Theory of enthalpy-entropy compensation

• Published in: Journal of physical chemistry (1952) Vol. 93; no. 25; pp. 8240 - 8243
• Main Authors: Boots, H. M. J, De Bokx, P. K
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 01-12-1989
• Subjects: 990200 > Mathematics & Computers; CALCULATION METHODS; CHEMICAL REACTIONS; Chemical thermodynamics; Chemistry; DATA; DATA ANALYSIS; ENTHALPY; ENTROPY; Exact sciences and technology; GENERAL AND MISCELLANEOUS//MATHEMATICS, COMPUTING, AND INFORMATION SCIENCE; General and physical chemistry; INFORMATION; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ION EXCHANGE; MATHEMATICAL MODELS; NUMERICAL DATA; PHYSICAL PROPERTIES; THEORETICAL DATA; THERMODYNAMIC PROPERTIES 400200 > Inorganic, Organic, & Physical Chemistry; Potential energy; Statistical method; Enthalpy; Theoretical study; Entropy; Thermodynamic properties; Modeling
• ISSN: 0022-3654; 1541-5740
• DOI: 10.1021/j100362a018

The ubiquitous nature of enthalpy-entropy compensation calls for a general model. The present model, which is formulated with compensation in ion exchange in mind, is an extension of an older general approach in that the molar fractions of the species that are exchanged in the process enter explicitly. In a different way, it is an extension to the theory of conformal solutions, which only leads to compensation under the condition of conformity. The present model allows one to decide from experiment whether interactions between exchanging species or interactions with third species (or external fields) are responsible for the compensation effect.