ECKART MATHIAS, EUGENIO SANHUEZA, I. C. HISATSUNE, and JULIAN HEICKLEN. Can. J. Chem. 52,3852 (1974).The chlorine atom initiated oxidation of CzC14 was studied both in the absence and presence of 0 3 at 24 and 32 "C. In the absence of 0 3 , the products are CCl,CCl(O) and CC120, and they are produced in a long-chain process in a ratio of 2.5 at 24 "C and 3.0 at 32 "C. The product producing step involves the decay of C2Cl50 radicals [6alThe ratio k6,/ksb is 5.0 at 24 "C and 6.0 at 32 "C since CCl, reacts with O2 to produce another CC1,O molecule. In the presence of O3 the ratio Q, {CC13CC1(0)}/@ {CC120) drops, C -is produced, and the chain length is reduced. The ratio kz/kIo = 6.7. The reduction in yield as 0, is added results from the terminating reaction t15blThe CIOz reacts further with O3 to produce C1207.The reaction of O3 with C2C14 at 24 "C also produces mainly CC13CC1(0) and CC12O with cC1, CC12b as a minor product. Other minor products detected after extended conversions included Cl,, CO, and C 0 2 . However c-C3C16 was not found. The ratio [CCI~CC~(O)]/[CC~ZO] is < 1. Moreover, the addition of O2 retarded the reaction, indicating a long chain mechanism in which both free radicals (species with an odd number of electrons) and CCl2 were absent. A diradical chain mechanism is presented which explains the main features. The chain step is the addition of CC1202 to C2C14 P5] cc1202 + c2c14 * c c I 2 o~c 2 c l 4The adduct then reacts with 0, in a chain regenerating step or with O2 in a chain terminating step.ECKART MATHIAS, EUGENIO SANHUEZA, I. C. HISATSUNE et JULIAN HEICKLEN. Can. J. Chem.
52,3852(1974).On a etudi6, a 24 et 32 "C, en presence et en absence de O,, l'oxydation initiee par des atomes de chlore de C,C14. En l'absence de O,, les produits sont CCl3CC1(0) et CCIZO; ils sont produits par un processus en chaine dans un rapport de 2.5 a 24 "C et de 3.0 a 32 "C. Les etapes amenant la formation de ces produits impliquent la decomposition des radicaux CzC150 L'adduit reagir alors avec 0, dans une Ctape regenerant la chaine ou avec 0, dans une Ctape terminant la chaine.[Traduit par le journal]
