Alkyl Halides In Water Research Articles

Kinetics of solvolytic reactions. Dependence of composition on time and of rate parameters on temperature

Kinetic parameters describing the solvolysis of alkyl halides in water at fixed temperature and pressure are considered in terms of both one-stage and two-stage processes. In the latter case the consequences are explored of using both the steady-state hypothesis and the fully integrated form of the rate expression. The first-order rate constant calculated from experimental data has not discriminated between these alternative descriptions. The integrated form based on a two-stage reaction is considered the correct approach. Calculations for model systems throw some doubt on the validity of the steady-state approximation for these systems. Further, the steady-state assumption leads to an underestimate of the apparent heat capacity of activation when compared with the values calculated using the fully integrated form of the rate expression.

The dependence on temperature of rate constants for solvolysis of alkyl halides and related compounds in water

Various explanations are considered for the observation that plots of In[k(obs)] against T–1 for solvolysis of alkyl halides in water are generally curved. It is suggested that the two stage reaction scheme proposed by Albery and Robinson accounts for the patterns of behaviour in derived parameters previously reported which were calculated assuming that the mechanism involves a single activation barrier.

Mechanism and solvent reorganization accompanying hydrolyses of anchimerically assisted alkyl halides in water

Mechanism and solvent reorganization accompanying hydrolyses of anchimerically assisted alkyl halides in water