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Hammond's postulate
Hammond's postulate, also referred to as the HammondLeffler postulate, is a hypothesis, derived from transition state theory, concerning the transition state of organic chemical reactions, which states that:[1] If two states, for example, a transition state and an unstable intermediate, occur consecutively during a reaction process and have nearly the same energy content, their interconversion will involve only a small reorganization of the molecular structures.
Hammond's postulate time to rearrange. Whether run at high or low temperatures, the mixture of the kinetic and thermodynamic products will eventually reach the same ratio, one in favor of the more stable thermodynamic product, when given time to equilibrate due to microreversal.
History
The postulate is named after its creator, George S. Hammond. He first stated it in 1955 while he was a professor of Chemistry at Iowa State. Hammond first put his postulate in print in the Journal of the American Chemical Society. John E. Leffler of Florida State University proposed a similar idea a few years before Hammond,[3] but Hammond's version became more popular. One alternate name giving credit to both scientists is the Hammond-Leffler postulate.
References
[1] Hammond, G. S. (1955). "A Correlation of Reaction Rates". J. Am. Chem. Soc. 77: 334338. doi:10.1021/ja01607a027. Solomons, T.W. Graham & Fryhle, Craig B. (2004). Organic Chemistry (8th ed.). John Wiley & Sons, Inc. ISBN 0-471-41799-8. Loudon, G. Marc. "Organic Chemistry" 4th ed. 2005. Yarnell, Amanda. Hammond Postulate: 1955 paper used transition-state theory to explain structure-reactivity relationships. Chemical & Engineering News May 19, 2003, 81(20), 42 (http:/ / pubs. acs. org/ cen/ science/ 8120/ 8120sci2. html) [2] A dimensionless reaction coordinate for quantifying the lateness of transition states Thomas A. Manz, David S. Sholl J. Comput. Chem.; 2009 (EarlyView) doi: 10.1002/jcc.21440 [3] Leffler, J. E. Parameters for the Description of Transition States. Science 1953, 117, 340341.
Further reading
Nic, M.; Jirat, J.; Kosata, B., eds. (2006). "Hammond principle (Hammond postulate)" (http://goldbook.iupac. org/H02734.html). IUPAC Compendium of Chemical Terminology (Online ed.). doi:10.1351/goldbook.H02734. ISBN0-9678550-9-8.
License
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