Temperature-Dependent Theory

The gradient model has been combined with two equations of state to successfully model the temperature dependence of the surface tension of polar and nonpolar fluids [54]. Widom and Tavan have modeled the surface tension of liquid He near the X transition with a modified van der Waals theory [55]. 

Figure B2.5.7 shows the absorption traces of the methyl radical absorption as a fiinction of tune. At the time resolution considered, the appearance of CFt is practically instantaneous. Subsequently, CFl disappears by recombination (equation B2.5.28). At temperatures below 1500 K, the equilibrium concentration of CFt is negligible compared witli (left-hand trace) the recombination is complete. At temperatures above 1500 K (right-hand trace) the equilibrium concentration of CFt is appreciable, and thus the teclmique allows the detennination of botli the equilibrium constant and the recombination rate [54, M]. This experiment resolved a famous controversy on the temperature dependence of the recombination rate of methyl radicals. Wliile standard RRKM theories [, ] predicted an increase of the high-pressure recombination rate coefficient /r (7) by a factor of 10-30 between 300 K and 1400 K, the statistical-adiabatic-chaunel model predicts a...

In order to Introduce thermal effects into the theory, the material balance equations developed in this chapter must be supplemented by a further equation representing the condition of enthalpy balance. This matches the extra dependent variable, namely temperature. Care must also be taken to account properly for the temperature dependence of certain parameters In... 

The shape of the (7 and curves is theoretically well established by critical scaling theory. The temperature dependence is given by... 

The development of combustion theory has led to the appearance of several specialized asymptotic concepts and mathematical methods. An extremely strong temperature dependence for the reaction rate is typical of the theory. This makes direct numerical solution of the equations difficult but at the same time accurate. The basic concept of combustion theory, the idea of a flame moving at a constant velocity independent of the ignition conditions and determined solely by the properties and state of the fuel mixture, is the product of the asymptotic approach (18,19). Theoretical understanding of turbulent combustion involves combining the theory of turbulence and the kinetics of chemical reactions (19—23). 

Solid 10-" 10- 10- io- 10- -10- Approximate theories exist strong temperature dependence... 

It follows from this discussion that all of the transport properties can be derived in principle from the simple kinetic dreoty of gases, and their interrelationship tlu ough k and c leads one to expect that they are all characterized by a relatively small temperature coefficient. The simple theory suggests tlrat this should be a dependence on 7 /, but because of intermolecular forces, the experimental results usually indicate a larger temperature dependence even up to for the case of molecular inter-diffusion. The Anhenius equation which would involve an enthalpy of activation does not apply because no activated state is involved in the transport processes. If, however, the temperature dependence of these processes is fitted to such an expression as an algebraic approximation, tlren an activation enthalpy of a few kilojoules is observed. It will thus be found that when tire kinetics of a gas-solid or liquid reaction depends upon the transport properties of the gas phase, the apparent activation entlralpy will be a few kilojoules only (less than 50 kJ). 

The temperature dependences of k, calculated by Hancock et al. [1989], are given in fig. 48. The crossover temperature equals 25-30 K. The weak increase of k T) with decreasing temperature below is an artefact caused by extending the gas-phase theory prefactor to low temperatures without taking into account the zero-point vibrations of the H atom in the crystal. For the same reason the values of the constants differ by 1-2 orders of magnitude from the experimental ones. 

The theory relating stress, strain, time and temperature of viscoelastic materials is complex. For many practical purposes it is often better to use an ad hoc system known as the pseudo-elastic design approach. This approach uses classical elastic analysis but employs time- and temperature-dependent data obtained from creep curves and their derivatives. In outline the procedure consists of the following steps ... 

S. Olive, U. Grafe, I. Steinbach. The modelling of Ostwald-ripening during non-isothermal heat treatments resulting in temperature dependent matrix solubihty of the precipitate forming elements a further development of the LSW-theory. Comput Mater Sci 7. 94, 1996. 

The numerical values of AG and A5 depend upon the choice of standard states in solution kinetics the molar concentration scale is usually used. Notice (Eq. 5-43) that in transition state theory the temperature dependence of the rate constant is accounted for principally by the temperature dependence of an equilibrium constant. 

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... 

Figure 5. Temperature development of the electronic density of states in fee FeaNi with the temperature dependent input taken from the Ginzburg-Landau theory (magnetic moments are given per atom).

A recent theoretical analysis of the temperature dependence of the magnetic response of neutral disorder-induced solitons 69], has revealed that these solitons may explain the low-temperature deviation from Curie behavior that is observed in experiments on Durham /ra/t.y-polyaeetylene [70]. A more stringent test of the theory would involve extending these experiments to even lower temperatures (down to 1 K or lower). 

The shapes of experimental and theoretical j(Fj curves are in mutual agreement. By comparison one arrives at injection barriers ranging from 0.4 eV (PPV imine) to 0.7 eV (PPPV). The agreement between theory and experiment is similarly good as far as the temperature dependence is concerned. Data shown in Figure 12-7 were taken with DASMB and confirm the analytic results for A=0.4eV. 

The calculation of the dependence of S upon AT does not seem to have been performed, however, as explained in Sect. 3.3 any theory which has a growth rate proportional to exp — (/ — lmin)/kT will display the correct temperature dependence. As Eq. (3.109) should be dominated by values of / close to lmin the correct functional form for the growth rate follows directly. 

If a data set containing k T) pairs is fitted to this equation, the values of these two parameters are obtained. They are A, the pre-exponential factor (less desirably called the frequency factor), and Ea, the Arrhenius activation energy or sometimes simply the activation energy. Both A and Ea are usually assumed to be temperature-independent in most instances, this approximation proves to be a very good one, at least over a modest temperature range. The second equation used to express the temperature dependence of a rate constant results from transition state theory (TST). Its form is... 

Show how collision theory and transition state theory account for the temperature dependence of reactions (Sections... 

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