A new kinetic model on hydrolysis of sulfur mustard non-dissolved and dissolved in aqueous solution.

Non-homogeneous hydrolysis extent was able to be accurately described by a product of logistic with exponential convex growth function because of slow collision-complex formation between activated H 2 O and HD molecule to non-linearly couple with transition state decay according to Chain Reaction and Transition State theory, while the homogeneous has grown up only in an exponential convex function because of fast collision-complex formation to make its initial extent ratio extremely quickly close to unity. [Display omitted] • Extent equations for hydrolysis of Sulfur mustard are newly proposed. • An exponential convex growth function for homogeneous hydrolysis extent. • Its product with a logistic growth function for non-homogeneous hydrolysis extent. • Their rate constants strongly depend on initial and boundary conditions. • They are limited by the internal quantum state number of bi-molecular structure. This paper aims to establish a hydrolysis extent equation and rate dependence of initial and boundary conditions for sulfur mustard (HD) non-dissolved and dissolved in water by the following work. Firstly, non-homogeneous hydrolysis extent was found to be accurately described by a product of logistic with exponential convex growth function because of slow collision-complex formation between activated H 2 O and HD molecule to non-linearly couple with transition state decay, while the homogeneous has grown up only in an exponential convex function because of fast collision-complex formation to make its initial extent ratio extremely quickly close to unity. Secondly, initial non-temperature effects from (ethanol, acid, base) additives, HD concentration and droplet size, and rotation speed on hydrolysis rate could be summarized into a Boltzmann function of rate constant with initial molar free energy because of a thermal equilibrium distribution of internal quantum state at a given energy for bi-molecular structures before and after complexing. The results from 5 mL solution under vortex was nearly similar to the stirring 100 mL solution and would helpfully clarify the detoxification kinetics to establish a standard method for evaluating reactivity of aqueous decontaminants against chemical warfare agents at necessarily specified conditions. [ABSTRACT FROM AUTHOR]