Heat capacity, standard

Instrumental methods in chemistry make it possible to characterize any chemical compound by a very large number of different kind of measurements. Such data can be called observables. Examples are provided by Spectroscopy (absorbtions in IR, NMR, UV, ESCA. ..) chromatography (retentions in TLC, HPLC, GLC. ..) thermodynamics (heat capacity, standard Gibbs energy of formation, heat of vaporization. ..) physical propery measures (refractive index, boiling point, dielectric constant, dipole moment, solubility. ..) chemical properties (protolytic constants, ionzation potential, lipophilicity (log P)...) structural data (bond lengths, bond angles, van der Waals radii...) empirical structural parameters (Es, [Pg.34]

According to Reichelt and Hemminger (144), the values of the calibration constant of a DSC apparatus obtained by means of heat of fusion standards are different from those of well-known heat capacity standards. Varying the container geometry, they were able to show that there was no influence of the disturbance of steady-state conditions of heat flux on the calculated value of the enthalpy of fusion of indium. An error of 20% in the enthalpy may result if incorrectly closed containers are employed. 

TABLE 6. Heat Capacity, Standard Entropy, Heats of Transformation, and Fusion of the Rare Earth Metals... 

For heat capacity determinations with normal DSC and MDSC systems, heat capacity calibration is performed by scanning a heat capacity standard, such as sapphire. This calibrates the system for Cp values and is used in separating the heat capacity component from the total heat flow. 

Thermal Heat Capacity - The heat capacity of SiOC-N312 BN 2-D composites was measured by differential scanning calorimetry (DSC). In this test a sample of dimensions 4.24 X 4.24 X 1 mm is placed in a calibrated heating chamber along with a known heat capacity standard, and the chamber is heated at a fixed heating rate. The temperature difference between the standard and the composite is recorded, and the heat capacity is calculated from the measured temperature difference, the heat capacity of the standard, and the calibration constraints for the system. 

Equation (2) represents the heat flow into the volume V and can be derived from Eq. (11) in Fig. 1.2. The symbols have the standard meanings p is the density and Cp, the specific heat capacity. Standard techniques of vector analysis now dlow the heat flow into the volume V to be equated with the heat flow across its surface. This operation leads to the Foimer differential equation of heat flow, given as Eq. (3). The letter k represents the thermal diffusivity, which is equal to the thermal conductivity k divided by the density and specific heat capacity. Its dimension is m /s. The Laplacian operator, v2, is 32/3j2 + 2/ 2 + a2/aj2 where x,y and z are the space coordinates. In the present example of cylindrical symmetry, the Laplacian operator, operating on temperature T, can be represented as — i.e., the... 

Enthalpies are referred to the ideal vapor. The enthalpy of the real vapor is found from zero-pressure heat capacities and from the virial equation of state for non-associated species or, for vapors containing highly dimerized vapors (e.g. organic acids), from the chemical theory of vapor imperfections, as discussed in Chapter 3. For pure components, liquid-phase enthalpies (relative to the ideal vapor) are found from differentiation of the zero-pressure standard-state fugacities these, in turn, are determined from vapor-pressure data, from vapor-phase corrections and liquid-phase densities. If good experimental data are used to determine the standard-state fugacity, the derivative gives enthalpies of liquids to nearly the same precision as that obtained with calorimetric data, and provides reliable heats of vaporization. 

The enthalpy of fomiation is obtained from enthalpies of combustion, usually made at 298.15 K while the standard entropy at 298.15 K is derived by integration of the heat capacity as a function of temperature from T = 0 K to 298.15 K according to equation (B 1.27.16). The Gibbs-FIehiiholtz relation gives the variation of the Gibbs energy with temperature... 

It is a standard result in the canonical ensemble that energy fluctuations are related to the heat capacity Cy=... 

Another way to improve the error in a simulation, at least for properties such as the energy and the heat capacity that depend on the size of the system (the extensive properties), is to increase the number of atoms or molecules in the calculation. The standard deviation of the average of such a property is proportional to l/ /N. Thus, more accurate values can be obtained by running longer simulations on larger systems. In computer simulation it is unfortunately the case that the more effort that is expended the better the results that are obtained. Such is life ... 

A lustrous metal has the heat capacities as a function of temperature shown in Table 1-4 where the integers are temperatures and the floating point numbers (numbers with decimal points) are heat capacities. Print the curve of Cp vs. T and Cp/T vs. T and determine the entropy of the metal at 298 K assuming no phase changes over the interval [0, 298]. Use as many of the methods described above as feasible. If you do not have a plotting program, draw the curves by hand. Scan a table of standard entropy values and decide what the metal might he. 

The heat capacity of thiazole was determined by adiabatic calorimetry from 5 to 340 K by Goursot and Westrum (295,296). A glass-type transition occurs between 145 and 175°K. Melting occurs at 239.53°K (-33-62°C) with an enthalpy increment of 2292 cal mole and an entropy increment of 9-57 cal mole °K . Table 1-44 summarizes the variations as a function of temperature of the most important thermodynamic properties of thiazole molar heat capacity Cp, standard entropy S°, and Gibbs function - G°-H" )IT. 

The thermal conductivity of soHd iodine between 24.4 and 42.9°C has been found to remain practically constant at 0.004581 J/(cm-s-K) (33). Using the heat capacity data, the standard entropy of soHd iodine at 25°C has been evaluated as 116.81 J/ (mol-K), and that of the gaseous iodine at 25°C as 62.25 J/(mol-K), which compares satisfactorily with the 61.81 value calculated by statistical mechanics (34,35). 

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). 

The standard Gibbs-energy change of reaction AG° is used in the calculation of equilibrium compositions. The standard heat of reaclion AH° is used in the calculation of the heat effects of chemical reaction, and the standard heat-capacity change of reaction is used for extrapolating AH° and AG° with T. Numerical values for AH° and AG° are computed from tabulated formation data, and AC° is determined from empirical expressions for the T dependence of the C° (see, e.g., Eq. [4-142]). 

Thus curvature in an Arrhenius plot is sometimes ascribed to a nonzero value of ACp, the heat capacity of activation. As can be imagined, the experimental problem is very difficult, requiring rate constant measurements of high accuracy and precision. Figure 6-2 shows a curved Arrhenius plot for the neutral hydrolysis of methyl trifluoroacetate in aqueous dimethysulfoxide. The rate constants were measured by conductometry, their relative standard deviations being 0.014 to 0.076%. The value of ACp was estimated to be about — 200 J mol K, with an uncertainty of less than 10 J moE K. ... 

Table 9.1 Standard heat capacities, entropies, enthalpies of formation, and Gibbs free energies of formation at T = 298.15 K. ...

The interpretation of AC is that it is the difference in the standard molar heat capacities of the transition state and the reactants. Values of AC for the solvolysis of neutral molecules lie in the range 0 to -400 J mol-1 K l. The need for high-precision determinations of k (and 77) is emphasized by these values. 

The temperature variation of the standard reaction enthalpy is given by Kirchhoff s law, Eq. 23, in terms of the difference in molar heat capacities at constant pressure between the products and the reactants. 

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