Surface activation energy migration

For many practically relevant material/environment combinations, thennodynamic stability is not provided, since E > E. Hence, a key consideration is how fast the corrosion reaction proceeds. As for other electrochemical reactions, a variety of factors can influence the rate detennining step. In the most straightforward case the reaction is activation energy controlled i.e. the ion transfer tlrrough the surface Helmholtz double layer involving migration and the adjustment of the hydration sphere to electron uptake or donation is rate detennining. The transition state is... 

Although the h.e.r. involves transport of HjO ions (or HjO molecules) to the metal surface by diffusion and migration, the activation energy for... 

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. 

As the working temperature of the substrate was increased, the induction period (the delay time) of increased conductivity decreased due to increased rate of lateral diffusion of hydrogen atoms towards the sensor. The activation energy for surface migration of particles along a Si02 substrate estimated from the tilt of the Arrhenius plot was found to be about 20 kj/mol. 

By varying the temperature at which the experiments were conducted and the distance between the activator and the sensor, the data were obtained (Fig. 4.17) which allowed us to calculate the activation energy of migration of hydrogen adatoms (protium and deuterium) along the carrier surface and coefficients of lateral diffusion of hydrogen atoms appearing due to the spillover effect (see Table 4.2). 

Migrating particle System Activation energy for migration, kj/mol Coefficient of surface diffusion at 345 K, m /s... 

It is particularly helpful that we can take the Cu-Ni system as an example of the use of successive deposition for preparing alloy films where a miscibility gap exists, and one component can diffuse readily, because this alloy system is also historically important in discussing catalysis by metals. The rate of migration of the copper atoms is much higher than that of the nickel atoms (there is a pronounced Kirkendall effect) and, with polycrystalline specimens, surface diffusion of copper over the nickel crystallites requires a lower activation energy than diffusion into the bulk of the crystallites. Hence, the following model was proposed for the location of the phases in Cu-Ni films (S3), prepared by annealing successively deposited layers at 200°C in vacuum, which was consistent with the experimental data on the work function. 

K and <0 being constants. The reaction constant k was shown to be proportional to the surface diffusion coefficient, so the activation energy for migration was computed from the temperature coefficient of k, i.e.,... 

Turning now to the applications considered in Secs. IX, X, and XI, we note that the activation energies of desorption and migration are conveniently measured by S.P. methods, while the results obtained for the adsorption of N2O on Pt show that there is considerable scope for the application of work-function measurements in investigating catalytic reactions at metal surfaces. 

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