Heat capacity model

The heat capacity models described so far were all based on a harmonic oscillator approximation. This implies that the volume of the simple crystals considered does not vary with temperature and Cy m is derived as a function of temperature for a crystal having a fixed volume. Anharmonic lattice vibrations give rise to a finite isobaric thermal expansivity. These vibrations contribute both directly and indirectly to the total heat capacity directly since the anharmonic vibrations themselves contribute, and indirectly since the volume of a real crystal increases with increasing temperature, changing all frequencies. The constant volume heat capacity derived from experimental heat capacity data is different from that for a fixed volume. The difference in heat capacity at constant volume for a crystal that is allowed to relax at each temperature and the heat capacity at constant volume for a crystal where the volume is fixed to correspond to that at the Debye temperature represents a considerable part of Cp m - Cv m. This is shown for Mo and W [6] in Figure 8.15. 

We now specify the equation of state used to model detonation products. For the ideal gas portion of the Helmholtz free energy, we use a polyatomic model including electronic, vibrational, and rotational states. Such a model can be conveniently expressed in terms of the heat of formation, standard entropy, and constant pressure heat capacity of each species. The heat capacities of many product species have been calculated by a direct sum over experimental electronic, vibrational, and rotational states. These calculations were performed to extend the heat capacity model beyond the 6000K upper limit used in the JANAF thermochemical tables (J. Phys. Chem. Ref. Data, Vol. 14, Suppl. 1, 1985). Chebyshev polynomials, which accurately reproduce heat capacities, were generated. 

The heat capacities of many product species have been calculated by a direct smn over experimental electronic, vibrational, and rotational states. These calculations were performed to extend the heat capacity model beyond the 6000K upper limit used in the JANAF thermochemical tables. Chebyshev polynomials, which accurately reproduce the heat capacities, were generated. 

This is probably the most comprehensive set of heat capacity results available for any nickel salt in aqueous solution. Apparent molar heat capacities of aqueous Ni(C104)2 were measured calorimetrically from 25 to 85°C over a molality range of 0.02 to 0.80 moFkg. Standard molar heat capacities of Ni for the same temperature range were obtained by using the additivity rule and data for HC104(aq), given in literature. The results for C° (Ni " ) can be fitted with a conventional heat capacity model valid from... 

Figure 4.13 Comparison of temperature-dependent specific heat capacity models of E-glass fibers [12]. (With permission from Elsevier.)...

Table 5 Group Contributions to the Coefficients for the Ideal Gas Heat Capacity Model C =A + BT -F Cr 4-DrT The Units for the Contributions are kJ kmol ...

Another important accomplislnnent of the free electron model concerns tire heat capacity of a metal. At low temperatures, the heat capacity of a metal goes linearly with the temperature and vanishes at absolute zero. This behaviour is in contrast with classical statistical mechanics. According to classical theories, the equipartition theory predicts that a free particle should have a heat capacity of where is the Boltzmann constant. An ideal gas has a heat capacity consistent with tliis value. The electrical conductivity of a metal suggests that the conduction electrons behave like free particles and might also have a heat capacity of 3/fg,... 

Phonons are nomial modes of vibration of a low-temperatnre solid, where the atomic motions around the equilibrium lattice can be approximated by hannonic vibrations. The coupled atomic vibrations can be diagonalized into uncoupled nonnal modes (phonons) if a hannonic approximation is made. In the simplest analysis of the contribution of phonons to the average internal energy and heat capacity one makes two assumptions (i) the frequency of an elastic wave is independent of the strain amplitude and (ii) the velocities of all elastic waves are equal and independent of the frequency, direction of propagation and the direction of polarization. These two assumptions are used below for all the modes and leads to the famous Debye model. 

Valleau J P and Torrie G M 1998 Heat capacity of the restricted primitive model J. Chem. Phys. 108 5169... 

The initial classification of phase transitions made by Ehrenfest (1933) was extended and clarified by Pippard [1], who illustrated the distmctions with schematic heat capacity curves. Pippard distinguished different kinds of second- and third-order transitions and examples of some of his second-order transitions will appear in subsequent sections some of his types are unknown experimentally. Theoretical models exist for third-order transitions, but whether tiiese have ever been found is unclear. 

The integral under the heat capacity curve is an energy (or enthalpy as the case may be) and is more or less independent of the details of the model. The quasi-chemical treatment improved the heat capacity curve, making it sharper and narrower than the mean-field result, but it still remained finite at the critical point. Further improvements were made by Bethe with a second approximation, and by Kirkwood (1938). Figure A2.5.21 compares the various theoretical calculations [6]. These modifications lead to somewhat lower values of the critical temperature, which could be related to a flattening of the coexistence curve. Moreover, and perhaps more important, they show that a short-range order persists to higher temperatures, as it must because of the preference for unlike pairs the excess heat capacity shows a discontinuity, but it does not drop to zero as mean-field theories predict. Unfortunately these improvements are still analytic and in the vicinity of the critical point still yield a parabolic coexistence curve and a finite heat capacity just as the mean-field treatments do. 

That analyticity was the source of the problem should have been obvious from the work of Onsager (1944) [16] who obtained an exact solution for the two-dimensional Ising model in zero field and found that the heat capacity goes to infinity at the transition, a logarithmic singularity tiiat yields a = 0, but not the a = 0 of the analytic theory, which corresponds to a finite discontinuity. (Wliile diverging at the critical point, the heat capacity is synnnetrical without an actual discontinuity, so perhaps should be called third-order.)... 

Figure A2.5.28. The coexistence curve and the heat capacity of the binary mixture 3-methylpentane + nitroethane. The circles are the experimental points, and the lines are calculated from the two-tenn crossover model. Reproduced from [28], 2000 Supercritical Fluids—Fundamentals and Applications ed E Kiran, P G Debenedetti and C J Peters (Dordrecht Kluwer) Anisimov M A and Sengers J V Critical and crossover phenomena in fluids and fluid mixtures, p 16, figure 3, by kind pemiission from Kluwer Academic Publishers.

We have seen in previous sections that the two-dimensional Ising model yields a syimnetrical heat capacity curve tliat is divergent, but with no discontinuity, and that the experimental heat capacity at the k-transition of helium is finite without a discontinuity. Thus, according to the Elirenfest-Pippard criterion these transitions might be called third-order. 

Its value at 25°C is 0.71 J/(g-°C) (0.17 cal/(g-°C)) (95,147). Discontinuities in the temperature dependence of the heat capacity have been attributed to stmctural changes, eg, crystaUi2ation and annealing effects, in the glass. The heat capacity varies weakly with OH content. Increasing the OH level from 0.0003 to 0.12 wt % reduces the heat capacity by approximately 0.5% at 300 K and by 1.6% at 700 K (148). The low temperature (<10 K) heat capacities of vitreous siUca tend to be higher than the values predicted by the Debye model (149). 

The basic phenomenon was observed in modeling studies by Bjoreskov and Slinko (1965) that sudden increase in inlet temperature caused a transient drop of the peak temperature. The wrong-way response name was given by Mechta et al (1981) after they experienced the opposite a sudden of inlet temperature resulted in an increase of the peak temperature (which may eventually cause a runaway.) The work used a pseudo-homogeneous reaction model and explained the phenomenon by the different speeds of transient response in gas and solid. The example in the last part of Chapter 7.4 explained the speed difference by the large difference in heat capacity of gas and solid phases. For this a two-phase model is needed and spatial and time changes must be followed. 

FIG. 12 The behavior of the internal energy U (per site), heat capacity Cy (per site), the average Euler characteristic (x) and its variance (x") — (x) close to the transition line and at the transition to the lamellar phase for/o = 0. The changes are small at the transition and the transition is very weakly first-order. The weakness of the transition is related to the proliferation of the wormhole passages, which make the lamellar phase locally very similar to the microemulsion phase (Fig. 13). Note also that the values of the energy and heat capacity are not very much different from their values (i.e., 0.5 per site) in the Gaussian approximation of the model [47]. (After Ref. 49.)... 

It is reasonable to expeet that models in ehemistry should be capable of giving thermodynamic quantities to chemical accuracy. In this text, the phrase thermodynamic quantities means enthalpy changes A//, internal energy changes AU, heat capacities C, and so on, for gas-phase reactions. Where necessary, the gases are assumed ideal. The calculation of equilibrium constants and transport properties is also of great interest, but I don t have the space to deal with them in this text. Also, the term chemical accuracy means that we should be able to calculate the usual thermodynamic quantities to the same accuracy that an experimentalist would measure them ( 10kJmol ). 

In this approach, connectivity indices were used as the principle descriptor of the topology of the repeat unit of a polymer. The connectivity indices of various polymers were first correlated directly with the experimental data for six different physical properties. The six properties were Van der Waals volume (Vw), molar volume (V), heat capacity (Cp), solubility parameter (5), glass transition temperature Tfj, and cohesive energies ( coh) for the 45 different polymers. Available data were used to establish the dependence of these properties on the topological indices. All the experimental data for these properties were trained simultaneously in the proposed neural network model in order to develop an overall cause-effect relationship for all six properties. 

Figure 25 ANN model (5-8-6) training and testing results for van der Waals volume, molar volume, heat capacity, solubility parameter, and glass transition temperature of 45 different polymers.

Indeed, the multi-layered model, applied to fiber reinforced composites, presented a basic inconsistency, as it appeared in previous publications17). This was its incompatibility with the assumption that the boundary layer, constituting the mesophase between inclusions and matrix, should extent to a thickness well defined by thermodynamic measurements, yielding jumps in the heat capacity values at the glass-transition temperature region of the composites. By leaving this layer in the first models to extent freely and tend, in an asymptotic manner, to its limiting value of Em, it was allowed to the mesophase layer to extend several times further, than the peel anticipated from thermodynamic measurements, fact which does not happen in its new versions. 

The process we have followed Is Identical with the one we used previously for the uranium/oxygen (U/0) system (1-2) and Is summarized by the procedure that Is shown In Figure 1. Thermodynamic functions for the gas-phase molecules were obtained previously (3) from experimental spectroscopic data and estimates of molecular parameters. The functions for the condensed phase have been calculated from an assessment of the available data, Including the heat capacity as a function of temperature (4). The oxygen potential Is found from extension Into the liquid phase of a model that was derived for the solid phase. Thus, we have all the Information needed to apply the procedure outlined In Figure 1. 

In the model equations, A represents the cross sectional area of reactor, a is the mole fraction of combustor fuel gas, C is the molar concentration of component gas, Cp the heat capacity of insulation and F is the molar flow rate of feed. The AH denotes the heat of reaction, L is the reactor length, P is the reactor pressure, R is the gas constant, T represents the temperature of gas, U is the overall heat transfer coefficient, v represents velocity of gas, W is the reactor width, and z denotes the reactor distance from the inlet. The Greek letters, e is the void fraction of catalyst bed, p the molar density of gas, and rj is the stoichiometric coefficient of reaction. The subscript, c, cat, r, b and a represent the combustor, catalyst, reformer, the insulation, and ambient, respectively. The obtained PDE model is solved using Finite Difference Method (FDM). 

In model equations, Uf denotes the linear velocity in the positive direction of z, z is the distance in flow direction with total length zr, C is concentration of fuel, s represents the void volume per unit volume of canister, and t is time. In addition to that, A, is the overall mass transfer coefficient, a, denotes the interfacial area for mass transfer ifom the fluid to the solid phase, ah denotes the interfacial area for heat transfer, p is density of each phase, Cp is heat capacity for a unit mass, hs is heat transfer coefficient, T is temperature, P is pressure, and AHi represents heat of adsorption. The subscript d refers bulk phase, s is solid phase of adsorbent, i is the component index. The superscript represents the equilibrium concentration. 

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