催化中的补偿效应.doc

补偿效应 Compensation Sometimes both E and A increase or both decrease. Consequently, k changes less than it would if only E or only A changed. Langmuir-Hinshelwood 机理 反应速率取决于吸附在催化剂表面的吸附态反应物分子的浓度。 当都很小时，反应对A B均是一级反应 一高一低时，对一个是一级反应，对另一个是负一级反应 吸附系数与温度的关系： Et是考虑吸附的真实活化能，，直观上解释为温度升高会降低反应物分子的覆盖度。 如果两种反应物都是强吸附，那么覆盖度随温度的变化就会小，吸附热就不用考虑到反应活化能中。 补偿效应： 如果活化能高了，反应的指前因子就会增加以“补偿compensation phenomena”活化能增高对反应速率的影响。 对于有补偿效应的体系，一定会存在这样的温度，使得相关各催化反应体系的反应速率均相同；低于这个温度时，更低的活化能才意味着更快的反应速率。 表观活化能随温度的变化是由于吸附热的贡献程度会随温度变化而造成的，真实的表面反应的活化能是保持不变的。 lnA = a + bE In which case the rate constant is the same for all reactions at one particular temperature T(theta) Above this temperature, the faster reaction has the higher activation energy. 过渡态：activated complex Compensation occurs if an increase in is associated with an increase in . In homogeneous systems this plausibly may happen, since in order for reaction to occur it is necessary both that a sufficiently low energy barrier exist and that a favorable configuration be made possible, accompanied by a change in entropy. is usually a negative number, and often one finds an approximate linear relationship between and . 补偿效应在不同溶剂中的homogeneous liquid-phase或同一类反应物但不同取代基的反应中观察到。 基于溶质-溶剂相互作用，Stronger bonding between solute and molecules and solvent will lower the enthalpy and increase the enthalpy change to form the intermediate complex . And b restricting freedom of vibration and rotation, will lower the entropy and increase the entropy change. 在多相催化中，A linear relationship may likewise exist between and upon chemisorption over a series of catalysts. 比如 calcination temperature, changing the calcination temperature might possibly alter both the number of sites (to which A is proportional) and the activation energy. It is also possible that molecules may surface-diffuse to the reaction site of a surrounding area, and as the temperature is increased, the rate of surface diffusion may increase, but the rate of desorption also increases, resulting in an eff