山大物理化学英文下7.pptVIP

7.3 Thermodynamic treatment of TST For nonideal systems, the intermolecular interaction makes the partition function complex. For these cases, the kinetic treatment becomes impossible. In 1933, LaMer tried to treat TST thermodynamically. Standard molar entropy of activation, standard molar enthalpy of activation The thermodynamic expression of the rate of TST is different from Arrhenius equation According to Gibbs-Holmholtz equation For liquid reaction: p?V = 0 For gaseous reaction: n is the number of reactant molecules thermodynamic expression of the rate of TST. is a general constant with unit of s-1 of the magnitude of 1013. The pre-exponential factor depends on the standard entropy of activation and related to the structure of activated complex. Example: reactions P exp(?S/R) (CH3)2PhN + CH3I 0.5 ? 10-7 0.9 ? 10-8 Hydrolysis of ethyl acetate 2.0 ? 10-5 5.0 ? 10-4 Decomposition of HI 0.5 0.15 Decomposition of N2O 1 1 suggests that the steric factor can be estimated from the activation entropy of the activated complex. John C. Polanyi 1986 Noble Prize Canada 1929/01/23 ~ Comments on TST §9.7 Transition state theory (TST) Theory of Absolute reaction Rates Theory of activated complex theory The transition state theory (TST), attempting to explain reaction rates on the basis of thermodynamics, was developed by H. Eyring and M. Polanyi during 1930-1935. TST treated the reaction rate from a quantum mechanical viewpoint involves the consideration of intramolecular forces and intermolecular forces at the same time. A + B-C ? A-B + C During reaction, energies are being redistributed among bonds: old bonds are being ripped apart and new bonds formed. H + H–H ? H????????? H????H ? H??????H??????H (Is it strange??) ? H????H????????????H ? H–H + H This process can be generalized as: A + B-C ?? [A-B-C]? ?? A-B + C Activated complex Transition state Activated complex is in