One-step kinetics

Interestingly, although many transition state analogs bind noncovalently to the target enzyme s active site via a one-step kinetic mechanism (Scheme la) and would therefore be expected to exhibit no time-dependent properties of inhibition, inhibitors with Kj values of < 10 10 M (like coformy-cin) usually have a slow onset of inhibition kobserved < 10 2 s 1 (i.e., an approach to equilibrium inhibition of > 1 min).161 This is merely an assay artifact due to... 

While the multiple steady-state phenomena may be, at least qualitatively, explained in terms of a simple one-step kinetic mechanism and interactions of the intraphase and interparticle heat and mass transfer (thermokinetic model), there is no acceptable explanation for the periodic activity (12). Since the values of the Lewis number are at least by a factor of 10 lower than those necessary to produce undamped oscillations, there is no doubt that the instability cannot be viewed in terms of mutual... 

Many further analyses of structures of stretched laminar flames have now been published [101]-[113]. With one exception [113], they essentially apply activation-energy asymptotics for one-step kinetics multistep kinetics can have a significant influence on the responses of flames to strain [113], through enhanced diffusive losses of reaction intermediaries from the reaction zone. Most of the analyses employ a constant-density approximation, but a few [106], [110]-[112] have taken density variations into account. As a consequence of these studies, we now have a good understanding of many aspects of the influences of strain. 

Tarkkinen P, Palenius T, Lovgren T (2002) Ultrarapid, ultrasensitive one-step kinetic immunoassay for C-reactive protein (CRP) in whole blood samples measurement of the entire CRP concentration range with a single sample dilution. Clin Chtan 48 269-277... 

Fig. 11.1 Diffusion flame structure determined on basis of one-step kinetics in an asymptotic approximation to the kinetic activation I - reaction zone II - convection-diffusion zone Fp - fuel concentration Fq - oxidizer concentration Daoc - the Damkohler number corresponds to an infinitely fast reaction Daext - the Damkohler number when flame extinction takes place...

Reaction measurement studies also show that the chemistry is often not a simple one-step reaction process (37). There are usually several key intermediates, and the reaction is better thought of as a network of series and parallel steps. Kinetic parameters for each of the steps can be derived from the data. The appearance of these intermediates can add to the time required to achieve a desired level of total breakdown to the simple, thermodynamically stable products, eg, CO2, H2O, or N2. 

In Chapter 1 we distinguished between elementary (one-step) and complex (multistep reactions). The set of elementary reactions constituting a proposed mechanism is called a kinetic scheme. Chapter 2 treated differential rate equations of the form V = IccaCb -., which we called simple rate equations. Chapter 3 deals with many examples of complicated rate equations, namely, those that are not simple. Note that this distinction is being made on the basis of the form of the differential rate equation. 

The latter mechanism is characterized by a transition-state structure of type 64 and by its being (in part) analogous to the mechanism at a saturated carbon. The preference of a two-step mechanism to the apparently simpler one-step mechanism is suggested by the isolation of Meisenheimer complexes and by the kinetics of their formation. The experimental evidence on these... 

In deriving the kinetics of activation-energy controlled charge transfer it was emphasised that a simple one-step electron-transfer process would be considered to eliminate the complications that arise in multistep reactions. The h.e.r. in acid solutions can be represented by the overall equation ... 

In Section 1.4 it was assumed that the rate equation for the h.e.r. involved a parameter, namely the transfer coefficient a, which was taken as approximately 0-5. However, in the previous consideration of the rate of a simple one-step electron-transfer process the concept of the symmetry factor /3 was introduced, and was used in place of a, and it was assumed that the energy barrier was almost symmetrical and that /3 0-5. Since this may lead to some confusion, an attempt will be made to clarify the situation, although an adequate treatment of this complex aspect of electrode kinetics is clearly impossible in a book of this nature and the reader is recommended to study the comprehensive work by Bockris and Reddy. ... 

No single mechanism accounts for all the reactions. One pathway involves a concerted one-step process involving a cyclic transition state. This of necessity affords a c -product. Another possibility, more favoured in polar solvents, involves a cationic 5-coordinate intermediate [IrX(A)(CO)L2]+, which undergoes subsequent nucleophilic attack by B-. Other possibilities include a SN2 route, where the metal polarizes AB before generating the nucleophile, and radical routes. Studies are complicated by the fact that the thermodynamically more stable isolated product may not be the same as the kinetic product formed by initial addition. 

Rather than always occurring in one step, reactions in the natural world often result from a series of simple processes between atoms and molecules resulting in a set of intermediate steps from reactants to products. The way multistep reactions occur can have a strong effect on the kinetics of the overall reaction. For instance, in... 

The kinetic equilibrium constant is estimated from the thermodynamic equilibrium constant using Equation (7.36). The reaction rate is calculated and compositions are marched ahead by one time step. The energy balance is then used to march enthalpy ahead by one step. The energy balance in Chapter 5 used a mass basis for heat capacities and enthalpies. A molar basis is more suitable for the current problem. The molar counterpart of Equation (5.18) is... 

As the large-scale computational fluid dynamics (CFD) simulations often invoke simplifying the kinetics as one-step overall reaction, the extraction of such bulk flame parameter as overall activation energy is especially useful when the CFD calculation with detailed chemistry is not feasible. Based on the experimental results, the deduced overall achvation energies of the three equivalence ratios are shown in Figure 4.1.10a. It can be observed that the variation of with is nonmonotonic and peaks near the stoichiometric condition. 

Now we get to the meaning of 2 in Sn2. Remember from the last chapter that nucleophilicity is a measure of kinetics (how fast something happens). Since this is a nucleophilic substitution reaction, then we care about how fast the reaction is happening. In other words, what is the rate of the reaction This mechanism has only one step, and in that step, two things need to find each other the nucleophile and the electrophile. So it makes sense that the rate of the reaction will be dependent on how much electrophile is around and how much nucleophile is around. In other words, the rate of the reaction is dependent on the concentrations of two entities. The reaction is said to be second order, and we signify this by placing a 2 in the name of the reaction. 

The kinetics of the reaction, as discussed in Chapter 7, are usually described in terms of a less detailed scheme, in which going from adsorbed thiophene to the first S-free hydrocarbon in the cycle, butadiene, is taken in one step. We derived a rate equation of the form ... 

In searching to formulate a mechanism of CuInSc2 phase formation by one-step electrodeposition from acid (pH 1-3) aqueous solutions containing millimolar concentrations of selenous acid and indium and copper sulfates, Kois et al. [178] considered a number of consecutive reactions involving the formation of Se, CuSe, and Cu2Se phases as a pre-requisite for the formation of CIS (Table 3.2). Thermodynamic and kinetic analyses on this basis were used to calculate a potential-pH diagram (Fig. 3.10) for the aqueous Cu+In-i-Se system and construct a distribution diagram of the final products in terms of deposition potential and composition ratio of Se(lV)/Cu(ll) in solution. 

One-step hydroxylation of aromatic nucleus with nitrous oxide (N2O) is among recently discovered organic reactions. A high eflSciency of FeZSM-5 zeolites in this reaction relates to a pronounced biomimetic-type activity of iron complexes stabilized in ZSM-5 matrix. N2O decomposition on these complexes produces particular atomic oj gen form (a-oxygen), whose chemistry is similar to that performed by the active oxygen of enzyme monooxygenases. Room temperature oxidation reactions of a-oxygen as well as the data on the kinetic isotope effect and Moessbauer spectroscopy show FeZSM-5 zeolite to be a successfiil biomimetic model. 

The exchange CD determined by different methods will coincide only in the case of quasi-one-step reactions mentioned above. Thus, when the value of if is so much higher than if that the extreme anodic section cannot be measured and there is no break in the polarization curve, all three methods of determination lead to the same value of if. This implies that step 1 has no effect at all on the kinetics of the overall reaction and that its (high) exchange CD cannot be determined. The same conclusion holds in the opposite case of if [Pg.227]

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