T H E J O U R N A L O F I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y Vol. 12, No.
I100
,/ J’
I
’
I
i
I
ffydreyen -nitref en mixture en-hehum mixture
tl
Presure. centimeter^ of water FIG
4-GAS
2
PRESSURES REQUIRED TO PRODUCE THE BLOW-OFR VELOCITIES SHOWN IN F I G .
3
to several centimeters of water, the results indicate t h a t as high as 18 per cent hydrogen can safely be used t o dilute helium when it is used in balloons. CONCLUSIONS
I-Under the most favorable conditions, a jet of helium containing more than 14 per cent of hydrogen can be ignited in the air. 2-Eighteen t o twenty per cent of hydrogen may be mixed with helium, without producing a mixture which will burn with a persistent flame when issuing from a n orifice under the conditions prevailing in balloon practice. 3-More than 2 0 per cent of hydrogen in a hydrogenhelium mixture cannot be used in a balloon without sacrificing safety from fire.
THE REACTION BETWEEN SELENIUM MONOCHLORIDE AND ETHYLENE By F. H. Heath and Waldo L. Semon UNIVERSITY OF
WASHINGTON,
SEATTLE, WASHINGTON
Received July 1 7 , 1920
I n t h e attempt t o prepare the selenium analog of P,P’-dichloroethyl sulfide (mustard gas), i t was necessary t o prepare selenium monochloride and t o attempt t h e preparation of selenium dichlpride.
too impure for use, since it contained much free selenium and considerable selenium tetrachloride. The reaction of selenium in sulfuric acid and hydrogen chloride as reported by Divers and Shimosel yielded a very good] product, but was much too slow for t h e preparation1 of large quantities of selenium monochloride. The method, as finally worked out, consisted in. dissolving IOO g. of selenium in 300 g. of 30 per cent oleum. This solution was placed in a distilling flask connected t o a condenser, and a stream of dry hydrogen chloride, prepared by dropping concentrated hydrochloric acid into concentrated sulfuric acid, was led in. The flask was now gently heated, at a temperature low enough so t h a t little of the selenium volatilized, and t h e current of hydrogen chloride was made rapid enough sol that a steady stream of selenium monochloride distilled over. I n this way, one run (130 g. of SezClt) could b e made in about 2 hrs. time. The sulfuric acid for making the hydrogen chloride was reconcentrated and use& over and over again. The crude product was purified by shaking with successive small portions of fuming sulfuric acid until the acid layer did not show t h e characteristic green color of SeS03. The selenium monochloride was allowed t o stand over dry sodium chloride for a week and then decanted into tubes which were sealed and’; kept until needed. The reaction according t o Divers and Shimose is as. follows:
+ SOS = SeSOs + +
Se
12.physik. Chem., 70, 1 .
+
2SeS03 zHC1 = SeSO3SeClz HzSOs SeS03SeC12 HC1 = SezClzf SOzHOCl An attempt was made t o prepare selenium dichloride, by passing chlorine into the monochloride until t h e theoretical gain in weight was obtained. The product consisted of a mixture of selenium monochloride, and selenium tetrachloride and was found t o react withi ethylene the same way as the monochloride, b u t with smaller yields. REACTION B E T W E E N E T H Y L E N E AND S E L E N I U M MONQC H L 0R I D E
On leading a slow stream of ethylene into selenium\ monochloride, the liquid became warm, selenium was precipitated, and hydrogen chloride was evolved. When the reaction was complete, hot chlosoform was added, and the selenium was filtered off. On cooling, long, white, needle-like crystals were precipitated. Upon recrystallization from chloroform they had &he characteristic selenium odor, and were found to melt with decomposition a t I 18 O (uncorr.). On analysis, the following results were obtained: of Analyses hT0.
Carbon . Hydrogen Chlorine
P R E P A R A T I O N O F S E L E N I U M MONOCHLORIDE
The method of direct union of chlorine and selenium suggested by Beckmannl was found t o give a product
IF
..........
............... ....... .........
1 1
Found Per cent 18.1 2 9
51.7 2
28 5 6
101.26
Theory for CiHsChSe Per cent 17.5 2.2
100.1
This shows t h e compound t o be GHBCLSe. 1
Chem. News, 49 (1894), 212
51.6 28.8
Nov., 1920
T H E J O U R N A L OF I N D U S T R I A L A N D ENGINEERING CHEMISTRY
IIOD
N O T E ON CATALYSIS I N THE MANUFACTURE OF When ethylene was led into a carbon tetrachloride ETHER1 solution of selenium monochloride or into the attempted selenium dichloride, the same product was obtained, By Hugo Schlatter HERCULES POWDER Co.,WILMINGTON, DELAWARE but in smaller yields. Received August 18, 1920 To establish the structural formula of C4H6C14Se1 Senderens,* discussing the action of aluminium we may reason by analogy from the sulfur compounds. I n the following equations may be found a brief resum6 sulfate as a catalyst in the manufacture of ether, of the work done by Guthrie,' as interpreted in the states t h a t the addition of about j per cent of t h e anhydrous sulfate t o t h e usual mixture of sulfuric light of our modern knowledge of chemistry. acid and alcohol lowers the temperature a t which S regular and rapid evolution of ether takes place from I1 11 140' C. t o 130' C. He explains this action by assumCaHio SzClz C1- C6Hio - S - CsHio - C1 (I) ing the formation of a double aluminium ethyl hySClz --f C1- CbHin - S - C1 C6Hio (2) drogen sulfate (Alz(S04)3.S04HCzHh), which breaks S up a t a lower temperature than ethyl sulfuric acid. il Although in plant operation the temperature of the C Z H ~ SzClz C1- CzH4 - S - C2H4 - C1 (3) still a t which regular and rapid evolution of ether CzH4 SzClz S takes place is about 1 2 j o .i t was thought of interest I/ t o determine whether the addition of aluminium Clz - CH - CH2 - S - CHz - CH -Clz (4) sulfate would result in lowering this temperature CzH4 SClz --f C1- CzH4 - S - C1 (5) still further, or in increasing the capacity of the still. C11.- CzHs - S - CzHs - Clz Clz + During the war any increase in the capacity of existing 'I apparatus was of supreme importance. S C1BC - CHz - S - CHz - CC13 ( 6 ) A small, glass, ether still with the necessary column I/ and condensers was charged with a mixture of sulS furic acid and alcohol. After the evolution of s ether had started, alcohol was fed into t h e still below I CzHs - S - C2H5 Cli ----f S the surface of the liquid a t a rate corresponding t o t h e It ether produced. Senderens' statement, t h a t evoluC13C - CHz - S - CHz - CCls (7) tion does not become regular until a temperature of Further work by Frederick Kont-Norwal12 shows 140O is reached, was confirmed. Amounts of alut h a t one selenium from selenium monochloride may minium s t lfate varying from 3 t o I O per cent by weight readily be split off from its compounds, as is sulfur in were introduced into the still in subsequent runs, and the manufacture of mustard gas. Equations 3 and 4 i t was found t h a t with 5 or I O per cent of aluminium show how the reaction between ethylene and selenium sulfate the temperature was lowered t o 130'. A somewhat larger still of 1.5-gal. capacity was then monochloride may quite probably run. Althou'gh we have no evidence of the existence of the compounds constructed of lead and equipped with a steam heating C1- C2H4 Se - CzH4 - C1 and CLCH CHZSe - CHZ- CHClz coil, so as t o approach factory conditions as closely as possible. Two runs of about jo hrs. duration were I1 1; Se Se made, one with and one without the addition of j per cent by weight of aluminium sulfate. The temi t is quite probable t h a t they may be formed and the peratures throughout the two runs were the same a s final product be C12CH.CH2.Se.CHz.CHClZ. Equations 6 and 7 show the symmetry of the atom, and by in factory operation, i. e . , from 1 2 0 ' t o 1 2 j " , and there analogy the selenium compound is assumed to be like- was no difference in the net yield of the two runs. When the still was opened after the completion mise symmetrical. of t h e run, it was found that severe pitting of the coils PHYSIOLOGICAL E F F E C T S had occurred when aluminium sulfate was present, Although the physiological effects of this compound possibly owing t o electrolytic action between the lead have not been studied, the experimenter has been con- of the coils and the aluminium sulfate. I n both tinually troubled with water blisters on his hands cases there was a sludge of sulfates. A short test was also made in t h e original glass while doing this work. A person working with this compound is also liable t o be overcome with a sense still with broken porcelain. I n this case the temof drowsiness. Whether this be due t o the compound perature a t which regular evolution occurred was lowered t o the same temperature (130') as with or t o some by-product is not known. aluminium sulfate in the glass still. CONCLUSIONS It is apparent, therefore, t h a t aluminium sulfate offers no advantages over the lead sulfate which is I-A simple method for the preparation of selenium normally present in lead ether stills, b u t is actually monochloride has been described. harmful, since i t causes pitting and rapid failure of the P - C C ~ H ~ C ~has ~ S ~been prepared and it has been coils. The action of lead sulfate could be explained shown t o be symmetrical tetrachlorodiethyl selenide.
+ +
*
+
* *
+
+
+
+
J Chem SOC.,12, 109, 13, 35, 135 Chem -Ztg , 16, 288,
* Oesterr
1 Presented a t the 60th Meeting of the American Chemical Society, Chicago, I11 , September 6 to 10, 1920 2 C o n p t r e n d , 1 5 1 (1910), 392
