By A. G. Sykes, Robert Robinson and L. D. K. Staveley (Auth.)
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Extra resources for Kinetics of Inorganic Reactions
C 58 KINETICS OF INORGANIC REACTIONS ion dependence. Under these conditions, then, the reaction can proceed by at least three different paths, F e 2 + + F e 3 + -► (1) F e 2 + + FeOH 2 + -> (2) F e 2 + + FeCl 2 + Λ (3) where (2) and (3) are faster than (1). Let us consider, first of all, the acid dependence, where [H + ] is always much in excess of metal-ion concentrations, so that buffering is not necessary. For any one experiment, Rate = fcobs[Fen][Fem], and A:obs varies as the acid concentration is varied.
Soc. 85, 680 EXPERIMENTAL TECHNIQUES 37 Rate constants for kt and k-x were evaluated and are shown in Table 2. TABLE 2 RATE CONSTANTS FOR THE FORMATION AND SUBSTITUTION OF SULPHATE COMPLEXES AT 25 °C M Be 2 + Mg 2 + Mn 2 + Co 2 + Ni 2+ · Cu 2 + &i(sec~*) 1 1 4 2 1 x 10 2 x 10 5 x 10 6 x 10 5 x 10-4 (10 4 ) A:_i(sec _1 ) 1-3 8 2 2-5 1 1 x x x x x x 10 3 10 5 10 7 10 6 10 5 10 6 Flash photolysis In flash photolysis, the reactants (in the gas phase or in solution) are subject to an intense burst of light energy (duration ~ 1 0 ~ 5 sec) such that energies of up to 105 joules can be absorbed in a few microseconds (10~ 6 -10" 4 sec).
The effect of back reactions: The stationary-state approximation For systems having more than one step, back reactions often play a significant role in determining the progress of the overall reaction. Thus a back reaction will be effective if its rate is of the same order of magnitude or greater than that of a subsequent forward reaction, where the two have a reactant in common. Often the latter is a free-radical intermediate, but this need not necessarily be so, and, in certain instances, the intermediate is a perfectly stable chemical.