Volumes of activation for the reaction of 1-chloro-2,4-dinitrobenzene and 2-chloro-1,3,5-trinitrobenzene with piperidine in aqueous ethanol

Abstract

Rate constants for the reaction of 1-chloro-2,4-dinitrobenzene and 2- chloro-1,3,5-trinitrobenzene with piperidine in 80% v/v aqueous ethanol have been measured as a function of pressure up to 1.7 kbar. The volumes of activation are -35.0 and -20.7 cm³ mol^-1 respectively, consistent with greater delocalization of charge and less solvent electrostriction in the transition state for the second reaction. The applicability of quadratic functionality for 1n k(P) is briefly discussed.