高等有机化学-chapter02.pptVIP

the Maxwell distribution law d nE=2pN( )3/2·E1/2 ·e-E/ktdE 1 pkT N: the total number of molecules. k : the Boltzman constant. ? A favourable DG is not of itself sufficient to promote reaction. ? Progress along the reaction coordination requires an initial increase in energy——Activation Energy. ? Only those molecules possessing sufficient energy to overcome the activation barrier are capable of reaction. 2.3.2 Reaction pathway There is one path between reactants and products that has a lower energy maximum than any other, this is the pathway that the reaction will follow. Involving the changes of structure and energy. Potential Energy Surface: The relationship between structure and potential energy, i.e., describing energy as a function of the spatial arrangement of the atoms involved in the reaction. For example: A—X + B A + X—B The two-dimensional energy profile for this exchange: A—X + B A + X—B A X B a b ? a b Saddle Point R P 2.3.3 the simplified model of raction coordinate H—H H* H H—H* The simplest possible reaction needs at least three parapmters to define the geometries changed fully during the procedure from ractant to product. Then, the change of geometrical coordinates during the course of a reaction is considered generally as “Reaction Coordinate”. DG? DGo R P TS Reaction Coordinate E TS (?) The saddle point is then the point of highest energy on the reaction pathway and is of particular interest, know as the trasition state (TS) or activated complex(?). DG? DGo R P Reaction Coordinate E TS (?) The activation energy: DE? The difference in energy between the energy of TS and that of reactants. DE? = ETS — Ereactants ( Activation Barrier) The reaction heat: DE The difference in energy between the energy of products and that of reactants. DE = Eproducts — Ereactants The energy profile of different types of reactions: Single-step reaction: Reaction Coordinate E DE? DEo A B TS (?) A