Inhibition Integrated rate laws

The rate law is of the form of Equation 17.5 in the previous section, and the equivalent law giving the net reaction rate is Equation 17.9. We can, therefore, account for the effect of catalysis on a redox reaction using the same formulation as the case of homogeneous reaction, if we include surface complexes among the promoting and inhibiting species. In Chapter 28, we consider in detail how this law can be integrated into a reaction path simulation. 

The values of a A, and EA must be determined from experimental data to establish the form of the rate law for a particular reaction. As far as possible, it is conventional to assign small, integral values to a2, etc., giving rise to expressions like first-order, second-order, etc. reactions. However, it may be necessary to assign zero, fractional and even negative values. For a zero-order reaction with respect to a particular substance, the rate is independent of the concentration of that substance. A negative order for a particular substance signifies that the rate decreases (is inhibited) as the concentration of that substance increases. 

To investigate the impact of inhibition on reactor design, the procedure again is as follows (i) we have to develop the pertinent kinetic rate equation, (ii) insert this rate law into the equation for the reactor we intend to operate, and (iii) integrate over all applicable degrees of conversion. As the two most frequent cases of inhibition are the occurrence of substrate and (even more often) product inhibition, we will treat those two cases in the following section. We will just mention the equation for substrate inhibition, but we will develop step-by-step the equation for product inhibition. 

A kinetic study of methanol oxidation over stoichiometric iron molybdate catalyst was performed in a fixed-bed integral reactor showing kinetic influences of reaction products. In the temperature range of 548-618 K it was not possible to fit the fomoation rate data to a single power rate law. Dimethyl ether formation presents only a second order dependence with respect to methanol. CO formation seems to be inhibited by water and formaldehyde and rate data fit well to the power rate law ... 

When a solid metal is attacked by oxygen gas, the product of the reaction is the metal oxide which, if it is not volatile, builds up as a surface layer on the metal. The oxide layer may be protective or non-protective. A non-protective layer does not inhibit the continued access of oxygen to the unchanged metal the rate of growth of such an oxide layer is independent of its thickness X and the law of growth is AX/At =. On integration this gives the linear law... 

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