Molecular theory of the volume change accompanying contact-complex formation reactions in solution
- 1 November 1984
- journal article
- research article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 81 (9), 4080-4086
- https://doi.org/10.1063/1.448152
Abstract
A theoretical expression of the volume change accompanying the contact‐complex formation in the hard‐sphere fluid at infinite dilution has been derived by using the radial distribution function and the equation of state. It is revealed that the volume change is composed of the two additive terms related to (i) the molecular packing and (ii) the thermal motion of molecules. In order to comprehend the volume change at the molecular level, the numerical calculation of the volume change based on the theory developed has been performed as a function of the solvent density and the size ratio of the solute to the solvent molecules. The volume changes obtained at liquid densities are dominated by the molecular packing term, and their values in solvents of the common size are in the range of −5 to −10 cm3 mol− 1 in reasonable agreement with the experimental results for the weak EDA complexes in solution.Keywords
This publication has 13 references indexed in Scilit:
- Volumetric study on the 1,3-dipolar cycloaddition reaction. 2. .alpha.-Benzoyl-N-phenylnitrone with several olefinsJournal of the American Chemical Society, 1983
- Volumetric Study on the 1,3-Dipolar Cycloaddition Reaction of Diazodiphenylmethane with Several OlefinsBulletin of the Chemical Society of Japan, 1983
- Effects of liquid structures on chemical reactions and conformational changes of non-rigid molecules in condensed phasesFaraday Discussions of the Chemical Society, 1978
- A scaled particle theory of aqueous and nonaqueous solutionsChemical Reviews, 1976
- What is "liquid"? Understanding the states of matterReviews of Modern Physics, 1976
- Roles of Repulsive and Attractive Forces in Liquids : The Equilibrium Theory of Classical FluidsAdvances in Chemical Physics, 1976
- Theories of LiquidsAnnual Review of Physical Chemistry, 1972
- Distribution functions of multi-component fluid mixtures of hard spheresMolecular Physics, 1972
- Effect of pressure on charge transfer complexes in solutionTransactions of the Faraday Society, 1968
- Thermodynamics of an activated complexTransactions of the Faraday Society, 1937