaNH2+C=Na2CN2+ 2H2 cyanides does not exceed 25,000 tons. The employment cyanic acid, a compound formed from its elements by an Na2CN2+C=2NaCN of cyanides has greatly increased since the introduction endothermic reaction in which 30.5 calories of heat per Castner's first idea was to produce sodium cyanide of the MacArthur and Forrest process in the metallurgy. gramme-molecule are absorbed, will always be more directly from its elements. As the combination is· exo­ of gold, in 1888. Before that date, the annual production costly than ammonia, which is formed by an exothermic thermic, evolving 50 calories per gramme-molecule, there of potassium cyanide, the only cyanide then utilized, did reaction, evolving 12 calories per gramme-molecule. can be no doubt of its possibility. I verified this theo­ not exceed 100 tons. retical deduction before I knew of Castner's researches. Four hundred and fifty tons were produced in 1888, I-U I obtained sodium cyanide by passing a CUITent of pure G 750 tons in 1890, 3,500 tons in 1895, and for several years '" m. • F nitrogen over a mixture of charcoal and sodium, but the there was a steady annual increment of about 1,000 tons, ==::J yield of cyanide was small Castner had previously, in consisting partly of sodium cyanide, which had been 1894, made similar experiments. He poured fused sod­ introduced meanwhile. Almost the entire output of T p:-.. BJ ium slowly on charcoal, heated in a vertical cylinder, G Ix to which a current of nitrogen was admitted by a lateral alkaline cyanides is used in the refining of gold, only a ff very small proportion being consumed in electroplating ... �- orifice. Sodium cyanide accumulated at the bottom of :>IK the cylinder. The quantity produced was greater than with gold and silver. But, though the cyanides occupy c- a comparatively small place in the great industry of was obtained by passing nitrogen over a mixture of char­ nitrogen compounds, nitrogen in the form of cyanogen IV coal and sodium carbonate, but Castner soon recognized commands a higher market price'than nitrogen in the Fig. 2.-Horizontal" section of retort for produc­ the advantage of SUbstituting ammonia for nitrogen. The original Castner process for the synthesis of form of. ammonia or. nitric acid, which' are worth not ing sodium amide. more than 1.5 francs per· kilogramme (13.2 cents per sodium cyanide was conducted in two successive stages, pound) of nitrogen, while the cyanides cost at least 6 sodium amide being produced in one apparatus at 300 francs per kilogramme (52.8 cents per potind) of nitrogen. The chea"pnesswilh which metallic sodiuni. can be pro­ to 400 deg. Cent. (572 to 752 deg. Fahr.) and converted In these eonditions, it would be profitable to convert duced . by electrolysis of fused soda, has made possible into sodium cyanide in a second 'apparatus at 700 to 800 nitric acid or ammonia into cyanides. The transforma­ the development of a process by which a large part of the deg. Cent. (1,292 to 1,472 deg.Fahr.). tion can be eff.ected by various reactions, none of which cyanide required by gold refiners is now produced from 2. Preparation of Sodium Amide.-The reaction be­ has been utilized for converting sodium nitrate into sodium, ammonia and carbon. tween ammonia and sodium takes place in a horizontal sodium cyanide, though cyanides are actually made from The English firm of Castner, whose name is intimately rectangular retort with a sloping .bottoill ' (A, Fig. 1). ammonia. The inverse transformation is still easier to associated with the history of sodium, first devised these The upper part of the retort is divided into compart­ accomplish, as cyanides evolve ammonia when they are methods of obtaining the metal and its cyanide, but the ments by vertical partitions. C which dip slightly into the heated in a current of water vapor. Hydrogen cyanide, industrial production of cyanide was made practicable liquid sodium M. These partitions, which do not extend in presence of water, tends to decompose into ammonia by improvements introduced by the Deutsche Gold- und entirely across the retort and are attached alternately to' and formic acid, while its salts, in similar conditions, Silberscheide Anstalt, of Frankfort. its two sides, compel the current of ammonia to pass yield ammonia and formates. At red heat, however, The chemical formula of sodium cyanide, NaCN, in the formates split up into carbonates, carbon monoxide which Na=23 and N=14, shows that nearly 2 kilo­ * Translated for the SCIENTIFIC AMERICAN SUPPLEMENT from grammes of sodium are reqUired in order to convert Revue des Sciences. 1 kilogramme of nitrogen from the ammonia form to the cyanide form, and thus to raise its market value from 1.5 francs to 6 francs. The Castner electrolytic process, using a cheap source of electricity, furnishes the 2 kilo­ grammes of sodium for 2 francs, leaving a margin of 2.5 francs to cover other expenses and profits. THE ORIGINAL CASTNER PROCESS FOR THE SYNTHESIS OF CYANIDES. 1. Theory of the Process.-It is well known that metallic sodium, at a temperature of about 400 deg. Cent. (752 deg.Fahr.) absorbs ammonia gas, forming an amide and liberating hydrogen. . NH3+Na=NaNH2+H One molecule of this amide and one molecule of sodium cyanide,.fused together, combine at 550 to 600 deg. Cent. (1,022 to 1,112. deg.Fahr.), yielding 1 molecule of sodium cyanide �Ild free hydrogen. . NaNH2+NaCN=Na2CN2+H2 Finally,'thi� molecule of cyanamide, mixed intimately with carbon, coni�ines with it at 750 to 800 deg. Cent. Fig. I.-Castner apparatus for producing sodium (1,382 to 1,472 deg.Fahr.), forming 2 molecules of sod� Fig. 3.-Castner apparatus for converting sodium amide. ium cyanide: amide into sodium cyanide.

A, horizontal retort; B, hearth; 0, partitions; M, fused Na2CN2+C=2NaCN A, retort; B, hearth; 0, funnel for introduCtion of char­ sodium; D, sodium inlet; N, ammonia inlet; F, hydrogen Thus the molecule' of cyanide used in the process is coal; D, inlet for fused Sodium a mide; E, siphon for outlet; J, siphon; EKN,N.. cocks. recovered and a second molecule is gained. drawing off sodium cyanide.

© 1914 SCIENTIFIC AMERICAN, INC. February 28, 1914 SCIENTIFIC AMERICAN SUPPLEMENT No. 1991 135

through the compartments successively and prolong its After many researches Roessler succeeded in convert­ the amide. irito cyanamide. Finally, the temperature contac.� with the sodium. ing ammonia almost completely into cyanide by dividing is raised to 800 deg. C. (1,472 deg. F.) to convert the The retort is heated to 300 to 400 deg. C. (572 to 752 the entire operation into three parts, producing succes­ cyanamide into cy�nide, which is drawn off into molds deg. F.) and a little very dry ammonia is passed through sively sodium amide, sodium cyanamide and sodium and, after solidification, is ready for the market, without it to expel the air. Fused sodium is then poured into cyanide. The first and second phases are conducted further treatment. The theoretical quantity of cyanide the funnel D until it begins to overflow at G and escape at a comparatively low temperature, 300 to 400 deg. C. is produced, the loss being �y that which is inherent through the siphon J. Ammonia, entering at N, is (572 to 752 deg. F.), at which the amide is stable; the ,to any industrial oper�tion, but .the temperature must absorbed by the liquid sodium, the pure surface of which third at a high temperature, 800 deg. C. (1,472 deg. F.), be rigorously controlled. The product contains from is continually renewed, as the sodium amide formed, which does not affect the cyanamide. As we have al­ ,90 to �8 per cent of pure sodium cyanide, equivalent to also liquid, but heavier than the sodium, falls to the ready seen, the amide can be converted into cyanamide .120 to 130 per cent·of potassium cyanide, which is the bottom of the retort, whence it flows,'through a small either by fusing it with an equivalent quantity of cyan­ :standard adopted for estimating the value of cyanides. orifice near the base of the wall G, into the chamber B, ide or by heating it with charcoal to 350 to 400 deg. C. This improved Castner process is employed in Ger­ and escapes through the siphon J. The ammonia is (662 to 752 deg. F.). In practice the fused amide is many by the Deutsche .. Gold- und Silberscheide Anstalt entirely consumed; the hydrogen evolved escapes at F.' heated with finely-divided charcoal to 380 deg. C. of Frankfort and the Elektrochemische Fabrik Natrium Sodium has recently acquired considerable importance (716 deg. F.). A violent evolution of hydrogen takes of Rheinfelden, in America by the Ni�ara Electro­ from its employment in.the synthesis of in�go. place and the mass gradually loses its fluidity, for the chemical Company, and in France by the Sooiete d'Elec- 3.· Conversion of SQd.ium-Amide into Sodium Cyanide. temperature of fusion of sodium cyanamide is 550 deg. C. trochimic. . -This transformation is accomplished in a cylindrical (1,022 deg. F.). In order to complete the transforma­ Germany annually export� about 7,000 tons of cyan­ retort with a conical bottom (A, Fig. 3). The retort is tion, therefore, it is necessary to raise the temperature ides and produces nearly otie third of the 25,000 tons filled with wood charcoal t1n;ough the funnel C, and is gradually to 550 to 600 deg. C. (1,022 to 1,112 deg. F.). which the world annually consumes. England pro­ heated to about 800 deg. C. (1,472 deg. F.). A stream In these conditions the theoretical yield of cyanamide is duces almost as much, and large quantities are made in of fused sodium is then admitted at D. The liberated obtained. France and the United StateS; hydrogen escapes at F and the liquid sodium cyanide The charcoal must be very finely divided in order to The Castner-Roessler process; although the newest, flows through the siphon E into molds, in which it supply every molecule of amide with the carbon required is by far the most important process of the cyanide solidifies. for its transformation. It has been proposed to sub­ industry, as its quantitative efficiency and the sim­ THE CASTNER-ROESSLER PROCESS. stitute liquid or gaseous hydrocarbons for charcoal. plicity of its apparatus enable it to produce cyanide at Roessler, of the Deutsche Gold- und Silberscheide Acetylene is especially suitable for this purpose, but its a price that defies competition. The future of the process Anstalt of Frankfort, recognized the possibility of employment would sensibly increase the cost of the appears less certain, owing to the development of a new greatly increasing the efficiency of the second of the product. industry, which is obtaining from distillery and sUgar above-described operations, which comprises two suc­ The Frankfort company and its licensees now conduct refinery wastes a great variety of substances, including cessive reactions. At the. temperature required for the three phases of cyanide synthesis successively in trimethylamine, which is subsequently converted into the formation of sodium cyanide, the sodium amide the same apparatus, consisting of a series of large iron cyanide by heating it with metallic sodium. begins to decompose, disengaging nitrogen and pro­ crucibles. Each crucil;>le is charged with 70 kilogrammes N(CHa)a+Na=NaCN +2CH.+H portionally diminishing the yield of cyanide. On the (144 pounds) of finely-

The Arms of the Venus of Milo spired with archreological enthusiasm. These two officers brought them aboard the "Estafette" carefully wrapped The End of a Mystery were on the alert for antique finds, and, naturally, they up in canvas. These scattered members included the chip from the shoulder and much of the two arms; and IN "La Roman d' une statue," M. Jean Aicard, of the got into communication with Bottonis, who showed them so most of the Venus of Milo was conveyed to Paris via French Academy, has given a final and authoritative the lower portion of the statue where it still stood, in the Marseilles. When this new wonder appeared in the answer to the enigmas of that wonderful antique which vault, and then the upper portion in his hut. Next day antique gallery of the Louvre, people naturally asked the world at large, following the French spelling, knows the "Chevrette" sailed for Constantinople. This, we must remember, all happened before the Kingdom of questions about the missing arms and the great chip on as "the Venus of Milo." For now almost a century-92 her shoUlder, perhaps the fractures showed fresh and years, to be exact-scholars and dilettanti have been Greece had come into existence, and when Melos was white by contrast with the other creamy, time-stained forming theories as to the exact pose of the missing arms still Turkishterritory; Arrived at Constantinople, they surfaces; perhaps the authorities were canny enough to and hands. Some woUld have it that this particular made haste to inform the French ambassador, the Mar­ use a little wash of coffee. But at all costs the French Venus had carried a lance. One theory, very plausibly quis de Rivi�re, of their discovery. Bottonis had given Government had to discourage inquisitiveness in this based upon certain lines in the "Hecuba" of Euripides, them, it seems, an option on the statue, promising not direction; it would never have done-it would have made the subject of this masterpiece not Venus, but to sell it without their consent, and this option was dUly raised a diplomatic scandal-to tell the international Polynena, calmly advancing to the altar on which she made over to their ambassador. If these French suitors of the goddess had not relied world about that unofficial scrimmage on the beach at is to be sacrificed, with: ''Lay no hand upon me, for I Castro. am a daughter of kings." Henceforth there need be no so implicitly on Bottonis's promise to them, the "Venus in Now so far as this, M. Aicard has told us, though in more guessing as to those arms, what they meant, or of Milo" might have taken her place the sight of men a circumstantial and more logical way, little more than what became of them. M. Aicard tells what they looked with her proper complement of arms and an unchipped what many artists and archreologists have long vaguely like before they were severed from the trunk, how they shoulder. But M. de Marcellus, commissioned py the understood, in spite of all theories to the contrary, were severed, and even why the whole story has been Marquis de Rivi�re to go and acquire the statue for his that the two arms were broken in a fight when the French left to obscurity and to guessing until now. And, as Government, was in no particUlar hurry. He did not Le Temps remarks in giving its resume �f M. Aicard's reach Castro, on the schooner "Estafette," until the sailors were taking Venus away from.her home of twenty centuries (the common story said that the fight was with monograph, when we know what this classic lady went 23d of May-just in time to see a brig, flying the Ottoman the natives), and that one hand had held an apple. But through in 1820, the wonder is not that she lost her flag, waiting in the roadstead, and a knot of Turkish the real importance of ."La Roman d'une statue" is in arms, but that she kept a head on her beautifUl shoulders. sailors marching toward the strand. The Turkish sailors The trouble began when Iorgos Bottonis, in the early were ca.rrjring between them something white and heavy its authoritative character, derived, firstfrom the hitherto unpublished memoranda of Lieutenant Matterer and spring of 1820, undertook, with his son Antonios and a on a wooden litter; through a telescope, M: de Marcellus, Engisn Dumont d' Urville and, next, from the testimony nephew, to clear a piece of ground on the Bottonis farm on the deck of the "Estafette," got his first view of the at Castro, in the island of Melos. While they were all Venus of Milo; and, for the moment, he feared it would of the late M. Jules Ferry. For reasons probably con­ nected with the recent turn of affairs in the Balkan three busy, the spade of one of them suddenly sank into be his iast. But Commandant Robert, appraised of the PeninsUla, as well as with the lapse of time; M. Aicard a cavity beneath the surface. They at once investigated, state of affairs, acted promptly, and a cutter loaded with believes that no harm can now come of laying the whole and found a sort of vaUlt. Breakingthrough the masonry French blue-jackets was soon pulling for the shore. The of this vaUlt, they found a statue of heroic size, repre­ sequel was a very lively scrimmage between French and story before the world and depositing the manuscripts'of Matterer and Dumont d'Urville in the archives of the senting a female, nude as to the upper half, but draped Turkish sailors-not between the naval forces of France Institute of France, for reference. As for the corrobora­ from the girdle to the feet, the drapery "held up below and the Ottoman Empire, or the incident woUld have tive statement of Jules Ferry, it relates how, when he the hips by the right hand, while the left arm was raised, been publicly acknowledged, and we should have known occupied the post of French ambassador at Athens, in partly flexed, the hand holding a sphere not larger than all its details long ago-only an unofficial scrimmage on 1872, he personally visited Castro and there found an apple." To the right and left of the statue were two the beach at Castro. The resUlts' of this unofficial action Antonios, the son, .and the nephew of Iorgos Bottonis. small figures, one the head of a woman, the other the were: first, the Turks dropped Venus and made for their These two remembered and were willing to substantiate head of an old man with a long beard. brig; secondly, the litter was smashed beyond any further storY of the discovery and the particUlars about the Bottonis knewthat every fragment of antique sculpture use; thirdly, the French sailors, surmizing that the Turks the appearance of the statue as it was when they found it. had a money value. He took measures to hide this woUld presently return with reinforcements, made all haste There can be no longer any doubt as to the original precious find. Itwas the easierof transportation because to haUl the upper half of the statue (which was all position of those much talked-of arms, or as to the much it was not one block of marble, but three; one block for that had been on the litter) with ropes over the rocks debated apple. The only subject now left open to {Jon­ the upper part, another for the lower part, and a third and loose stones down to where their cutter was beached. jecture is the fate of the two heads-the woman's and for the right arm, which was attached to the shoUlder It turned out, on inquiry, that the pedestal and lower . the bearded old man's. by an iron peg. Still, the work was difficUlt to :Perform half had already been tak,en aboard the Turkish brig, quietly, without letting the neighbors know. In the but M. de Marcellus entered into negotiations, and the event, Bottonis, his son and his nephew succeeded in Turkish captain was induced to surrender his half of the A Remarkable Achievement in Slow FlyJng.-After removing the upper half of the statue to their little hut, prize. After all, why shoUld a good Moslem fight, and & the close' of the Paris exPosition the Paul . Schmidt leaving the lower half, with its pedestal, in the vault. perhaps forego substantial bak&kisk, for the sake of biplane was tested at Chartres before an Ita1ian mili­ It was only a few weeks later, on the 20th of April, fragmentary heathen abomination? tary commission. The minimum .speed realized wa. that the good genius of the Louvre sent the French The French sailors were carefUl to pick up all the pieces actually miles an hour, and the ease of landing man-of-war "Chevrette" into the harbor of Castro, hav­ that were knocked off in the course of their hauling. or 24� a.t tha.t speed was remarkable. It was the world'. ing :first arranged that two of her officers, Lieutena.nt of the rough-and-tumble unofficial action which preceded record for slow flying. Matterer and Eugn Dumont d'Urville, shoUld be in- it. That is, they picked up all they coUld find and

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