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

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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

Fingerprint

isothermal processes
Molecular modeling
Calorimetry
Titration
titration
affinity
heat measurement
engineering
Liquids
liquids
Complexation
Enthalpy
enthalpy
Phenols
phenols
regeneration
acetic acid
Acidity
Acetic acid
acidity

Keywords

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

Cite this

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title = "Molecular design and engineering for affinity separation processes using isothermal titration calorimetry (ITC) and molecular modeling (MM)",
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.",
keywords = "Isothermal titration calorimetry, Molecular modeling, Reactive extraction, Solvent design",
author = "Sprakel, {Lisette M.J.} and Boelo Schuur",
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AB - 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.

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