IUPAC > Gold Book > alphabetical index > T > transition state theory
icon


Indexes

transition state theory
A theory of the rates of elementary reactions which assumes a special type of equilibrium, having an equilibrium constant Math - ei, to exist between reactants and activated complexes. According to this theory the rate constant is given by:
Math - e
where Math - ei is the Boltzmann constant and Math - ei is the Planck constant. The rate constant can also be expressed as:
Math - e
where Math - text, the entropy of activation, is the standard molar change of entropy when the activated complex is formed from reactants and Math - text, the enthalpy of activation, is the corresponding standard molar change of enthalpy. The quantities Math - text (the energy of activation) and Math - text are not quite the same, the relationship between them depending on the type of reaction. Also:
Math - e
where Math - text, known as the Gibbs energy of activation, is the standard molar Gibbs energy change for the conversion of reactants into activated complex. A plot of standard molar Gibbs energy against a reaction coordinate is known as a Gibbs-energy profile; such plots, unlike potential-energy profiles, are temperature-dependent. In principle the equations above must be multiplied by a transmission coefficient, Math - text, which is the probability that an activated complex forms a particular set of products rather than reverting to reactants or forming alternative products. It is to be emphasized that Math - text, Math - text and Math - text occurring in the former three equations are not ordinary thermodynamic quantities, since one degree of freedom in the activated complex is ignored. Transition-state theory has also been known as absolute rate theory, and as activated-complex theory, but these terms are no longer recommended.
Source:
PAC, 1996, 68, 149 (A glossary of terms used in chemical kinetics, including reaction dynamics (IUPAC Recommendations 1996)) on page 190
Interactive Link Maps
First LevelSecond LevelThird Level
GraphGraphGraph
Cite as:
IUPAC. Compendium of Chemical Terminology, 2nd ed. (the "Gold Book"). Compiled by A. D. McNaught and A.Wilkinson. Blackwell Scientific Publications, Oxford (1997). XML on-line corrected version: http://goldbook.iupac.org (2006-) created by M. Nic, J. Jirat, B. Kosata; updates compiled by A. Jenkins. ISBN 0-9678550-9-8. doi:10.1351/goldbook.
Last update: 2008-10-07; version: 2.0.2.
DOI of this term: doi:10.1351/goldbook.T06470.
Original PDF version (may be out of date): http://www.iupac.org/goldbook/T06470.pdf.
Version for print | History of this term
picture