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Lindemann mechanism
In chemical kinetics, the Lindemann mechanism (also called the Lindemann–Christiansen mechanism[1] or the Lindemann–Hinshelwood mechanism[2][3]) is a schematic reaction mechanism for unimolecular reactions. Frederick Lindemann and J. A. Christiansen proposed the concept almost simultaneously in 1921,[4][1] and Cyril Hinshelwood developed it to take into account the energy distributed among vibrational degrees of freedom for some reaction steps.[5][6]
It breaks down an apparently unimolecular reaction into two elementary steps, with a rate constant for each elementary step. The rate law and rate equation for the entire reaction can be derived from the rate equations and rate constants for the two steps.
The Lindemann mechanism is used to model gas phase decomposition or isomerization reactions. Although the net formula for decomposition or isomerization appears to be unimolecular and suggests first-order kinetics in the reactant, the Lindemann mechanism shows that the unimolecular reaction step is preceded by a bimolecular activation step so that the kinetics may actually be second-order in certain cases.[7]
- ^ a b Laidler, Keith J. (1987). Chemical Kinetics (3rd ed.). Harper and Row. p. 152. ISBN 0-06-043862-2.
A few days after Lindemann made his oral presentation, Christiansen published his Ph.D. thesis in which the same treatment was included.
- ^ Atkins, Peter; de Paula, Julio (2006). Physical Chemistry (8th ed.). W.H. Freeman. p. 820. ISBN 0-7167-8759-8.
- ^ Steinfeld J.I., Francisco J.S. and Hase W.L. Chemical Kinetics and Dynamics (2nd ed., Prentice-Hall 1999) p.334. ISBN 0-13-737123-3
- ^ Moore, John W.; Pearson, Ralph G. (1981). Kinetics and Mechanism (3rd ed.). John Wiley & Sons. p. 122. ISBN 0-471-03558-0.
- ^ Di Giacomo, F. (2015). "A Short Account of RRKM Theory of Unimolecular Reactions and of Marcus Theory of Electron Transfer in a Historical Perspective". Journal of Chemical Education. 92 (3): 476. Bibcode:2015JChEd..92..476D. doi:10.1021/ed5001312.
- ^ Lindemann, F. A.; Arrhenius, S.; Langmuir, I.; Dhar, N. R.; Perrin, J.; Mcc. Lewis, W. C. (1922). "Discussion on "the radiation theory of chemical action"". Transactions of the Faraday Society. 17: 598. doi:10.1039/TF9221700598.
- ^ [1] "Gas phase decomposition by the Lindemann mechanism" by S. L. Cole and J. W. Wilder. SIAM Journal on Applied Mathematics, Vol. 51, No. 6 (Dec., 1991), pp. 1489-1497.
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