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Current Status of Enthalpy–Entropy Compensation Phenomenon


Affiliations
1 Centre for Surface Science, Department of Chemistry, Jadavpur University, Kolkata 700 032, India
2 Department of Chemistry, Sundarban Hazi Desarat College, University of Calcutta, Pathankhali 743 611, India
3 Indian Society for Surface Science and Technology, Department of Chemistry, Jadavpur University, Kolkata 700 032, India
 

For similar physical–chemical processes in chemistry and biology, the phenomenon of linear enthalpy– entropy compensation (EEC) is a thermodynamic puzzle remaining unexplained for a long time. The basic thermodynamic rules do not rigorously support the EEC phenomenon. In some restricted conditions EEC may appear linear with nonrealistic (i.e. hypothetical) values of the slope (the compensation temperature), and the intercept (the compensation free energy). The compensation temperature (Tcomp) is normally higher than the experimental temperature. Compensation temperature may even become negative, and the related phenomenon is called anti-enthalpy–entropy compensation (AEEC). Negative Tcomp is unrealistic. Both EEC and AEEC are not explainable; the derived Tcomp and ΔGcomp (free energy of compensation) of the EEC plot are impractical. The neglect of the Gibbs free energy changes (of similar processes in the EEC plot) makes the phenomenon arbitrary. In a restricted condition (i.e. narrow free energy window range) linear compensation is an assumed solution. In overall consideration, the reported correlations are physicochemically uncertain. The said compensation may arise for both kinetic and equilibrium processes. The manifestations are nearly same. Our demonstration and discussion in this paper pertain to equilibrium processes.

Keywords

Anti-Compensation, Current Status, Enthalpy– Entropy Compensation, Free Energy Window.
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  • Cornish-Bowden, A., Enthalpy–entropy compensation: a phantom phenomenon. J. Biosci., 2002, 27, 121–126.
  • Lumry, R. and Rajender, S., Enthalpy–entropy compensation phenomena in water solutions of proteins and small molecules: a ubiquitous property of water. Biopolymers, 1970, 9, 1125–1227.
  • Starikov, E. B. and Norden, B., Enthalpy−entropy compensation: a phantom or something useful? J. Phys. Chem. B, 2007, 111, 14431–14435.
  • Linert, W. and Jameson, R. F., The isokinetic relationship. Chem. Soc. Rev., 1989, 18, 477–505.
  • Liu, L. and Guo, Q., Isokinetic relationship, isoequilibrium relationship, and enthalpy–entropy compensation. Chem. Rev., 2001, 101, 673–696.
  • Pan, A., Biswas, T., Rakshit, A. K. and Moulik, S. P., Enthalpy– entropy compensation (EEC) effect: a revisit J. Phys. Chem. B, 2015, 119, 15876–15884.
  • Pan, A., Rakshit, A. K. and Moulik, S. P., Micellization thermodynamics and the nature of enthalpy–entropy compensation. Colloid. Surf. A, 2016, 495, 248–254.
  • Pan, A., Kar, T., Rakshit, A. K. and Moulik, S. P., Enthalpy– entropy compensation (EEC) effect: decisive role of free energy. J. Phys. Chem. B, 2016, 120, 10531–10539.
  • Starikov, E. B., Entropy–enthalpy compensation and its significance in particular for nanoscale events. J. Appl. Solution Chem. Model, 2013, 2, 126–135.
  • Mandal, B., Rakshit, A. K., Moulik, S. P. and Pan, A., A rational study of the origin and generality of anti-enthalpy–entropy compensation (AEEC) phenomenon. Z. Phys. Chem., 2018, 232, 373– 391.
  • Ford, D. M., Enthalpy–entropy compensation is not a general feature of weak association. J. Am. Chem. Soc., 2005, 127, 16167– 16170.
  • Piguet, C., Enthalpy–entropy correlations as chemical guides to unravel self-assembly processes. Dalton Trans., 2011, 40, 8059– 8071.
  • Graziano, G., Case study of enthalpy–entropy noncompensation. J. Chem. Phys., 2004, 120, 4467–4471.
  • Dunitz, J. D., Win some, lose some: enthalpy–entropy compensation in weak intermolecular interactions. Chem. Biol., 1995, 2, 709–712.
  • Fox, J. M., Zhao, M., Fink, M. J., Kang, K. and Whitesides, G. M., The molecular origin of enthalpy/entropy compensation in biomolecular recognition. Annu. Rev. Biophys., 2018, 47, 223–250.
  • Chatterjee, A., Moulik, S. P., Sanyal, S. K., Mishra, B. K. and Puri, P. M., Thermodynamics of micelle formation of ionic surfactants: a critical assessment for sodium dodecyl sulfate, cetyl pyridinium chloride and dioctyl sulfosuccinate (Na salt) by microcalorimetric, conductometric and tensiometric measurements. J. Phys. Chem. B, 2001, 105, 12823–12831.
  • Moulik, S. P. and Mitra, D., Amphiphile self-aggregation: an attempt to reconcile the agreement–disagreement between the enthalpies of micellization determined by the van’t Hoff and calorimetry methods. J. Colloid Interf. Sci., 2009, 337, 569–578.
  • Rao, K. S., Trivedi, T. J. and Kumar, A., Aqueous-biamphiphilic ionic liquid systems: self-assembly and synthesis of gold nanocrystals/ microplates. J. Phys. Chem. B., 2012, 116, 14363–14374.
  • Blandamer, M. J., Cullis, P. M. and Gleeson, P. T., Three important calorimetric applications of a classic thermodynamic equation. Chem. Soc. Rev., 2003, 32, 264–267.
  • Sharp, K., Entropy–enthalpy compensation: fact or artifact? Protein Sci., 2001, 10, 661–667.
  • Krug, R. R., Detection of the compensation effect (θ rule). Ind. Eng. Chem. Fundamen., 1980, 19, 50–59.
  • Cooper, A. C., Johnson, M., Lakey, J. H. and Nöllmann, M., 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., 2001, 93, 215–230.
  • Khrapunov, S., The enthalpy–entropy compensation phenomenon. Limitations for the use of some basic thermodynamic equations. Curr. Protein Pept. Sci., 2018, 19, 1088–1091.
  • Dragan, A. I., Read, C. M. and Crane-Robinson, C., Enthalpy– entropy compensation: the role of solvation. Eur. Biophys. J., 2017, 46, 301–308.
  • Khakhel, O. A. and Romashko, T. P., The origin of extrathermodynamic compensations. Heliyon, 2019, 5, e01839.
  • Vázquez-Tato, M. P., Meijide, F., Seijas, J. A., Fraga, F. and Vázquez Tato, J., Analysis of an old controversy: the compensation temperature for micellization of surfactants. Adv. Colloid. Interf. Sci., 2018, 254, 94–98.
  • Chen, L.-J., Lin, S.-Y. and Huang, C.-C., Effect of hydrophobic chain length of surfactants on enthalpy–entropy compensation of micellization. J. Phys. Chem. B, 1998, 102, 4350–4356.
  • Rao, K. S., Singh, T., Trivedi, T. J. and Kumar, A., Aggregation behaviour of amino acid ionic liquid surfactants in aqueous media. J. Phys. Chem. B, 2011, 115, 13847–13853.
  • Ben-Naim, A. and Marcus, Y., Solvation thermodynamics of nonionic solutes. J. Chem. Phys., 1984, 81, 2016–2027.

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  • Current Status of Enthalpy–Entropy Compensation Phenomenon

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Authors

Satya Priya Moulik
Centre for Surface Science, Department of Chemistry, Jadavpur University, Kolkata 700 032, India
Bappaditya Naskar
Department of Chemistry, Sundarban Hazi Desarat College, University of Calcutta, Pathankhali 743 611, India
Animesh Kumar Rakshit
Indian Society for Surface Science and Technology, Department of Chemistry, Jadavpur University, Kolkata 700 032, India

Abstract


For similar physical–chemical processes in chemistry and biology, the phenomenon of linear enthalpy– entropy compensation (EEC) is a thermodynamic puzzle remaining unexplained for a long time. The basic thermodynamic rules do not rigorously support the EEC phenomenon. In some restricted conditions EEC may appear linear with nonrealistic (i.e. hypothetical) values of the slope (the compensation temperature), and the intercept (the compensation free energy). The compensation temperature (Tcomp) is normally higher than the experimental temperature. Compensation temperature may even become negative, and the related phenomenon is called anti-enthalpy–entropy compensation (AEEC). Negative Tcomp is unrealistic. Both EEC and AEEC are not explainable; the derived Tcomp and ΔGcomp (free energy of compensation) of the EEC plot are impractical. The neglect of the Gibbs free energy changes (of similar processes in the EEC plot) makes the phenomenon arbitrary. In a restricted condition (i.e. narrow free energy window range) linear compensation is an assumed solution. In overall consideration, the reported correlations are physicochemically uncertain. The said compensation may arise for both kinetic and equilibrium processes. The manifestations are nearly same. Our demonstration and discussion in this paper pertain to equilibrium processes.

Keywords


Anti-Compensation, Current Status, Enthalpy– Entropy Compensation, Free Energy Window.

References





DOI: https://doi.org/10.18520/cs%2Fv117%2Fi8%2F1286-1291