Kinetics, chemical zero-order

The first detailed investigation of the reaction kinetics was reported in 1984 (68). The reaction of bis(pentachlorophenyl) oxalate [1173-75-7] (PCPO) and hydrogen peroxide cataly2ed by sodium saUcylate in chlorobenzene produced chemiluminescence from diphenylamine (DPA) as a simple time—intensity profile from which a chemiluminescence decay rate constant could be determined. These studies demonstrated a first-order dependence for both PCPO and hydrogen peroxide and a zero-order dependence on the fluorescer in accord with an earher study (9). Furthermore, the chemiluminescence quantum efficiencies Qc) are dependent on the ease of oxidation of the fluorescer, an unstable, short-hved intermediate (r = 0.5 /is) serves as the chemical activator, and such a short-hved species "is not consistent with attempts to identify a relatively stable dioxetane as the intermediate" (68). 

Saturation kinetics are also called zero-order kinetics or Michaelis-Menten kinetics. The Michaelis-Menten equation is mainly used to characterize the interactions of enzymes and substrates, but it is also widely applied to characterize the elimination of chemical compounds from the body. The substrate concentration that produces half-maximal velocity of an enzymatic reaction, termed value or Michaelis constant, can be determined experimentally by graphing r/, as a function of substrate concentration, [S]. 

The reaction was studied for all coinage metal nanoparticles. In the case of GMEs the rate follows zero-order kinetics with IT for all the coinage metal cases. The observed IT for the Cu catalyzed reaction was maximum but its rate of reduction was found to be minimum. Just the reverse was the case for Au and an intermediate value was obtained for the Ag catalyzed reaction (Figure 7). The adsorption of substrates is driven by chemical interaction between the particle surface and the substrates. Here phe-nolate ions get adsorbed onto the particle surface when present in the aqueous medium. This caused a blue shift of the plasmon band. A strong nucleophile such as NaBH4, because of its diffusive nature and high electron injection capability, transfers electrons to the substrate via metal particles. This helps to overcome the kinetic barrier of the reaction. 

When microorganisms use an organic compound as a sole carbon source, their specific growth rate is a function of chemical concentration and can be described by the Monod kinetic equation. This equation includes a number of empirical constants that depend on the characteristics of the microbes, pH, temperature, and nutrients.54 Depending on the relationship between substrate concentration and rate of bacterial growth, the Monod equation can be reduced to forms in which the rate of degradation is zero order with substrate concentration and first order with cell concentration, or second order with concentration and cell concentration.144... 

The parameter [3 is related to the contrast. If (3A> > 1, equation 1 reduces to that of a simple first order reaction (such as CEL materials are usually assumed to follow (6)). If 3A< < 1, the reaction becomes second order in A In a similar manner, the sensitized reaction varies between zero order and first order. For the anthracene loadings required by the PIE process (13,15), A is close to 1M, so (3 > > 1 is required for first order unsensitized kinetics. Although in solution, 3 for DMA is -500, and -25 for DPA (20), we have found [3 =3 for DMA/PEMA, and (3=1 for DPA/PBMA. Thus although the chemical trends are in the same direction in the polymer as in solution, the numbers are quite different, indicating a substantial... 

Based on these rate laws, various equations have been developed to describe kinetics of soil chemical processes. As a function of the adsorbent and adsorbate properties, the equations describe mainly first-order, second-order, or zero-order reactions. For example. Sparks and Jardine (1984) studied the kinetics of potassium adsorption on kaolinite, montmorillonite (a smectite mineral), and vermiculite (Fig. 5.3), finding that a single-order reaction describes the data for kaolinite and smectite, while two first-order reactions describe adsorption on vermiculite. 

V = V max [S]// m- A reaction of higher order is called pseudo-first-order if all but one of the reactants are high in concentration and do not change appreciably in concentration over the time course of the reaction. In such cases, these concentrations can be treated as constants. See Order of Reaction Half-Life Second-Order Reaction Zero-Order Reaction Molecularity Michaelis-Menten Equation Chemical Kinetics... 

Referring to reactions in which the reaction velocity is independent of the reactant under consideration. For example, for the reaction A + B C, if the empirical rate expression is v = A [B], the reaction is first order with respect to B but zero order with respect to A. See Chemical Kinetics Rate Saturation Michaelis-Menten Equation... 

CHEMICAL KINETICS RATE SATURATION MICHAELIS-MENTEN EQUATION ZERO-ORDER REACTIONS ORDER OF REACTION MOLECULARITY... 

For carrier-mediated transport, the rate of movement across a membrane will now be constant, since flux is dependent on the capacity of the membrane carriers and not the mass of the chemical to be transported. These processes are described by zero-order kinetic rate equations of the form ... 

Reaction Order. Studies of the reaction of oxygen with carbon at temperatures of interest for AFBC s suggest that it is near zero order in oxygen (62). Most models have been based on an assumed first order reaction but they can be readily modified to accommodate the more realistic lower reaction order (63, 64). The correction for order of reaction will be most important for the prediction of the combustion of recycled fines which are in the size range in which chemical kinetics dominate and for predicting the performance of pressurized fluidized beds. 

The fact that a plot of H2 volumes initially generated vs. time gave a straight line is indicative of pseudo zero order kinetics. For borohydride hydrolysis, Kaufman and Sen3 and Holbrook and Twist4 also found zero order kinetics. Zero order kinetics for Reaction [1] imply that hydrolysis is independent of the concentrations of the reacting chemical species. This can be explained by assuming that the initial reaction step probably involves a surface catalyzed reaction, most likely BH" adsorption on the catalyst. Since the number... 

When an explosive slowly decomposes, the products may not follow the previously described hierarchy or be at the maximum oxidation states. The nitro, nitrate, nitramines, acids, etc., in an explosive molecule can break down slowly. This is due to low-temperature kinetics as well as the influence of light, infrared, and ultraviolet radiation, and any other mechanism that feeds energy into the molecule. Upon decomposition, products such as NO, NO2, H2O, N2, acids, aldehydes, ketones, etc., are formed. Large radicals of the parent explosive molecule are left, and these react with their neighbors. As long as the explosive is at a temperature above absolute zero, decomposition occurs. At lower temperatures the rate of decomposition is infinitesimally small. As the temperature increases, the decomposition rate increases. Although we do not always, and in fact seldom do, know the exact chemical mechanism, we do know that most explosives, in the use range of temperatures, decompose with a zero-order reaction rate. This means that the rate of decomposition is usually independent of... 

Rel. (9) indicates that the kinetics of a catalytic reaction described by equation (7) does not depend on the concentration of the reacting gas (is of zero order as a function of gas concentration). For rel. (9) the evaluation of k is based on statistical thermodynamics applied to transition state theory for chemical reactions [12]. This theory shows that k has the following expression ... 

When C is much greater than Ks, V approaches independence of C and the rate approximates zero-order kinetics (i.e., there is no dependence on the chemical concentration),... 

Although first-order models have been used widely to describe the kinetics of chemical reactions on natural materials, a number of other simple kinetic models, such as zero-order, second-order, Elovich, power function, and parabolic diffusion models have also been employed. The final forms of these equations are given in Table 5.1. Complete details and applications of these models can be obtained in work by Sparks (1990, 1999, 2003). 

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