Kinetic sonication effects in light of molecular dynamics simulation of the reaction medium

Siim Salmar; Aleksei Kuznetsov; Ants Tuulmets; Jaak Järv; Sander Piiskop

doi:10.1016/j.ultsonch.2012.10.010

Kinetic sonication effects in light of molecular dynamics simulation of the reaction medium

Ultrason Sonochem. 2013 Mar;20(2):703-7. doi: 10.1016/j.ultsonch.2012.10.010. Epub 2012 Oct 26.

Authors

Siim Salmar¹, Aleksei Kuznetsov, Ants Tuulmets, Jaak Järv, Sander Piiskop

Affiliation

¹ Institute of Chemistry, University of Tartu, 14A Ravila St., 50411 Tartu, Estonia. siim.salmar@ut.ee

PMID: 23137655
DOI: 10.1016/j.ultsonch.2012.10.010

Abstract

Molecular dynamics (MD) simulation of the structure of ethyl acetate solutions in two water-ethanol mixtures was performed at 280 and 330K. The MD simulations revealed that ethyl acetate was preferentially solvated by ethanol, water being mainly located in the next solvation layer. With increasing temperature ethanol was gradually replaced by water in the first solvation shell. These findings explain the decrease in the rate of ester hydrolysis with increasing molar ratio of ethanol in the solution as the reaction rate was linearly dependent on the relative ethanol content in the first solvation shell of the ester. Predominance of ethanol results in decreased polarity and water activity in the shell and accordingly in a decreased reaction rate. Based on the results of the MD simulations, the principal conclusion of this work is that ultrasound enhances the kinetic energy (the effective temperature) of species in the solution and, in this way, evokes shifts in the solvation equilibria thus affecting the reaction rate. It appears that ultrasound does not completely break down the solvent shells or clusters in the solution as previously believed. Phenomena of thermo-solvatochromism and reaction rate levelling by ultrasound in binary solvents are described.