Transition-state rate model
Transition-state theory relates an elementary rate coefficient to a constrained activated-complex equilibrium and a crossing frequency.
Key knowledge
Transition-state theory relates an elementary rate coefficient to a constrained activated-complex equilibrium and a crossing frequency. For a unimolecular standard-state model, k=κ(kBT/h)exp(−ΔG‡/RT). κ accounts for successful passage to the specified products; the activation free energy is not simply the overall reaction Gibbs energy.
Values and equations
k = κ(kBT/h) exp(−ΔG‡/RT)
- k
- unimolecular rate coefficient s⁻¹
- κ
- transmission coefficient 1
- kB
- Boltzmann constant J K⁻¹
- h
- Planck constant J s
- T
- absolute temperature K
- ΔG‡
- standard molar activation Gibbs energy J mol⁻¹
- R
- molar gas constant J mol⁻¹ K⁻¹
Conditions and scope
- The displayed coefficient has units s⁻¹; bimolecular conventions require consistent concentration standard factors.
- Equilibrium, dividing-surface and recrossing assumptions require assessment; tunnelling and dynamical effects can need extensions.
Sources · 1
References
Sources retain their recorded scope. A source link alone does not establish verification of every statement.
Evidence and review
Inspected IUPAC activated-complex relation, thermodynamic activation quantities and transmission coefficient.
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Entry details
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- uni-chem-transition-state-theory
- Revision
- core.1
- Structured reference record
- University core expansion