Solvent-Jump Relaxation Kinetic and Equilibrium Studies of the Reaction of NOCl with n-BuOH

Article abstract of DOI:10.1021/j100438a006

The kinetics and mechanism of the reaction between NOCl and n-BuOH is investigated at 5 and 22 deg C in CCl4-HOAc mixtures, ranging from pure CCl4 to 75percent v/v HOAc.In the solvent mixtures, the use of the solvent-jump relaxation method is demonstrated on this reaction which is insensitive to concentration-jump but is perturbable by a sudden change of the reaction medium.The experimental relaxation amplitudes are in agreement with the ones calculated theoretically, and the ratios of the rate constants k₁/k_-1 agree with the equilibrium constants K determined photometrically.The variation of the thermodynamic and activation parameters is discussed as a function of solvent composition.