Activation energy controlled process

Systems that are governed by reaction kinetics show well-defined behaviors as a function of temperature and potential. If the system can be described as being controlled by a single activation-energy-controlled process, graphical methods can be used to cause the data to superpose. 

Impedance data taken at different temperatures for systems governed by single-step activation-energy-controlled processes may be expected to superpose when properly normalized. 

P21.17 If diffusion is analogous to viscosity JSection 21.5, eqn 21.26] in that it is also an activation energy controlled process, then we expect... 

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 ... 

The Nyquist plot is a very convenient representation of the R - R circuit process, as it shows an ideal semicircle as an indication of the activation-energy-controlled charge-transfer process. A depressed semicircle in the Nyquist plot is an indication of multiple processes with similar relaxation time constants, or distributed non-ideal kinetics. These ambiguities can be resolved in the "original" and modified Bode plots, as shown in Figures 2-3 and 2-4. The departure of the slope of log vs. log frequency dependency from the unity indicates a distributed process, with a characteristic frequency that may not even correspond to the highest peak value of... 

The Langmuir-Hinshelwood picture is essentially that of Fig. XVIII-14. If the process is unimolecular, the species meanders around on the surface until it receives the activation energy to go over to product(s), which then desorb. If the process is bimolecular, two species diffuse around until a reactive encounter occurs. The reaction will be diffusion controlled if it occurs on every encounter (see Ref. 211) the theory of surface diffusional encounters has been treated (see Ref. 212) the subject may also be approached by means of Monte Carlo/molecular dynamics techniques [213]. In the case of activated bimolecular reactions, however, there will in general be many encounters before the reactive one, and the rate law for the surface reaction is generally written by analogy to the mass action law for solutions. That is, for a bimolecular process, the rate is taken to be proportional to the product of the two surface concentrations. It is interesting, however, that essentially the same rate law is obtained if the adsorption is strictly localized and species react only if they happen to adsorb on adjacent sites (note Ref. 214). (The apparent rate law, that is, the rate law in terms of gas pressures, depends on the form of the adsorption isotherm, as discussed in the next section.)... 

Inert gas pressure, temperature, and conversion were selected as these are the critical variables that disclose the nature of the basic rate controlling process. The effect of temperature gives an estimate for the energy of activation. For a catalytic process, this is expected to be about 90 to 100 kJ/mol or 20-25 kcal/mol. It is higher for higher temperature processes, so a better estimate is that of the Arrhenius number, y = E/RT which is about 20. If it is more, a homogeneous reaction can interfere. If it is significantly less, pore diffusion can interact. 

In contrast to the influence of velocity, whose primary effect is to increase the corrosion rates of electrode processes that are controlled by the diffusion of reactants, temperature changes have the greatest effect when the rate determining step is the activation process. In general, if diffusion rates are doubled for a certain increase in temperature, activation processes may be increased by 10-100 times, depending on the magnitude of the activation energy. 

Film-free conditions It has been observed for many metals that the magnitude of / i, (see Section 1.4) increases with temperature and that the activation energy for dissolution is low, suggestive of a diffusion-limited anode process when the migration of corrosion products away from the surface is rate controlling. Some examples of the value of the activation energy for this process are given in Table 2.4. 

Degradation is appreciable only if K > l/tr this occurs whenever the coefficient a M e offsets the dissociation energy term — U0. It is physically unrealistic that an elementary chemical process can have negative activation energy, therefore the permissible maximum for K is controlled by the pre-exponential factor A (i — 1). 

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