Thermodynamics of Deuterium Exchange Reactions in Water-Thiol and Alcohol-Thiol Systems

Abstract

Thermodynamic properties at 298 K are obtained for the deuterium exchange reactions

RSH + SHD → O + RSD + H₂O RSH + DO₂ → O + RSD + HDO RSH + R?OD → O + RSD + R?OH Equilibrium constants and enthalpies of the gas phase reactions with R = R' = CH₃ are calculated from statistical mechanical equations using recently published harmonic frequencies. Experimental properties, including the molar excess enthalpies of C₂H₅SH + CH₃OH, C₂H₅SH + CH₃OD, C₂H₅SH + C₂H₅OH and C₂H₅SH + C₂H₅OD reported in this paper, are used to obtain the equilibrium constants and enthalpies of the liquid and gas phase reactions with R = C₂H₅, R' = CH₃ and C₂H₅.