Two-step sequences with extended temkin nonuniform reactivity—Rate-determining step revisited
✍ Scribed by Vlad T. Popa; James A. Schwarz
- Publisher
- Elsevier Science
- Year
- 1996
- Tongue
- English
- Weight
- 581 KB
- Volume
- 51
- Category
- Article
- ISSN
- 0009-2509
No coin nor oath required. For personal study only.
✦ Synopsis
Within the Temkin-type approach for two-step mechanisms, the problem of the rate-determining step (rds) and its possible shift on a nonuniform surface is reexamined. The nonuniformity concept is extended to its maximum limits and a new transfer rule is derived for the model's intrinsic linear free energy relationships. For any thermodynamically allowable coupling of the two steps, this provides a quantitative estimation of rds shift, which is unimportant for reasonable model parameters. The proposed transfer rule leads to a unique analytical solution for the local turnover rate, whatever the steps' coupling. Copyright ~ 1996 Elsevier Science Ltd 1. BACKGROUND