Develop a rate law for the HBr reaction that is consistent with the experimental observations given above. | |||
SolutionIt is customary in discussions of reactions of this sort to let the species formula enclosed in parentheses represent its concentration. In the azomethane reaction, we saw that a rate law of the form |
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could account for the change in the apparent reaction order when going from low to high concentration. | |||
For the HBr reaction | |||
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(CDE7-1.1) | ||
where [s1] represents a reaction constant or the concentration of one of the species that will be determined later | |||
and |
(CDE7-1.2) | ||
We see that the concentration dependence of bromine given
in Equation (CDE7-1.1) is consistent with experimental data. Next consider the HBr dependence. |
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One rate expression in which the concentration dependence of HBr is consistent with experimental observation is | |||
Going to the extremes of high and low concentration |
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(CDE7-1.3) |
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Consequently, the concentration dependence of HBr denoted
by Equation (CDE7-1.31) is consistent with experimental observation. This concentration dependence of the species H2, Br2, and HBr in the rate expression are, respectively, |
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Comparing Equations (CDE7-1.1) and (CDE7-1.3) we see that [s1] in Equation (CDE7-1.1) could be (HBr) and that [s2] in Equation (CDE7-1.3) could beTherefore, Equations (CDE7-1.1) and (CDE7-1.3) are combined to give | |||
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(CDE7-1.5) | ||
If we now incorporate dependence of the reaction rate on H2 [Equation (CDE7-1.4)] into Equation (CDE7-1.5), we arrive at the rate expression | |||
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(CDE7-1.6) | ||
or, identically, | |||
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(CDE7-1.7) | ||
which is consistent with all experimental observations. |