Effective molarity: Difference between revisions
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In [[chemistry]], the '''Effective Molarity''' (denoted |
In [[chemistry]], the '''Effective Molarity''' (denoted ''EM'')<ref name=Kirby>{{cite book|last=Kirby, AJ in|title=Advances in Physical Organic Chemistry|year=1980|publisher=Academic Press|location=London|isbn=9780120335176|pages=183-278}}</ref> is defined as the ratio between the first-order rate constant of an [[intramolecular reaction]] and the second-order rate constant of the corresponding intermolecular reaction (''Kinetic Effective Molarity'')<ref name=Kirby /><ref>{{cite book|last=Dougherty|first=Eric V. Anslyn ; Dennis A.|title=Modern physical organic chemistry|year=2006|publisher=University Science Books|location=Sausalito, Calif.|isbn=9781891389313|pages=496|edition=Dodr.}}</ref> or the ratio between the [[equilibrium constant]] of an [[intramolecular reaction]] and the [[equilibrium constant]] of the corresponding intermolecular reaction (''Thermodynamic Effective Molarity'')<ref name=Kirby /><ref>{{cite journal|last=Hunter|first=Christopher A.|coauthors=Anderson, Harry L.|title=What is Cooperativity?|journal=Angewandte Chemie International Edition|date=28 September 2009|volume=48|issue=41|pages=7488–7499|doi=10.1002/anie.200902490}}</ref>. |
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<math>EM_{kinetic} = {k_{intramolecular} \over k_{intermolecular}}</math> |
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<math>EM_{thermo} = {K_{intramolecular} \over K_{intermolecular}}</math> |
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EM has the dimension of concentration. High EM values always indicate greater ease of intramolecular processes over the corresponding intermolecular ones. Effective molarities can be used to get a deeper understanding of the effects of intramolecularity on reaction courses.<ref>{{cite journal|last=Krishnamurthy|first=Vijay M.|coauthors=Semetey, Vincent; Bracher, Paul J.; Shen, Nan; Whitesides, George M.|title=Dependence of Effective Molarity on Linker Length for an Intramolecular Protein−Ligand System|journal=Journal of the American Chemical Society|date=1 February 2007|volume=129|issue=5|pages=1312–1320|doi=10.1021/ja066780e}}</ref> In last decades, the frequency of use of effective molarity in scientific literature has shown a marked decrease, because this formalism is being progressively replaced by more important [[physical quantities]]. |
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==See also== |
==See also== |
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*[[Intramolecular reaction]] |
*[[Intramolecular reaction]] |
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*[[Polymerization]] |
*[[Polymerization]] |
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==References== |
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{{Reflist}} |
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[[Category:Physical organic chemistry]] |
[[Category:Physical organic chemistry]] |
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Revision as of 22:32, 2 January 2013
In chemistry, the Effective Molarity (denoted EM)[1] is defined as the ratio between the first-order rate constant of an intramolecular reaction and the second-order rate constant of the corresponding intermolecular reaction (Kinetic Effective Molarity)[1][2] or the ratio between the equilibrium constant of an intramolecular reaction and the equilibrium constant of the corresponding intermolecular reaction (Thermodynamic Effective Molarity)[1][3].
EM has the dimension of concentration. High EM values always indicate greater ease of intramolecular processes over the corresponding intermolecular ones. Effective molarities can be used to get a deeper understanding of the effects of intramolecularity on reaction courses.[4] In last decades, the frequency of use of effective molarity in scientific literature has shown a marked decrease, because this formalism is being progressively replaced by more important physical quantities.
See also
References
- ^ a b c Kirby, AJ in (1980). Advances in Physical Organic Chemistry. London: Academic Press. pp. 183–278. ISBN 9780120335176.
- ^ Dougherty, Eric V. Anslyn ; Dennis A. (2006). Modern physical organic chemistry (Dodr. ed.). Sausalito, Calif.: University Science Books. p. 496. ISBN 9781891389313.
{{cite book}}: CS1 maint: multiple names: authors list (link) - ^ Hunter, Christopher A. (28 September 2009). "What is Cooperativity?". Angewandte Chemie International Edition. 48 (41): 7488–7499. doi:10.1002/anie.200902490.
{{cite journal}}: Unknown parameter|coauthors=ignored (|author=suggested) (help) - ^ Krishnamurthy, Vijay M. (1 February 2007). "Dependence of Effective Molarity on Linker Length for an Intramolecular Protein−Ligand System". Journal of the American Chemical Society. 129 (5): 1312–1320. doi:10.1021/ja066780e.
{{cite journal}}: Unknown parameter|coauthors=ignored (|author=suggested) (help)