Molecular design and engineering for affinity separation processes using isothermal titration calorimetry (ITC) and molecular modeling (MM)

Lisette M.J. Sprakel, Boelo Schuur*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

2 Citations (Scopus)

Abstract

A molecular design approach based on isothermal titration calorimetry (ITC) and molecular modeling (MM) was investigated for the development of new extractants in liquid-liquid extraction (LLX) systems. The molecular designs were validated in LLX experiments. Key in the regeneration of a solvent by temperature-swing back-extraction is the temperature dependency of the complexation equilibrium, which is related to the enthalpy of complexation ∆H. The relation between the molecular structure of extractants and the thermodynamics of complexation in LLX was studied for extraction of acetic acid by basic extractants and 4-cyanopyridine by phenols. For the basic extractants longer alkyl chains and additions of rings decreased ∆H, whereas for the phenols the acidity of the phenolic proton, and hence the complexation enthalpy, could be increased by electron withdrawing substituents. Using ∆H as determined with ITC, the temperature dependency of the liquid-liquid equilibrium could indeed be described. Also enthalpy-entropy compensation (EEC) could be observed in the data obtained by ITC, i.e. for extractants of the same family with a larger enthalpy, an opposite effect on the entropic contribution was observed.

Original languageEnglish
Pages (from-to)312-324
Number of pages13
JournalJournal of molecular liquids
Volume283
Early online date16 Mar 2019
DOIs
Publication statusPublished - 1 Jun 2019

Keywords

  • Isothermal titration calorimetry
  • Molecular modeling
  • Reactive extraction
  • Solvent design

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