Catalytic reactions rate limiting steps

As with the other surface reactions discussed above, the steps m a catalytic reaction (neglecting diffiision) are as follows the adsorption of reactant molecules or atoms to fomi bound surface species, the reaction of these surface species with gas phase species or other surface species and subsequent product desorption. The global reaction rate is governed by the slowest of these elementary steps, called the rate-detemiming or rate-limiting step. In many cases, it has been found that either the adsorption or desorption steps are rate detemiining. It is not surprising, then, that the surface stmcture of the catalyst, which is a variable that can influence adsorption and desorption rates, can sometimes affect the overall conversion and selectivity. 

See also Enzyme cofactors downhill trajectories for, 196,197 mechanism of catalytic reaction, 190-192 metal substitution, 200-204 potential surfaces for, 192-195,197 rate-limiting step of, 190 reference solution reaction for, 192-195,... 

Evans found that molecular hydrogen was efficiently generated by the reaction of a simple diiron complex [CpFe(CO)2]2 (Fp2) with acetic acid (pA a = 22.3) in acetonitrile [202]. Electrochemical simulations revealed that Ep2, [CpEe(CO)2] (Fp ), and [CpFe(CO)2H] (FpH) were key intermediates in this catalytic mechanism (Scheme 61). Reduction of Fp2 produces both an Fp anion and an Fp radical, which is further reduced to give an Fp anion. The oxidation of the Fp anion by proton affords FpH. This protonation was found to be the rate-limiting step. The dimerization of the FpH generates Fp2 and H2. Alternatively, the FpH is reduced to afford the FpH anion, which is subsequently protonated... 

Unlike other enzymes that we have discussed, the completion of a catalytic cycle of primer extension does not result in release of the product (TP(n+1)) and recovery of the free enzyme. Instead, the product remains bound to the enzyme, in the form of a new template-primer complex, and this acts as a new substrate for continued primer extension. Catalysis continues in this way until the entire template sequence has been complemented. The overall rate of reaction is limited by the chemical steps composing cat these include the chemical step of phosphodiester bond formation and requisite conformational changes in the enzyme structure. Hence there are several potential mechanisms for inhibiting the reaction of HIV RT. Competitive inhibitors could be prepared that would block binding of either the dNTPs or the TP. Alternatively, noncompetitive compounds could be prepared that function to block the chemistry of bond formation, that block the required enzyme conformational transition(s) of turnover, or that alter the reaction pathway in a manner that alters the rate-limiting step of turnover. 

It is the reaction characterized by fc2(lim) that exhibits the specificity toward the position of the phenyl group substituent, and is responsible for the accelerated rates of appearance of phenol. The rate-limiting step of the overall reaction, however, is the hydrolysis of the acyl-cycloamylose. The overall reaction, then, will be catalytic only if k3 exceeds the rate constant for the alkaline hydrolysis of a particular ester. This situation is true only for highly unreactive esters. If, therefore, the cycloamyloses are to be uti-... 

As an example, consider an early calculation of isotope effects on enzyme kinetics by Hwang and Warshel [31]. This study examines isotope effects on the catalytic reaction of carbonic anhydrase. The expected rate-limiting step is a proton transfer reaction from a zinc-bound water molecule to a neighboring water. The TST expression for the rate constant k is... 

The rate data display curvature for Pco, and the authors supposed that the rate limiting step was preceded by CO addition to the metal complex. Therefore, they proposed that the rate limiting step was reaction of either MCO+ or M2CO +, M = Rh(CO)2(4-pic)x + with H20. Interestingly, the turnover frequency increased as the concentration decreased. The authors ascribed this behavior to a higher activity for Rh complexes with lower nuclearity ( e.g., mononuclear). They proposed a mechanistic scheme (Scheme 43) whereby mononuclear and dinuclear complexes exhibit parallel catalytic cycles, joined by an equilibrium for monomer-dimer formation. 

In the case that the chemical reaction proceeds much faster than the diffusion of educts to the surface and into the pore system a starvation with regard to the mass transport of the educt is the result, diffusion through the surface layer and the pore system then become the rate limiting steps for the catalytic conversion. They generally lead to a different result in the activity compared to the catalytic materials measured under non-diffusion-limited conditions. Before solutions for overcoming this phenomenon are presented, two more additional terms shall be introduced the Thiele modulus and the effectiveness factor. 

It can be seen in the plot in Figure 11 that EA . shows a clear temperature dependence. For rising temperatures the mass transport limitation can be observed, which leads to a lowering of EAs by a factor of V2 in the pore diffusion regime down to 0, owing to the shift of the reaction from the interior of the pore system of the catalytic particle to the outer surface. In the final state, the diffusion through the boundary layer becomes the rate-limiting step of the reaction. 

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