Preexponential factor temperature dependence

It should be emphasized that the recommended rate-coefficient parameters listed are no more than pragmatic representations of experimental data no physical interpretation is made of the significance of the preexponential factor, temperature dependence, or activation energy. The error limits given include allowance for systematic errors, in spite of the difficulty of estimating these, and are therefore larger than the usually stated error limits that only reflect statistical precision of measurements and not true uncertainty of results. 

A more interesting possibility, one that has attracted much attention, is that the activation parameters may be temperature dependent. In Chapter 5 we saw that theoiy predicts that the preexponential factor contains the quantity T", where n = 5 according to collision theory, and n = 1 according to the transition state theory. In view of the uncertainty associated with estimation of the preexponential factor, it is not possible to distinguish between these theories on the basis of the observed temperature dependence, yet we have the possibility of a source of curvature. Nevertheless, the exponential term in the Arrhenius equation dominates the temperature behavior. From Eq. (6-4), we may examine this in terms either of or A//. By analogy with equilibrium thermodynamics, we write... 

Several points are worth noting about these formulae. Firstly, the concentrations follow an Arrhenius law except for the constitutional def t, however in no case is the activation energy a single point defect formation energy. Secondly, in a quantitative calculation the activation energy should include a temperature dependence of the formation energies and their formation entropies. The latter will appear as a preexponential factor, for example, the first equation becomes... 

When the temperature of the analyzed sample is increased continuously and in a known way, the experimental data on desorption can serve to estimate the apparent values of parameters characteristic for the desorption process. To this end, the most simple Arrhenius model for activated processes is usually used, with obvious modifications due to the planar nature of the desorption process. Sometimes, more refined models accounting for the surface mobility of adsorbed species or other specific points are applied. The Arrhenius model is to a large extent merely formal and involves three effective (apparent) parameters the activation energy of desorption, the preexponential factor, and the order of the rate-determining step in desorption. As will be dealt with in Section II. B, the experimental arrangement is usually such that the primary records reproduce essentially either the desorbed amount or the actual rate of desorption. After due correction, the output readings are converted into a desorption curve which may represent either the dependence of the desorbed amount on the temperature or, preferably, the dependence of the desorption rate on the temperature. In principle, there are two approaches to the treatment of the desorption curves. 

Figure 8.75 shows the dependence of the apparent activation energy Ea and of the apparent preexponential factor r°, here expressed as TOF°, on Uwr. Interestingly, increasing Uwr increases not only the catalytic rate, but also the apparent activation energy Ea from 0.3 eV (UWr=-2 V) to 0.9 eV (UWr-+2V). The linear variation in Ea and log (TOF°) with UWr leads to the appearance of the compensation effect where, in the present case, the isokinetic point (T =300°C) lies outside the temperature range of the investigation. 

Arrhenius proposed his equation in 1889 on empirical grounds, justifying it with the hydrolysis of sucrose to fructose and glucose. Note that the temperature dependence is in the exponential term and that the preexponential factor is a constant. Reaction rate theories (see Chapter 3) show that the Arrhenius equation is to a very good approximation correct however, the assumption of a prefactor that does not depend on temperature cannot strictly be maintained as transition state theory shows that it may be proportional to 7. Nevertheless, this dependence is usually much weaker than the exponential term and is therefore often neglected. 

Various statistical treatments of reaction kinetics provide a physical picture for the underlying molecular basis for Arrhenius temperature dependence. One of the most common approaches is Eyring transition state theory, which postulates a thermal equilibrium between reactants and the transition state. Applying statistical mechanical methods to this equilibrium and to the inherent rate of activated molecules transiting the barrier leads to the Eyring equation (Eq. 10.3), where k is the Boltzmann constant, h is the Planck s constant, and AG is the relative free energy of the transition state [note Eq. (10.3) ignores a transmission factor, which is normally 1, in the preexponential term]. 

Holroyd (1977) finds that generally the attachment reactions are very fast (fej - 1012-1013 M 1s 1), are relatively insensitive to temperature, and increase with electron mobility. The detachment reactions are sensitive to temperature and the nature of the liquid. Fitted to the Arrhenius equation, these reactions show very large preexponential factors, which allow the endothermic detachment reactions to occur despite high activation energy. Interpreted in terms of the transition state theory and taking the collision frequency as 1013 s 1- these preexponential factors give activation entropies 100 to 200 J/(mole.K), depending on the solute and the solvent. 

The simultaneous desorption peaks observed at 560-580 K in TPR are of reaction-limited desorption. The peak temperatures of these peaks do not depend on the coverage of methoxy species, indicating that the desorption rate (reaction rate) on both surfaces has a first-order relation to the coverage of methoxy species. Activation energy (Ea) and the preexponential factor (v) for a first-order process are given by the following Redhead equation [12] ... 

The temperature dependence of luminescent metal complexes can be controlled by molecular design that affects the energy gap between the emitting state and the deactivating d-d or by altering the preexponential factor for thermal deactivation. The sometimes large temperature dependencies of lifetime and quantum yields for metal complexes also suggest their use as temperature sensors. 

The Horiuti group treats the temperature coefficient of the rate differently from the way it is usually treated in TST. They clearly identify E as the experimentally observed activation energy, but according to TST [cf. Eq. (5)] the (E — RT) quantity of Eq. (52) is the enthalpy of activation. The RT term in Eq. (5) arises because the assumption that the Arrhenius plot is linear is equivalent to the assumption that the preexponential factor A of the Arrhenius equation is constant, whereas, according to TST, A always contains the factor (kT/h). In addition, the partition function factors of Table I are also part of A, and most of them are functions of T. Since the Horiuti group takes this temperature dependency of the preexponential factor into account, the factor exp[(5/2)(vi -I- V2)] (where 5/2 is replaced by 3 for nonlinear molecules) arises. 

Fig. 7 Dependence of activation enthalpy H, preexponential factor A and compensation temperature f, in pure Alfor 38.2° ( )and 40.5° (M)< 111 >-tilt grain boundaries.

By comparison of (M) and (F), it can be seen that the preexponential factor A in the Arrhenius equation can be identified with PaA]i(8kT/Tr/ji,y/2 and the activation energy, a, with the threshold energy Eu. It is important to note that collision theory predicts that the preexponential factor should indeed be dependent on temperature (Tl/2). The reason so many reactions appear to follow the Arrhenius equation with A being temperature independent is that the temperature dependence contained in the exponential term normally swamps the smaller Tl/Z dependence. However, for reactions where E.t approaches zero, the temperature dependence of the preexponential factor can be significant. 

Again the preexponential factor is seen to be temperature dependent, but for large activation energies, the exponential term dominates the temperature dependence of the rate constant. 

As discussed in Chapter 5, kinetic theories predict that the preexponential factor should have a temperature dependence that manifests itself in curved Arrhenius plots if the reactions are studied over a sufficiently broad temperature range. This is the case for OH-al-kane reactions, where there has been great interest in the high-temperature kinetics for combustion systems. Table 6.2 also shows the temperature dependence for the OH reactions in the form k = BT"e c/l, where C = E.JR and in the form recommended by Donahue et al. (1998a). 

Experiments snch as the one illnstrated in Fignre 4.38 not only give us self-diffusion coefficients for certain snbstances, bnt as the temperatnre of the experiment is varied, they give us the temperature dependence of the process and a measurement of the activation energy barrier to diffnsion. Diffusion in solid systems, then, can be modeled as an activated process that is, an Arrhenius-type relationship can be written in which an activation energy, Ea, and temperatnre dependence are incorporated, along with a preexponential factor. Do, sometimes called ht frequency factor ... 

Thus, the energy E has the meaning of effective activation energy. With decreasing temperature, the effective activation energy and the preexponential factor /(E ) diminish. The reaction rate constant is proportional to the averaged reaction probability. The characteristic temperature dependence of the reaction rate constant is shown in Fig. 24. 

The temperature dependence of the relative rates, and therefore the differences in the activation energies and the ratios of the preexponential factors, have been determined (29) for several olefins by the nitrous oxide technique. The values are summarized in Table IV. In all cases the... 

A few comments on (2.27), (2.29), and (1.12) are appropriate at this point. The activation energy in the Arrhenius region is independent of 17, since friction changes only the velocity at which a classical particle crosses the barrier and thus affects only the preexponential factor. However, friction reduces both kc and Tc and thereby widens the Arrhenius region. Dissipation has a noticeable effect on the temperature dependence of... 

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