JOURNAL 



o 



OF THE 



Elisha Mitchell Scientific Society 



Volume XXXV JUNE, 1920 Nos. 3 and 4 



CHLORINATION BY MIXED CARBON MONOXIDE 

 AND CHLORINE 



By Francis P. Venable and D. H. Jackson 



This investigation was undertaken to see if a mixture of carbon 

 monoxide and chlorine could not be substituted for carbonyl chloride 

 in certain chlorinations. It may be worth while to draw attention to 

 this reaction as the use of phosgene in the industries has been sug- 

 gested, but the dangers connected with its shipment and use may be 

 prohibitive. 



Chlorination with joint action of some reducing agent has been 

 practiced for a long time. At first carbon and chlorine were used 

 by d'Oerstedt and many others. The carbon has l)een replaced with 

 carbon tetrachloride by Demarcayi and Camboulives- ; with carbon 

 plus carbon monoxide by Ribau'' ; with sulfur by Matignon and 

 Bourion-^; with sulfur monochloride by Bourion'^; and with carbonyl 

 chloride by Chauvenet^'. The experiments detailed below show that 

 carbon monoxide with admixed carbon reacts readily in conjunction 

 with chlorine, and in the references given it will be noted that both 

 carbon tetrachloride and carbonyl chloride react when used alone. 

 Carbon^-l chloride, especially, reduces and chlorinates with ease ox- 

 ides, sulphides and some very stable salts. 



The experiments reported here were necessarily limited in number 

 but may be extended at some more convenient time. The substance 

 ^ to be acted on was placed in a boat in a hard glass tube and the mixed 



CO ^Compt. Rend., 104 (1887), 111. 



^Cnmiit. Rend., 150 (litlO), 175, 221. 

 »-H '^ Hull. Sor. C'liiw.. 39 (1SS3), 14. 



*Cnmi,l. Rend., 138 (l!iii4), 631, 760. 

 —J ^Compt. Rend., 146 (1!)07), 62. 



^^ oCompt. Rend., 152 (I'.tll), 87. 12.'>0. 



-3 I ««7 1 



