By J. F. Le Page
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Extra resources for Applied Heterogeneous Catalysis: Design, Manufacture, and Use of Solid Catalysts
1 4) This equation of rate invites certain comments, as follows: • Even for strong diffusional limitations, the observed rate still depends on the chemical activity because V remains proportional to N · Under such conditions, the energy of activation therefore tends toward half of the value observed when the chemical reaction is limiting . } e (which also can be achieved by increasing the porosity and in certain cases the macroporosity. See Fig. 2. 1 3 (Ref. ). • The limitations of internal diffusion generally involve modifications of the selectivity of combined reactions; and this is what is observed for concurrent reactions between two diffusing reactants with different rates and especially for consecutive reactions of the type A -+ B -+ C where C is the desired product.
_ + bACA or V = kbACA + k k bA CA 1 1. bACA � 1 RT (1 + E b 1C1) 2 i = A, B, P, s Second order on the catalyst Overall kinetics bACAba Ca b,C, b 8C8 Catalyst slightly covered Apparent ftrst order with respect to A and B Eexp = Etrue - J HA - Ll Ha Certain interesting kinetic relations merit special attention. The apparent order is zero for some reactions, such as the hydrogenation of o-xylene (Fig. 4) where zero order is observed as much in relation to xylene as in relation to hydrogen. For such reactions, the rate is independent of the concentration; and the quantity transformed per unit mass of catalyst depends only on time, or for unit time on the catalyst mass.
1 3 (Ref. ). • The limitations of internal diffusion generally involve modifications of the selectivity of combined reactions; and this is what is observed for concurrent reactions between two diffusing reactants with different rates and especially for consecutive reactions of the type A -+ B -+ C where C is the desired product. JK, as can be shown from a comparison of Eq. (2. 1 1 ) and Eq. (2. 1 3). On the other hand, other combined reactions, such as twin reactions of the same order, do not involve a variation of selectivity with the appearance of internal diffusional limitations.
Applied Heterogeneous Catalysis: Design, Manufacture, and Use of Solid Catalysts by J. F. Le Page
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