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A Generalized Statement of the Law of Mass Action

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James K. Baird

The University of Alabama in Huntsville, Department of Chemistry, Huntsville, AL 35899

J. Chem. Educ., 1999, 76 (8), p 1146

DOI: 10.1021/ed076p1146

Publication Date (Web): August 1, 1999

Section:

History, Education, and Documentation

Abstract

When expressed in a generalized form in terms of thermodynamic activities, the law of mass action can be made to take into account the non-ideal behavior of reactants in solution in a way that is consistent with both equilibrium and non-equilibrium thermodynamics. Specifically, when combined with the principle of detailed balance, the generalized law of mass action predicts the thermodynamically exact result linking the forward and reverse rate constants, the equilibrium activities, and the equilibrium constant. For a reaction approaching equilibrium, it predicts in agreement with non-equilibrium thermodynamics a proportionality between the net reaction rate and the instantaneous Gibbs free energy of reaction. In the case of an irreversible reaction between ions in solution, the generalized law leads to the Brönsted-Bjerrum equation connecting the rate constant to the ionic strength. For reactions in the gas phase or in dilute ideal solution, the generalized law assumes the familiar form of the original Guldberg and Waage law of mass action (1864). Because of its universal character, the generalized law can be used as a unique starting point for a course in chemical kinetics.

Keywords (Audience):

Upper-Division Undergraduate

Keywords (Domain):

Physical Chemistry

Keywords (Subject):

Aqueous Solution Chemistry

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This article has been cited by 5 ACS Journal articles (5 most recent appear below).

Reaction Kinetics and Critical Phenomena: Iodination of Acetone in Isobutyric Acid + Water near the Consolute Point
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The Journal of Physical Chemistry A2010 114 (1), 355-359
- Reaction Kinetics and Critical Phenomena: Iodination of Acetone in Isobutyric Acid + Water near the Consolute Point
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  The Journal of Physical Chemistry A2010 114 (1), 355-359
  The rate of iodination of acetone has been measured as a function of temperature in the binary solvent isobutyric acid (IBA) + water near the upper consolute point. The reaction mixture was prepared by the addition of acetone, iodine, and potassium iodide ...
  Abstract | Full Text HTML | Hi-Res PDF | PDF w/ Links
Reaction Kinetics and Critical Phenomena: Rates of Some First Order Gas Evolution Reactions in Binary Solvents with a Consolute Point
Yeong Woo Kim and James K. Baird
The Journal of Physical Chemistry A2005 109 (21), 4750-4757
- Reaction Kinetics and Critical Phenomena: Rates of Some First Order Gas Evolution Reactions in Binary Solvents with a Consolute Point
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  The Journal of Physical Chemistry A2005 109 (21), 4750-4757
  We have measured the rate of carbon dioxide evolution in the aniline catalyzed decomposition of acetone dicarboxylic acid in a mixture of isobutyric acid + water near its consolute point. Within a temperature interval of 1 C, which included the critical ...
  Abstract | Full Text HTML | Hi-Res PDF
Fluctuation-Dissipation Theorem for Chemical Reactions near a Critical Point
James K. Baird and Yeong Woo Kim
The Journal of Physical Chemistry A2003 107 (48), 10241-10242
- Fluctuation-Dissipation Theorem for Chemical Reactions near a Critical Point
  James K. Baird and Yeong Woo Kim
  The Journal of Physical Chemistry A2003 107 (48), 10241-10242
  In a fluid mixture near a critical point, there are long-range fluctuations in the component concentrations that exceed the range of the intermolecular forces. If the components are linked by a chemical reaction, then the fluctuations in the ...
  Abstract | Full Text HTML | Hi-Res PDF
Kinetics of S_N1 Reactions in Binary Liquid Mixtures near the Critical Point of Solution
Yeong Woo Kim and James K. Baird
The Journal of Physical Chemistry A2003 107 (41), 8435-8443
- Kinetics of S_N1 Reactions in Binary Liquid Mixtures near the Critical Point of Solution
  Yeong Woo Kim and James K. Baird
  The Journal of Physical Chemistry A2003 107 (41), 8435-8443
  We have measured the rates of the SN1 hydrolysis reactions of 2-chloro-2-methylbutane in isobutyric acid + water and 2-bromo-2-methylpropane in trietylamine + water near their respective consolute points. In the former mixture, two phases coexist below ...
  Abstract | Full Text HTML | Hi-Res PDF
The Application of the Concept of Extent of Reaction
Adela E. Croce
Journal of Chemical Education2002 79 (4), 506
- The Application of the Concept of Extent of Reaction
  Adela E. Croce
  Journal of Chemical Education2002 79 (4), 506
  The concept of extent of reaction permits the definition of the related variable, degree of advancement. The expression of the concentrations in the reaction rate equation as a function of one degree of advancement variable leads to considerable ...
  Abstract | Hi-Res PDF | PDF w/ Links