Kinetic and Equilibrium Studies of the Reactions of Cyanide Ion with 1,3,5-Trinitrobenzene, 2,4,6-Trinitroanisole, and 2,4,6-Trinitrotoluene in Isopropanol

Abstract

Equilibrium constants for the formation of 1 : 1 cyanide ion o-complexes with 1,3,5-trinitrobenzene, 2,4,6-trinitroanisole, and 2,4,6-trinitrotoluene have been determined spectrophotometrically over a range of temperatures. Standard enthalpy ( A H 0 ) and entropy (AS0) changes associated with each reaction have been evaluated. The kinetics of formation of the o-complexes have been investigated by means of a stopped-flow technique and the activation parameters characterizing the formation of each complex have been determined. Evidence is presented which indicates the cyanide ion -2,4,6-trinitroanisole o-complex formed in isopropanol contains the cyanide ion bonded exclusively at the C-3 position.Les constantes dlCquilibres pour la formation d'un complexe-o 1 : 1 ion cyanure -trinitro-1,3,5 benzene, trinitro-2,4,6 anisole et trinitro-2,4,6 toluene ont t t t dtterminies dans un intervalle d e temptratures a I'aide de la spectrophotornCtrie. Les changements d'enthalpie standard (AH0) et d'entropie (AS0) associCs a chaque reaction ont Ctt Cvalues. La cinktique de formation des complexes-o a 6t6 ttudite a I'aide de la technique a dtbit interrompu et les parametres d'activation se rattachant a la formation de chaque complexe ont ete dtterminks. On apporte des preuves pour montrer que le complexe-cr ion cyanuretrinitro-2,4,6 anisole form6 dans I'isopropanol contient I'ion cyanure lie exclusivement a la position C-3.[Traduit par le journal]Can. J. Chem., 52,8 (1974)