La Spécificité des Halogénations Atomiques VI‐Réactions de compétition

Abstract

The photochemical reaction between gaseous CI,, C,CI, and C,CI,H has been further investigated. From the general reaction scheme previously proposed equations have been calculated and tested experimentally for I ) the rate of the reaction CI, +-C2CI,H+ C,Cl, i -HCI yielding 2 relations between rate constants;2) the total rate of disappearance of Clz in mixtures of C,CI, 1-CICI, H ; 3) the competition addition-substitution; 4) the competition substitution-dehydrohalogenation ; 5) the competition dehydrohalogenation-addition;With the previously studied relations for : 6) the rate of addition at low temperatures; 7) the rate of addition at high temperatures; 8) the rate of dehydrohalogenation; 9 relations are now available between 6 rate constants. But since these relationships are not independent, complex rate constants can be determined only e.g. for the four independent combinations. lo(--" 2 T 5720 14 57 T) k,lk'* kdk, kdks'2 k,'/2 k','/?lk,% = ]0(-13 8 16280/4 57 T ) ]O( t 2 56-3020/4,57 T ) 101 t 9 05 -:3085/4 57 T)Since 9 rate equations are available each of these c3mplexe rate constants has been determined by at least 2 independent methods yielding thus a very reliable proof of the mechanism.