Kinetic parameters, programmed temperature

Carroll, B., and E. P. Manche Kinetic Parameters from Temperature-Programmed Reactions The Pyrolysis of Polytetrafluorethylene. J. Appl. Polymer Sci. 9, 1895 (1965). 

Determination of kinetic parameters by temperature programmed methods... 

Miller JB, Siddiqui HR, Gates SM, etal. (1987) Extraction of kinetic parameters in temperature programmed desorption A comparison of methods. Journal of Chemical Physics 87 6725-6732. 

TPD Temperature programmed desorption After pre-adsorption of gases on a surface, the desorption and/or reaction products are measured while the temperature Increases linearly with time. Coverages, kinetic parameters, reaction mechanism... 

Using the same values of the kinetic parameters as in Type 1, and given C o = 0-1 mo 1/1, it is possible to solve Equation 6-155 with Equations 6-127 and 6-128 simultaneously to determine the fractional conversion X. A computer program was developed to determine the fractional conversion for different values of (-iz) and a temperature range of 260-500 K. Eigure 6-30 shows the reaction profile from the computer results. 

Kinetic studies at several temperatures followed by application of the Arrhenius equation as described constitutes the usual procedure for the measurement of activation parameters, but other methods have been described. Bunce et al. eliminate the rate constant between the Arrhenius equation and the integrated rate equation, obtaining an equation relating concentration to time and temperature. This is analyzed by nonlinear regression to extract the activation energy. Another approach is to program temperature as a function of time and to analyze the concentration-time data for the activation energy. This nonisothermal method is attractive because it is efficient, but its use is not widespread. ... 

The techniques referred to above (Sects. 1—3) may be operated for a sample heated in a constant temperature environment or under conditions of programmed temperature change. Very similar equipment can often be used differences normally reside in the temperature control of the reactant cell. Non-isothermal measurements of mass loss are termed thermogravimetry (TG), absorption or evolution of heat is differential scanning calorimetry (DSC), and measurement of the temperature difference between the sample and an inert reference substance is termed differential thermal analysis (DTA). These techniques can be used singly [33,76,174] or in combination and may include provision for EGA. Applications of non-isothermal measurements have ranged from the rapid qualitative estimation of reaction temperature to the quantitative determination of kinetic parameters [175—177]. The evaluation of kinetic parameters from non-isothermal data is dealt with in detail in Chap. 3.6. 

Finally, although both temperature-programmed desorption and reaction are indispensable techniques in catalysis and surface chemistry, they do have limitations. First, TPD experiments are not performed at equilibrium, since the temperature increases constantly. Secondly, the kinetic parameters change during TPD, due to changes in both temperature and coverage. Thirdly, temperature-dependent surface processes such as diffusion or surface reconstruction may accompany desorption and exert an influence. Hence, the technique should be used judiciously and the derived kinetic data should be treated with care ... 

Figure 7.14. The temperature-programmed reaction and corresponding Arrhenius plot based on rate expression (21) enables the calculation of kinetic parameters for the elementary surface reaction between CO and O atoms on a Rh(lOO) surface.

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 ... 

Explain how the kinetic parameters of an elementary step can be derived from temperature-programmed experiments with surfaces on which the reacting species have been preadsorbed. 

Figure 16 Simulated and experimental temperature-programmed desorption spectra for OlPt(lll). The solid lines are experimental spectra. The crosses indicate simulated spectra for a model of the lateral interactions with nearest and next-nearest pair interactions, and also a linear 3-particle interaction. The O2 is formed from two atoms at next-nearest-neighbor positions. The kinetic parameters are — 206.4 kj/mol, v = 2.5 x 10 s a = 0.773, cpxN — 19.9 kjjmol, tp NN = 5.5 kjjmol, and (punear = 6.1 kJImol. In each plot the curves from top to bottom are for initial oxygen coverage of 0.194, 0.164, 0.093, and 0.073 ML, respectively. The heating rate is 8 Kjs ...

Temperature programmed desorption (TPD) is an experimental technique to measure surface kinetic parameters. The most straightforward analysis of TPD is due to Redhead [331], Assuming that the surface has some fractional coverage 0 of adsorbed A molecules, the desorption rate of A from the surface r(j (1/s) is taken to be... 

Temperature-programmed DSC, or DTA measurements, can only suggest the autocatalytic nature of the decomposition. Neither the influence of the thermal history and contamination can be detected by them, nor can the kinetic parameters be determined from a single experiment. 

Figure 3.1 gives a Matlab program that sizes the reactor given the conversion, reactor temperature, feed conditions, coolant properties, and kinetic parameters. Then the coefficients of the linear model are evaluated, and the poles and zeros of the openloop transfer function are calculated. If any of the poles have positive real parts, the system is openloop-unstable. 

In the case of a temperature programmed reaction (reduction, desorption with reaction or oxidation), the products desorbed are formed on the surface via a chemical reaction when the temperature increases. Kinetic laws of the phenomenon have been established for different systems. It is thus possible to derive the kinetic parameters of the reaction under consideration (in particular, the activation energy). 

Kinetic data measured for the decomposition of calcium carbonate under isothermal and under programmed-temperature conditions [11] and varied reaction environments influencing the ease of removal of the CO2 product, show that the apparent values of the kinetic parameters k, A and may be influenced by sample heating rate, reactant self-cooling, sample mass, geometry and particle size, which determine the rate because of the reversible nature of the decomposition [12]. These effects can lead to compensation behaviour [13]. 

Figure 40. Twelve different patterns of temperature programs used to study the effect of temperature programs on kinetic parameters estimated by nonisothemal prediction. (Reproduced from Ref. 334 with permission.)...

The kinetic parameters for coke combustion were obtained by fitting to eq. (14) the experimental data of weight loss rate, dC/dt, obtained in thermogravimetric equipment by working under a programmed sequence of temperature-time [9]. 

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