Oxidizing kinetic parameters

Table 2.5. Short Table of Char Oxidation Kinetic Parameters For Petroleum Coke Compared to Representative Eastern Bituminous and Powder River Basin Coals...

The Linde Division of Union Carbide Corporation, now Praxair, developed a series of oxidation kinetic parameters for selected hazardous wastes, as is shown in Table 7.15. Note, again, the high reactivity associated with typical hazardous wastes. 

The SCR catalyst is considerably more complex than, for example, the metal catalysts we discussed earlier. Also, it is very difficult to perform surface science studies on these oxide surfaces. The nature of the active sites in the SCR catalyst has been probed by temperature-programmed desorption of NO and NH3 and by in situ infrared studies. This has led to a set of kinetic parameters (Tab. 10.7) that can describe NO conversion and NH3 slip (Fig. 10.16). The model gives a good fit to the experimental data over a wide range, is based on the physical reality of the SCR catalyst and its interactions with the reacting gases and is, therefore, preferable to a simple power rate law in which catalysis happens in a black box . Nevertheless, several questions remain unanswered, such as what are the elementary steps and what do the active site looks like on the atomic scale ... 

Controlled elimination of mass and heat transport resistances is an important prerequisite for obtaining intrinsic kinetic parameters of the fast exothermic reaction of partial oxidation of methane to synthesis gas. It has been demonstrated that under conditions of strong transport limitations erroneous conclusions concerning the reaction scheme can be derived [7-9]. It was determined in this laboratory that transport limitations are practically absent over a wide range of operating conditions if one portion of the catalyst (< 40 pm) is diluted with -5 portions of an... 

It is basically irrelevant in steady-state measurements in which direction the polarization curves are recorded that is, whether the potential is moved in the direction of more positive (anodic scan) or more negative (cathodic scan) values. But sometimes the shape of the curves is seen to depend on scan direction that is, the curve recorded in the anodic direction does not coincide with that recorded in the cathodic direction (Eig. 12.3). This is due to changes occurring during the measurements in the properties of the electrode surface (e.g., surface oxidation at anodic potentials) and producing changes in the kinetic parameters. 

The first set of experiments was conducted in methanol. The substrate concentration was varied from 15 to 50 mM at a 200 pM concentration of 1 for the determination of kinetic parameters for the transformation of 8 into 9. The catalytic rate constant was determined to be 0.04 min and the Michael constant was determined to be 40 mM at 30°C. The rate constant is comparable to those reported for other dinuclear Cu(ll) complexes with a comparable Cu -Cu distance of 3.5 A, but about one magnitude lower than those observed for complexes with a shorter intermetallic distances (12-14), e.g. 2.9 A (kcat = 0.21 min ) (12) or 3.075 A (kcat = 0.32 min (13). The rate constant Aion for the spontaneous (imcatalyzed) oxidation of 8 into 9 was determined to be 6 x 10" min and corresponds to the oxidation without catalyst under otherwise identical conditions. The rate acceleration (Arca/Aion) deduced from these values is 60,000-fold. 

Table 8.6. Kinetic parameters of CO, propane and propene oxidation over M/A1203 and M/Ce02—A1203 catalysts (M = Pt, Pd or Rh)...

In this paper we summarize some of the results of our measurements of rates of dry oxidation. Results of chemical analyses of residues produced by heating in flowing nitrogen atmosphere (distillation) are also reported and combined with our kinetic data to obtain values of kinetic parameters. Preliminary results of measurements of rates of wet oxidation are presented. 

Table I. Values of Kinetic Parameters for Low Temperature Oxidation of Athabasca Bitumen...

Another important catalytic reaction that has been most extensively studied is CO oxidation catalyzed by noble metals. In situ STM studies of CO oxidation have focused on measuring the kinetic parameters of this surface reaction. Similar to the above study of hydrogen oxidation, in situ STM studies of CO oxidation are often conducted as a titration experiment. Metal surfaces are precovered with oxygen atoms that are then removed by exposure to a constant CO pressure. In the titration experiment, the kinetics of surface reaction can be simplified and the reaction rate directly measured from STM images. 

The kinetic parameters characterizing the oxidation of transition metal ions by dioxygen are collected in Table 10.8. 

Values of Kinetic Parameter a=w-t 1/2 = frp[PH](2fct) 1/2 for Oxidation of Solid Polymers ... 

This reaction is very exothermic (A// —180 to —200kJ mol-1) and, therefore, seems to be very probable from the thermochemical point of estimation. The pre-exponential factor is expected to be low due to the concentration of the energy on three bonds at the moment of TS formation (see Chapter 3). To demonstrate that this reaction is responsible for the oxidative destruction of polymers, PP and PE were oxidized in chlorobenzene with an initiator and analyzed for the rates of oxidation, destruction (viscosimetrically), and double bond formation (by the reaction with ozone) [131]. It was found that (i) polymer degradation and formation of double bonds occur concurrently with oxidation (ii) the rates of all three processes are proportional to v 1/2, (iii) independent of p02, and (iv) vs = vdbf in PE and vs = 1.6vdbf in PP (vdbf is the rate of double bond formation). Thus, the rates of destruction and formation of double bonds, as well as the kinetic parameters of these reactions, are close, which corroborates with the proposed mechanism of polymer destruction. Therefore, the rate of peroxyl macromolecules degradation obeys the kinetic equation ... 

Kinetic Parameters of Macromolecules Degradation in Oxidized Polymers... 

Depending on the oxidation conditions and its reactivity, the inhibitor InH and the formed radical In can participate in various reactions determining particular mechanisms of inhibited oxidation. Of the various mechanisms, one can distinguish 13 basic mechanisms, each of which is characterized by a minimal set of elementary steps and kinetic parameters [38,43 15], These mechanisms are described for the case of initiated chain oxidation when the initiation rate v = const, autoinitiation rate fc3[ROOH] -C vy and the concentration of dissolved dioxygen is sufficiently high for the efficient conversion of alkyl radicals into peroxyl radicals. The initiated oxidation of organic compounds includes the following steps (see Chapter 2). 

Kinetic Parameters of Peroxyl Radicals of Oxidized Styrene with Phosphites and their Complexes with CuCI in Chlorobenzene Solution [89]... 

Semiquantitative analysis. In a preliminary investigation, the analysis using Eq. (1) of space relaxation data, obtained by testing under shift conditions the catalyst at high oxidation state by a CO, H O, N. mixture at constant PH 0 = °>40 bar and various p and at different temperature leve s between 180°C and 260 C, resulted in the following kinetic parameters for the power law rate r = k-p Q ... 

The catalysts were synthesized as films, with ceria prepared by spray pyrolysis of 0.1 M solutions of Ce(N03)3 onto nonporous alumina wafers held at 250 °C. The ceria was then calcined at 300 °C, resulting in a crystallite size of 10 nm. Pt, Pd, or Rh was vapor deposited onto the oxide film. For kinetics testing, the temperature was 300 °C. To determine the reaction order of H20, Pco was maintained constant at 0.026 atm. For the reaction order on CO, Ph2o was maintained constant at 0.02 atm. The kinetic parameters are tabulated in Table 69. 

An irreversible reaction shows no oxidation (anodic peak) and the kinetic parameters (cccn and k0) can be obtained from the shift in peak potentials as a function of scan rate... 

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