THE PREPARATION OF HEXACHLOROETHANE IN THE LIQUID PHASE BY CHLORINATION OF TETRA—AND PENTACHLOROETHANE

1946 ◽  
Vol 24f (5) ◽  
pp. 369-379 ◽  
Author(s):  
Jesse A. Pearce

Preliminary investigations showed a slow rate of production of hexachloroethane from chlorine-saturated liquid tetrachloroethane. The addition of some materials that often accelerate similar reactions was not effective here. However, rapid production was obtained by chlorinating tetrachloroethane in the presence of ultra-violet light. The effective wave-lengths appeared to lie between 3150 Å and 3540 Å, and the temperature coefficient between 75° and 100 °C. was 1.10. The result indicated that production of hexachloroethane from chlorine-saturated liquid tetrachloroethane was feasible. For the same conditions of illumination and temperature hexachloroethane was produced from chlorine-saturated pentachloroethane at a rate two and one-half times as fast as that in chlorine-saturated tetrachloroethane.

It was first shown by Dreyer and Hanssen (1) in 1917 that ultra-violet light produced a change in protein solutions which appeared to be similar to coagulation by heat. They exposed various solutions in quartz chambers to the light of a Bang lamp with iron and silver electrodes. Vitellin was found most easily coagulated, while globulin, albumin and fibrinogen showed a decreasing sensitivity to ultra-violet rays in the order mentioned. These investigators also discovered that acids markedly increase the rate of precipitation. Soret (2) had shown in 1883 that there are absorption bands in the extreme ultra-violet region of the spectrum of various proteins, e. g. , casein, ovalbumin, mucin and globulin. Tyrosine likewise has this band in the ultra-violet and Soret attributed to this constituent of the protein molecule its power of absorbing ultra-violet rays. In this connection Harris and Hoyt (3) carried out some interesting experiments on the protective power of various substances for paramœcium cultures exposed to ultra-violet radiations. They found that gelatin peptone, amino-benzoic acid, cystine, leucine and especially tyrosine possessed the power of detoxicating ultra-violet rays when placed as a thin layer of aqueous solution over paramœcium cultures under a quartz-mercury lamp. The toxicity of the radiations for paramœcia or protoplasm in general can be understood in the light of the discovery of Dreyer and Hanssen coupled with that of Soret. From a physico- chemical standpoint Bovie (4) has published a study of the coagulation of proteins by ultra-violet light. By exposing solutions of crystalline ovalbumin, both dialysed and containing electrolytes, to the light of a mercury-vapour lamp, he came to the conclusion that there were two reactions involved in the coagulation of ovalbumin by ultra-violet light. The first is a photochemical one with a low temperature coefficient,—denaturation; and the second is one with a higher temperature coefficient of two and is dependent upon the electrolytes present,—coagulation. While using solutions dialysed against tap water Bovie made the observation that the protein appeared to become sensitive to light of longer wave-length, for his control tubes in glass were slowly coagulated.


BMJ ◽  
1925 ◽  
Vol 1 (3364) ◽  
pp. 1152-1153
Author(s):  
A. Blakiston

BMJ ◽  
1925 ◽  
Vol 2 (3376) ◽  
pp. 495-495 ◽  
Author(s):  
A. Blakiston

BMJ ◽  
1928 ◽  
Vol 1 (3501) ◽  
pp. 237-238
Author(s):  
H. S. Banks

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