山大物理化学英文下4.pptVIP

4.4 Isolation method When cB and cC were controlled Three methods: Fixation of concentration method; Excess concentration method; Application of stoichiometric ratio 1) Fix the concentration of other reactants Rate equation of 2NO + 2H2 ? N2 + 2H2O is r = k[NO]? [H2]?. No. Initial pressure / Pa Initial rate NO H2 1 50662.5 20265 486.36 2 50662.5 10132.5 243.18 3 25331.25 20265 121.59 2) Excess concentration C12H22O11 + H2O ? C6H12O6 + C6H12O6 In excess concentration method, the concentration of B and C is made very much larger than that of A。 This technique is particularly useful in determining rate constants for reactions involving water in aqueous solution. Pseudo order reaction. 3) Using stoichiometric ratio aA + bB ? P Initial concentration 1 b/a Conversion concentration x bx/a Residual concentration 1-x (b/a)(1-x) r = k[A]? [B]? = k (b/a)?(1-x)?+? = k(b/a)?(1-x)n Other methods: Unit of k Dependence of t1/2 on c0 §9.4 Determination of the reaction order c c0,1 t c0,2 c0,3 r0,1 r0,2 r0,3 r = k [A]?[B] ?[C] ? Once we determine the order of a reaction, we can write out the rate equation of the reaction and tell the detail of the kinetic characteristics of the reaction according to the rate equation. Otherwise, the rate equation can provide useful information about the mechanism of the reaction. Therefore, determination of the order of the reaction is a work of great importance. Significance Methods for determination of reaction order 4) Isolation method 1) Integration method 2) Differential method 3) Partial order method (1) attempt method (trial-and–error ) (2) graphic method (3) half-life method (1) Graphic method (2) Calculation method 4.1 Integration methods The integration methods are to use the integrated rate equation to determine the order of the reaction. The attempt method: the values of k can be calculated f