Case I: High pressure 高压,碰撞失活远 大于反应 k1[M]>>k2 级反应 k,k,lAJ[MI Kk2LAJLMI k1[M]+k2k1[M] k[4] 高压限速率常数
Case II: High pressure 1 2 k [M] k − 1 2 1 2 [ ] [ ][ ] k M k k k A M r + = − 1 2 1 [ ][ ] [ ] [ ] k k A M k M k A − = = 高压, 碰撞失活 远 大于 反应 一级反应 高压限速率常数
k r=k[a] kk2LAJM k1[M]+k2 r=kLAJLMI
[ ][ ] r = k1 A M r k [A] = 1 2 1 2 [ ] [ ][ ] k M k k k A M r + = −
experimental Lindemann
Sir Cyril n. hinshelwood Rudolpha. Marcus 1956 Noble prize 1992 Noble prize Mechanisms of chemical Theories of electron reactions transfer
1956 Noble Prize Mechanisms of chemical reactions Sir Cyril N. Hinshelwood Rudolph A. Marcus 1992 Noble Prize Theories of electron transfer
RRKM theory, 19301950 Rice-Ramsperger-Kassel-M arcus A+M—A"+M k A≠ P
RRKM theory, 1930 ~ 1950 Rice-Ramsperger-Kassel-Marcus A + M A* + M k1 k-1 A* A P k2 k E *