11章_化学动力学基础(一)解析.ppt

The rates of chemical reactions The variation with time of the concentration of a reactant in a second-order reaction. The grey line is the corresponding decay in a first-order reaction with the same initial rate. For this illustration, klarge = 3ksmall. The rates of chemical reactions The rates of chemical reactions The approach of concentrations to their equilibrium values as predicted by eqn 19 for a reaction A 3/4 B that is first-order in each direction, and for which k = 2k. The rates of chemical reactions The relaxation to the new equilibrium composition when a reaction initially at equilibrium at a temperature T1 is subjected to a sudden change of temperature, which takes it to T2. The rates of chemical reactions The Arrhenius plot of ln k against 1/T for the decomposition of CH3CHO, and the best straight line. The slope gives (Ea/R and the intercept at 1/T = 0 gives ln A. The rates of chemical reactions The concentrations of A, I, and P in the consecutive reaction scheme A ?I ?P. The curves are plots of eqns 33-35 with ka = 10kb. If the intermediate I is in fact the desired product, it is important to be able to predict when its concentration is greatest. The rates of chemical reactions The rates of chemical reactions The basis of the steady-state approximation. It is supposed that the concentrations of intermediates remain small and hardly change during most of the course of the reaction. 解：因H+是催化剂，反应过程中浓度保持不变，可将其并入k项，则速率方程为: r=k’[A]α (1) 从第1、第2组数据看，298K时，t1/2: t1/4=1:2，这是一级反应的特点，所以α =1, r=k’[A] 。 第1组: k’=ln2/t1/2= k[H+]β 第2组: k’=ln2/t1/2= k[H+]β 两式相除： 所以β =1 则速率方程为: r=k[A][H+] (2) 一级反应的半衰期 t1/2 =ln2/ k’ = ln2/k[H+], 所以 k(298K)=1.9 ×10-2 mol-1·dm3·s-1 k(308K)=3.8 ×10-2 mol-1·dm3·s-1 (3) 将两个速率常数代入阿累尼乌斯公式 例8、100℃时, HI(g)在Pt上催化分解速率方程： 高压下 r = k1 = 5.0×104 Pa·s-1 低压下 r = k2 pHI , k2 = 50 s-1 假定r与HI在Pt上的吸附量成正比，计算100℃, r = 2.5×104 Pa·s-1时pHI 解：本题先要求出反应速率方程的表达式。根据题意，反应速率r与HI在Pt上的吸附量成正比，设吸附符合Langmuir吸附等温式： 即要求出表达式中的k和b 根据题意,高压下: ∴ k = 5.0