Internal Degrees of Freedom as a Basis for Isotopic Effects in Thermodiffusion

Semen N. Semenov, Martin E. Schimpf

Research output: Contribution to journalArticlepeer-review

3 Scopus citations

Abstract

We present a model that relates isotope effects in thermodiffusion to changes in internal degrees of freedom associated with rotational and vibrational motion. The model uses general material transport equations for binary non-isothermal liquid systems, derived using non-equilibrium thermodynamics in our previous work. The equilibrium chemical potentials of the components at constant pressure are derived using statistical mechanics. In evaluating the model, we use experimental data on changes in the Soret coefficient of various hydrocarbons in perprotonated and perdeuterated cyclohexane. We also compare predictions of the model with experimental data on the Soret coefficient in isotopic mixtures. In all cases, the model is consistent with experimental data and computations.

Original languageAmerican English
Pages (from-to)11512-11519
Number of pages8
JournalJournal of Physical Chemistry B
Volume125
Issue number41
DOIs
StatePublished - 21 Oct 2021

Keywords

  • molecular dynamics
  • molecules
  • solvents
  • theoretical and computational chemistry
  • thermodynamic properties

EGS Disciplines

  • Chemistry

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