89.7 Theory for Gaseous bimolecular reaction Transition state theory tst) Extensive reading Levine, pp. 882-889 23.2 potential-energy surfaces
§9.7 Theory for Gaseous bimolecular reaction ---- Transition state theory (TST) Extensive reading: Levine, pp. 882-889. 23.2 potential-energy surfaces
89.7 Transition state theory (TST) 9.7.1 Brief introduction Quantum mechanics time Person Main contribution 1900 Max Planck black-body radiation 1905 Albert einstein Photoelectric effect oo Hydrogen Wave Function ():一, 1920s Erwin Schrodinger Early quantum theory Werner Heisenberg Max born 8 1927 Heitler-London Nature of chemical 回飞() 至 theory bond 圣兴#·
9.7.1 Brief introduction §9.7 Transition state theory (TST) Quantum mechanics time Person Main contribution 1900 Max Planck black-body radiation 1905 Albert Einstein Photoelectric effect 1920s Erwin Schrödinger Werner Heisenberg Max Born Early quantum theory 1927 Heitler-London theory Nature of chemical bond
89.7 Transition state theory (TST) 9.7.1 Brief introduction Polanyi mihaly Henry Eyring The transition state theory (TST), attempting to explain reaction rates on the basis of thermodynamics(potential energy -the nature of chemical bond), was developed by H. ring 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
The transition state theory (TST), attempting to explain reaction rates on the basis of thermodynamics (potential energy – the nature of chemical bond), 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. 9.7.1 Brief introduction Henry Eyring Polányi Mihály §9.7 Transition state theory (TST)
89.7 Transition state theory (TST) 9.7.1 Brief introduction FEBRUARY. 1935 JOURNAL OF CHEMICAL PHYSICS VOLUME 3 The Activated Complex in Chemical Reactions HENRY EYRING, Frick Chemical Laboratory, Princeton Universily Received November 8, 1934) The calculation of absolute reaction rates isIformulated complex, in degrees of free SOME APPLICATIONS OF THE I TRANSITION rms of quantities which are a vanable from the potential the original molecules, lea STATE METHOD TO THE CALCULATION OF surfaces which can be constructed at the present time. The isotopes quite different ir REACTION VELOCITIES. ESPECIALLY IN probability of the activated state is calculated using ordi- simple kinetic theory, Th SOLUTION nary statistical mechanics. This probability multiplied by general statistical treatmen the rate of decomposition gives the specific rate of reaction. treatment are given The occurrence of quantized vibrations in the activated BY M. G. EVANS AND M. PolanYi Received 12th March, 1935 The calculation of absolute reaction rates is formulated I. Introduction in terms of quantities which are available from the potential surfaces which can be constructed at the influence of pressure on the velocity of chemical reactions in solution, e One of the main objects of this discussion will be to consider th present time. The probability of the activated state is established the fact that, in certain cases, the velocity of re action could calculated using ordinary statistical mechanics. This pressure could be atributed to secondary effects, which, in their turn, probability multiplied by the rate of decomposition explanation based on the change of association of the solvent(aqueous gives the specific rate of reaction alcohol), which may be applicable in special cases. The extensive work of Cohen 2 and his collaborators, however. removed to some extent
The calculation of absolute reaction rates is formulated in terms of quantities which are available from the potential surfaces which can be constructed at the present time. The probability of the activated state is calculated using ordinary statistical mechanics. This probability multiplied by the rate of decomposition gives the specific rate of reaction. 9.7.1 Brief introduction §9.7 Transition state theory (TST)
89.7 Transition state theory (TST) 9.7.1 Brief introduction A+BC→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→HH+H This process can be generalized as: A+BC—[ABC->A-B+C Activated complex /Transition state
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 ⎯→ [ABC] ⎯→ A-B + C Activated complex / Transition state 9.7.1 Brief introduction §9.7 Transition state theory (TST)