Encyclopedia of Biophysics

Living Edition
| Editors: Gordon Roberts, Anthony Watts, European Biophysical Societies

Van’t Hoff Analysis and Hidden Thermodynamic Variables

  • Alan Cooper
Living reference work entry
DOI: https://doi.org/10.1007/978-3-642-35943-9_10066-1

Synonyms

Definition

Van’t Hoff analysis is a procedure in classical chemical thermodynamics that may be used to estimate the apparent enthalpy (ΔHvH) of a process from the temperature dependence of its equilibrium constant (Keq), usually determined from the slope of a (linear) van’t Hoff plot of ln Keq vs 1/T.

Introduction

For any thermodynamic equilibrium process that proceeds with non-zero enthalpy (heat of reaction), the equilibrium will be perturbed by change in temperature (Le Chatelier principle). This is the basis for van’t Hoff analysis that has previously been used extensively as a way to characterize the temperature dependence of thermodynamic equilibrium processes and is often applied in biophysical and biochemical investigations as an indirect method for estimating standard enthalpy changes. Although now largely superseded by more direct calorimetric methods, careful application of this kind of analysis can yield useful additional...

This is a preview of subscription content, log in to check access.

References

  1. Baker BM, Murphy KP (1996) Evaluation of linked protonation effects in protein binding reactions using isothermal titration calorimetry. Biophys J 71(4):2049–2055CrossRefPubMedPubMedCentralGoogle Scholar
  2. Chaires JB (1997) Possible origin of differences between van’t Hoff and calorimetric enthalpy estimates. Biophys Chem 64(1–3):15–23CrossRefPubMedGoogle Scholar
  3. Cooper A (2010) Protein heat capacity: an anomaly that maybe never was. J Phys Chem Lett 1(22):3298–3304CrossRefGoogle Scholar
  4. Cooper A, Converse CA (1976) Energetics of primary processes in visual excitation: photocalorimetry of rhodopsin in rod outer segment membranes. Biochemistry 15(14):2970–2978CrossRefPubMedGoogle Scholar
  5. Cooper A, Johnson CM et al (2001) Heat does not come in different colours: entropy-enthalpy compensation, free energy windows, quantum confinement, pressure perturbation calorimetry, solvation and the multiple causes of heat capacity effects in biomolecular interactions. Biophys Chem 93(2–3):215–230CrossRefPubMedGoogle Scholar
  6. Dunitz JD (1995) Win some, lose some – enthalpy-entropy compensation in weak intermolecular interactions. Chem Biol 2(11):709–712CrossRefPubMedGoogle Scholar
  7. Engel J, Schwarz G (1970) Cooperative conformational transitions of linear biopolymers. Angew Chem Int Ed Engl 9(6):389–400CrossRefPubMedGoogle Scholar
  8. Horn JR, Russell D et al (2001) van’t Hoff and calorimetric enthalpies from isothermal titration calorimetry: are there significant discrepancies? Biochemistry 40(6):1774–1778CrossRefPubMedGoogle Scholar
  9. Liu YF, Sturtevant JM (1997) Significant discrepancies between van’t Hoff and calorimetric enthalpies .3. Biophys Chem 64(1–3):121–126CrossRefPubMedGoogle Scholar
  10. Mabrey S, Sturtevant JM (1976) Investigation of phase-transitions of lipids and lipid mixtures by high sensitivity differential scanning calorimetry. Proc Natl Acad Sci U S A 73(11):3862–3866CrossRefPubMedPubMedCentralGoogle Scholar
  11. Naghibi H, Tamura A et al (1995) Significant discrepancies between Van’t Hoff and calorimetric enthalpies. Proc Natl Acad Sci U S A 92(12):5597–5599CrossRefPubMedPubMedCentralGoogle Scholar
  12. van’t Hoff JH (1884) Études de Dynamique Chimique (Studies in dynamic chemistry). Frederik Muller, AmsterdamGoogle Scholar
  13. Wyman J (1964) Linked functions and reciprocal effects in hemoglobin: a second look. Adv Protein Chem 19:223–286CrossRefPubMedGoogle Scholar
  14. Zhou Y, Hall CK et al (1999) The calorimetric criterion for a two-state process revisited. Protein Sci 8(5):1064–1074CrossRefPubMedPubMedCentralGoogle Scholar

Copyright information

© European Biophysical Societies’ Association (EBSA) 2018

Authors and Affiliations

  1. 1.School of ChemistryUniversity of GlasgowGlasgowUK

Section editors and affiliations

  • Alan Cooper
    • 1
  1. 1.School of Chemistry, University of GlasgowGlasgowUK