Premium
New Approach to Determine the Activation and Reaction Volumes of Low Polar Molecular Processes
Author(s) -
Kornilov Dmitry A.,
Kiselev Vladimir D.
Publication year - 2015
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.20916
Subject(s) - chemistry , bar (unit) , polar , reaction rate constant , thermodynamics , logarithm , volume (thermodynamics) , ambient pressure , equilibrium constant , reaction rate , atmospheric temperature range , analytical chemistry (journal) , kinetics , organic chemistry , mathematical analysis , physics , mathematics , quantum mechanics , astronomy , meteorology , catalysis
ABSTRACT For low polar molecular processes, we found the reliable relationship between the logarithm changes of the rate or equilibrium constants in the pressure range 1–1000 bar, [Ln( K P = 1000 / K P = 1 )/1000], and tangent modulus at P = 1 bar, ∂Ln( K P )/∂ P : ∂Ln( K P )/∂ P = 1.15·[Ln( K P = 1000 / K P = 1 )/1000], R = 0.995, which allows to predict the value of activation and reaction volume at ambient pressure. Therefore, it is sufficient to determine the values of the rate or equilibrium constants only at ambient pressures and at 1000 bar for the reliable estimation of the values of activation or reaction volume.