An examination of parameters describing the dependance of rate constants on temperature for solvolysis of various organic esters in water and aqueous mixtures

Abstract

The consequences are examined of fitting rate constants and temperatures for a solvolytic reaction to the equation log k = A/T + B log T + C. The coefficients A, B, and C for 150 reactions involving organic derivatives are linearly dependent. Possible mechanistic reasons for this underlying pattern of behaviour are considered. The linearity stems from the least squares analysis used to obtain the coefficients and as a result these quantifies are not truly independent. Consequently, the validity of employing this type of analysis based on the three parameter equation is questioned.