Temperature dependence capacity

Thermosets are often used in intimate contact with materials of much lower coefficient of linear thermal expansion p. A thermoset film may be coated on a surface, or sandwiched between two surfaces as an adhesive. A thermoset matrix may be filled with high-modulus fibers in aerospace structural materials and in other composite materials. A residual stress other material(s) to changes in temperature. The value of or typically reflects the balance between the driving force to produce residual stresses due to differential shrinkage upon cooling and the temperature-dependent capacity to relax these stresses. The worst such effects... 

Heat Capacity (or Specific Heat) The temperature dependence of the heat capacity is complex. If the temperature range is restricted, the heat capacity of any phase may be represented adequately by an expression such as ... 

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). 

Evaluation of the integrals requires an empirical expression for the temperature dependence of the ideal gas heat capacity, (3p (8). The residual Gibbs energy is related to and by equation 138 ... 

The temperature dependence of the open circuit voltage has been accurately determined (22) from heat capacity measurements (23). The temperature coefficients are given in Table 2. The accuracy of these temperature coefficients does not depend on the accuracy of the open circuit voltages at 25°C shown in Table 1. Using the data in Tables 1 and 2, the open circuit voltage can be calculated from 0 to 60°C at concentrations of sulfuric acid from 0.1 to 13.877 m. 

From this equation, the temperature dependence of is known, and vice versa (21). The ideal-gas state at a pressure of 101.3 kPa (1 atm) is often regarded as a standard state, for which the heat capacities are denoted by CP and Real gases rarely depart significantly from ideaHty at near-ambient pressures (3) therefore, and usually represent good estimates of the heat capacities of real gases at low to moderate, eg, up to several hundred kPa, pressures. Otherwise thermodynamic excess functions are used to correct for deviations from ideal behavior when such situations occur (3). 

Thns, the pressure or vohime dependence of the heat capacities may be determined from PVT data. The temperature dependence of the heat capacities is, however, determined empirically and is often given by equations such as... 

The ideal-gas-state heat capacity Cf is a function of T but not of T. For a mixture, the heat capacity is simply the molar average X, Xi Cf. Empirical equations giving the temperature dependence of Cf are available for many pure gases, often taking the form... 

These heat capacity approximations take no account of the quantal nature of atomic vibrations as discussed by Einstein and Debye. The Debye equation proposed a relationship for the heat capacity, the temperature dependence of which is related to a characteristic temperature, Oy, by a universal expression by making a simplified approximation to the vibrational spectimii of die... 

The implicit Crank-Nicholson integration method was used to solve the equation. Radial temperature and concentrations were calculated using the Thomas algorithm (Lapidus 1962, Carnahan et al,1969). This program allowed the use of either ideal or non-ideal gas laws. For cases using real gas assumptions, heat capacity and heat of reactions were made temperature dependent. 

The T3 relationship for heat capacity represented by equation (4.4) applies to most solids at low temperatures, but there are exceptions. Summarized in the table below are the different types of temperature dependencies on Cp that have been observed at low temperatures. 

For Cy/T to approach zero as T approaches zero, CV must go to zero at a rate at least proportional to T. Earlier, we summarized the temperature dependence of Cy on T for different substances and showed that this is true. For example, most solids follow the Debye low-temperature heat capacity equation of low T for which... 

One of the more interesting results of these calculations is the contribution to the heat capacity. Figure 10.10 shows the temperature dependence of this contribution to the heat capacity for CH3-CCU as calculated from Pitzer s tabulation with 7r = 5.25 x 10-47 kg m2 and VQ/R — 1493 K. The heat capacity increases initially, reaches a maximum near the value expected for an anharmonic oscillator, but then decreases asymptotically to the value of / expected for a free rotator as kT increases above Vo. The total entropy calculated for this molecule at 286.53 K is 318.86 J K l-mol l, which compares very favorably with the value of 318.94T 0.6 TK-1-mol 1 calculated from Third Law measurements.7... 

Extraordinarily precise kinetic data are required to detect the further temperature dependence of an activation parameter. If A// is temperature-dependent, then the temperature profile will be curved. By analogy with the equation relating AH and AC , we may define the heat capacity of activation by... 

From this definition, we can obtain an expression for the temperature dependence of AH of a reaction, if the heat capacity at constant pressure is known. For the pressure dependence, the following fundamental relationship offers a good start ... 

The thermal conductivity plateau has traditionally been considered by most workers as a separate issue from the TLS. In addition to the rapidly growing magnitude of phonon scattering at the plateau, an excess of density of states is observed in the form of the so-called bump in the heat capacity temperature dependence divided by T. The plateau is interesting from several perspectives. For one thing, it is nonuniversal if scaled by the elastic constants (say, co/)... 

A number of other thermodynamic properties of adamantane and diamantane in different phases are reported by Kabo et al. [5]. They include (1) standard molar thermodynamic functions for adamantane in the ideal gas state as calculated by statistical thermodynamics methods and (2) temperature dependence of the heat capacities of adamantane in the condensed state between 340 and 600 K as measured by a scanning calorimeter and reported here in Fig. 8. According to this figure, liquid adamantane converts to a solid plastic with simple cubic crystal structure upon freezing. After further cooling it moves into another solid state, an fee crystalline phase. 

Figure 8. The temperature dependence of the heat capacity in the condensed state for adamantane [5] as measured by a scanning calorimeter. Tu, stands for temperature of transition from rigid crystal (fee) to plastic crystal (cubic) state of adamantane and Tfas stands for fusion temperature.

The temperature dependency of heat capacity can usually be described by a polynomial expression, e.g.,... 

For cases where AH0 is essentially independent of temperature, plots of in Ka versus 1/T are linear with slope —(AH°/R). For cases where the heat capacity term in equation 2.2.7 is appreciable, this equation must be substituted in either equation 2.5.2 or equation 2.5.3 in order to determine the temperature dependence of the equilibrium constant. For exothermic reactions (AH0 negative) the equilibrium constant decreases with increasing temperature, while for endothermic reactions the equilibrium constant increases with increasing temperature. 

Equations I and J indicate that for the temperature range of interest (640 to 830 °K), the heat capacity per unit mass is substantially independent of the conversion level. Furthermore, the temperature dependent contribution to the heat capacity will not vary much over the temperature range involved. Hence without introducing errors comparable to those inherent in the use of a one-dimensional model, we may take the heat capacity as constant at 0.250 cal/g-°K or 0.250 BTU/(lb-°F). 

Although Equation (4) is conceptually correct, the application to experimental data should be undertaken cautiously, especially when an arbitrary baseline is drawn to extract the area under the DSC melting peak. The problems and inaccuracy of the calculated crystallinities associated with arbitrary baselines have been pointed out by Gray [36] and more recently by Mathot et al. [37,64—67]. The most accurate value requires one to obtain experimentally the variation of the heat capacity during melting (Cp(T)) [37]. However, heat flow (d(/) values can yield accurate crystallinities if the primary heat flow data are devoid of instrumental curvature. In addition, the temperature dependence of the heat of fusion of the pure crystalline phase (AHc) and pure amorphous phase (AHa) are required. For many polymers these data can be found via their heat capacity functions (ATHAS data bank [68]). The melt is then linearly extrapolated and its temperature dependence identified with that of AHa. The general expression of the variation of Cp with temperature is... 

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