(2-2) Example of a chain reaction having a complicated rate law - The formation of HBr from hydrogen and bromine.

As we had seen in the introductory section of chemical kinetics, although the stoichiometric equation for the reaction between hydrogen and bromine to give HBr looks very simple, the rate law is very complicated indicting a complex mechanism (see fig 1) i.e.:

Fig. 1: The A schematic representation of the mechanism of the reaction between hydrogen and bromine. Note how the reactants and products are shown as arms to the circle, but the intermediates (H and Br) occur only within the circle. Similar diagrams are used to depict the action of catalysts.

The proposed mechanism for this reaction (see Fig. 1.) is:

termination: The third body M removes the energy of recombination.e.e. However it turns out that only Br atom recombination it important.: and: i.e.: which substituted back in (i) gives: i.e. Other possible termination steps include the combination of H atoms to form H2 and the combination of H and Br atoms to from HBr.e.Note regarding step (d). Through this mechanism.: i.: . it may be deduced that the net rate of formation of HBr (product) is given by: where the concentrations of the intermediates may be determined by invoking the steady state approximation. i. from (ii) + (i) we obtain: i.

i. the net rate of formation of HBr may be written solely in terms of reactants.: which simplifies to: as predicted by the empirical rate law: where: .e.or: dividing 'top' and 'bottom' by k`b : Thus.

These runs began with stoichiometric proportions of hydrogen and bromine. 2). . the observed rate laws are reproduced by the mechanisms. the presence of [Br2] stems from the role of Br2 in the removal of the reactive hydrogen radicals from the chain. that used to be essentially the end of the calculation (but not of the experimental investigation). can be used to explore how the concentration of HBr changes with time. Mathematical software may also be used to integrate the original coupled rate laws without needing to invoke the steady-state approximation. and reducing the rate of formation of product. (2) In the examples we have considered. the curves are labelled with the value of 2k'-1. we can make use of computers to integrate the approximate rate law numerically. However.and: Note: (1) The presence of [HBr] in the denominator is a sign that HBr is acting as an inhibitor. In the past. Likewise. 2: The numerical integration of the the HBr rate law. (See Fig. and hence predict the time dependence of the HBr concentration. Fig.

In this case. In this case. where represents the rate at which photons of the appropriate frequency are absorbed by the volume in which the reaction occurs. the rate of formation of HBr in this case is given by: . the initiation step is of the form: whilst the other steps are as in the thermal process (b-d).(3) HBr may also be produced through in a process where the initiation step is photochemical.

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