Catalysts activation energies affected

The use of a catalyst affects the rate of reaction by enabling the products to form by an alternative route. Each stage has lower activation energy than the uncatalyzed reaction. 

An enzyme—usually a large protein—is a substance that acts as a catalyst for a biological reaction. Like all catalysts, an enzyme doesn t affect the equilibrium constant of a reaction and can t bring about a chemical change that is otherwise unfavorable. An enzyme acts only to lower the activation energy for a reaction,... 

It is well known that Rh(I) complexes can catalyze the carbonylation of methanol. A heterogenized catalyst was prepared by ion exchange of zeolite X or Y with Rh cations.126 The same catalytic cycle takes place in zeolites and in solution because the activation energy is nearly the same. The specific activity in zeolites, however, is less by an order of magnitude, suggesting that the Rh sites in the zeolite are not uniformly accessible. The oxidation of camphene was performed over zeolites exchanged with different metals (Mn, Co, Cu, Ni, and Zn).127 Cu-loaded zeolites have attracted considerable attention because of their unique properties applied in catalytic redox reactions.128-130 Four different Cu sites with defined coordinations have been found.131 It was found that the zeolitic media affects strongly the catalytic activity of the Cd2+ ion sites in Cd zeolites used to catalyze the hydration of acetylene.132... 

Our studies at Atomic Weapons Establishment (AWE) have confirmed that at elevated temperatures, especially when using dry inert gas conditions, there is considerable difficulty in pushing the reaction (see scheme 5) to completion.18 Moisture was found to affect the rate of the reaction and the nature of the synthesized polymer. The introduction of additional catalyst to the reaction mixture was found to aid the forward reaction. Overall, our observations suggest the existence of a complex series of reactions, possibly having distinctly different activation energies. 

A catalyst increases the rate of reaction as it offers an alternative reaction pathway (1) of lower activation energy (1). The position of equilibrium is not affected as the rates of both the forward and backward reactions are increased (1) to the same extent (1). 

In general, TPR measurements are interpreted on a qualitative basis as in the example discussed above. Attempts to calculate activation energies of reduction by means of Expression (2-7) can only be undertaken if the TPR pattern represents a single, well-defined process. This requires, for example, that all catalyst particles are equivalent. In a supported catalyst, all particles should have the same morphology and all atoms of the supported phase should be affected by the support in the same way, otherwise the TPR pattern would represent a combination of different reduction reactions. Such strict conditions are seldom obeyed in supported catalysts but are more easily met in unsupported particles. As an example we discuss the TPR work by Wimmers et al. [8] on the reduction of unsupported Fe203 particles (diameter approximately 300 nm). Such research is of interest with regard to the synthesis of ammonia and the Fischer-Tropsch process, both of which are carried out over unsupported iron catalysts. 

The published values for the activation energies and pre-exponential factors of transesterification and glycolysis vary significantly. Catalysts and stabilizers influence the overall reaction rate markedly, and investigations using different additives cannot be compared directly. Most investigations are affected by mass transport and without knowledge of the respective mass transport parameters, kinetic results cannot be transferred to other systems. 

The overall effect is to lower the activation energy, which increases the rate of reaction. The activation energy is lowered the same amount for the forward and reverse reactions, however. There is the same increase in reaction rates for both reactions. As a result, a catalyst does not affect the position of equilibrium. It only affects the time that is taken to achieve equilibrium. 

The affect of diffusion on catalyst selectivity in porous catalysts operating under non-isothermal conditions has been examined by a number of workers. The mathematical problem has been comprehensively stated in a paper [21] which also takes into account the affect of surface diffusion on selectivity. For consecutive first-order exothermic reactions, the selectivity increases with an increase in Thiele modulus when the parameter A (the difference between the activation energy for reaction... 

A catalyst is a substance that increases the rate at which a chemical reaction approaches equilibrium, while not being consumed in the process. Thus, a catalyst affects the kinetics of a reaction, through provision of an alternative reaction mechanism of lower activation energy, but cannot influence the thermodynamic constraints governing its equilibrium. 

The main features of this investigation are the following. First, a "deactivation process similar to that observed on the pure nickel oxide was found on the modified catalysis as well, with the same logarithmic law to represent its evolution with time. Second, the kinetic equations which were found to fit the data on pure nickel oxide also apply to the modified catalysts. Thus there is a low-temperature mechanism operative between 100° and 180°C. For all the samples assembled in Table II, the activation energies were practically the same, about 2 kcal./mole and essentially equal to the value for pure nickel oxide. This indicates that, for this particular mechanism of the reaction, the added ions and the semiconductivity changes do not affect directly the catalytic process. 

A c tal st is a substance that affects the rate of a chemical reaction without itself being consumed or chemically altered. The catalyst takes part in the reaction by providing an alternative route to the production of products. Tlic catalyzed reaction has a lower activation energy than that of Xht uncatalyzed reaction, as shown in Figure 1.15. By lowering the activation energy there are more molecules with sufficent energy that can react and thus the rate of the reaction is affected. 

Edward Koubeck, "An Experiment To Demonstrate How a Catalyst Affects the Rate of a Reaction," /. Chem. Educ., Vol. 76,1999, 1714-1715. Describes a chemistry experiment that allows students to calculate rates of reaction, orders of reaction, and activation energies. 

In the literature, higher values for the activation energy are also found [82, 83]. One reason for this could be the neglect of a pre-reduction of the platinum catalyst and also the low porosity of the sputtered catalyst. Another possibly important aspect is that here we actually measured intrinsic kinetic data compared with the diffusion-affected kinetic data in refs. [82] and [83]. 

In developing mathematical expressions for selectivities, knowledge of the rate equations are required. This is because the instantaneous selectivity is defined in terms of the rate ratios. The parameters that affect the instantaneous and the overall selectivities are exactly the same as those influencing the reaction rates, namely, the concentration, temperature, activation energy, time of reaction (residence time in flow reactors), catalysts, and the fluid mechanics. 

This paper focuses on the influence of the support on the H/D exchange of CP over supported Pt catalysts. It will be shown that kinetics and selectivities are largely affected by the support material. Particle size effects are separated from support effects. The activity shows a compensation effect, and the apparent activation energy and pre-exponential factor show an isokinetic relationship . This can be explained by different adsorption modes of the CP on the metallic Pt surface. The change in adsorption modes is attributed to a change in the electronic structure of the Pt particles, which in turn is induced by changes in the acid/base properties of the support. 

Note that expressing the catalyst activity in terms of TOF allows tailoring the catalyst activity to the requirements of process design. Because the activation energy remains constant, the only affected parameter is the pre-exponential factor A, which in turn is proportional to the weight fraction of the active center, in this case the metal. Table 10.2 shows two situations. In the first case the preexponential factor is taken from the original TOF data, which corresponds to a fast... 

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