12章_化学动力学基础(二)全解.ppt

Molecular reaction dynamics Molecular reaction dynamics A reaction profile. The horizontal axis is the reaction coordinate, and the vertical axis is potential energy. The activated complex is the region near the potential maximum, and the transition state corresponds to the maximum itself. Molecular reaction dynamics Molecular reaction dynamics In an elementary depiction of the activated complex close to the transition state, there is a broad, shallow dip in the potential energy surface along the reaction coordinate. The complex vibrates harmonically and almost classically in this well. However, see footnote 5. Molecular reaction dynamics Molecular reaction dynamics Changes in the reaction profile when a bond undergoing cleavage is deuterated. The only significant change is to the zero-point energy of the reactants, which is lower for C-D than for C-H. As a result, the activation energy is greater for C-D than for C-H. Molecular reaction dynamics Molecular reaction dynamics For a related series of reactions, as the magnitude of the standard reaction Gibbs energy increases, so the activation barrier decreases. The approximate linear correlation between (G and (rG( is the origin of linear free energy relations. Note how a high value of (G for reaction a correlates with a low value of ?rG((for that reaction (green), but a smaller value of (G, as for reaction b (black) correlates with a larger value of ?vG((. Molecular reaction dynamics Molecular reaction dynamics Experimental tests of the kinetic salt effect for reactions in water at 298 K. The ion types are shown as spheres, and the slopes of the lines are those given by the Debye-Hukel limiting law and eqn 73. Molecular reaction dynamics Molecular reaction dynamics The experimental ionic strength dependence of the rate constant of a hydrolysis reaction: the slope gives information about the charge types involved in the activated complex of the rate-determining step. Molecular reaction dynamics Molecular reactio