11.

6 MEASUREMENTS OF SPECIFIC HEATS Specific heat enters heat transfer processes directly due to enthalpy or internal energy changes of the materials involved and indirectly by means of the thermal diffusivity in all unsteady cases. The methods described for thermal conductivity and diffusivity in the previous sections of this paper obviously can be applied also for the measurements of specific heat when in addition the density of the material is known. The discussion of the measurements of specific heats will refer in some cases to methods already described. By definition the specific heat is given by and in principle can be evaluated by measuring the heat (dQ) needed to increase the temperature by dT in a mass m of the specimen. Since the specific heat is temperature dependent the observation must be carried out with small changes of T\ otherwise the so-called "mean specific heat" cm is measured From this relationship c can be obtained only when its temperature dependence is known. Normally it is necessary to observe cm many times at different values of T1 - T2. The change of temperature in the material normally causes a change in volume; this needs additional energy to overcome the intermolecular forces. Measurements under constant pressure, therefore, will yield a higher value than measurements at constant volume: where a is the volumetric expansion coefficient, p the density, and K the compressibility. For solids and liquids, measurements normally are carried out under constant pressure and cv is determined by means of Eq. (11.41). Equation (11.41) also is used for measurements of gasesthose in addition can be determined indirectly by means of thermodynamic relationships or experimentally. 11.6.1 Measurements of the Specific Heat of Solids and Liquids The methods applied differ from each other mainly by different means of measuring the heat causing the temperature change in the specimen of known mass. The sample might be heated directly electrically (in a few cases by a chemical reaction) or indirectly, by observing the effect on a calorimeter body when brought in heat exchange with the sample. The direct heating methods have been used in many varieties and are most common for adiabatic calorimeters. The adiabatic calorimeter consists of a container with the sample or the sample itself heated by an internal heater and surrounded by a shield heated to the same temperature as the calorimeter. Moser [95] heated the shield to undergo a small linear temperature change and heated the calorimeter to follow the temperature of the shield. Schmidt and Leidenfrost [96], West and Ginnings [97], Stansbury et al. [98], and others heated the sample and forced the shield to follow the temperature change. This approach is simpler in respect to determining the heat generated in the sample. The instrument developed by Schmidt and Leidenfrost is shown in Fig. 11.16. A small heater sphere is surrounded by the test substance (liquids or solid granulates) in a wide spherical annulus. The outside of the calorimeter is surrounded by a spherical shield which in turn is insulated by radiation shields in a vacuum. These investigators solved the temperature distribution in the test sample undergoing a linear temperature change. They proved that after a certain initial time has elapsed the temperature within the sample will increase at the same rate

everywhere. Under those conditions the recorded temperature change with time in the sample is directly proportional to the specific heat: where T is the temperature change with time, q the constant heat input, and wc the heat capacity of the calorimeter body (heater sphere, outer shell, and wires). The specific heat observed will be of high accuracy whenever the rate of temperature change is chosen so that the temperature difference within the sample is small enough for the assumption of c = constant, but high enough to detect the temperature change accurately. The spherical arrangement has some advantages for reasons of eliminating end-losses which are encountered in cylindrical arrangements and providing for the maximum volume-to-surface ratio. The latter minimized the potential heat transfer surface relative to the heat supplied to the specimen. Schmidt and Leidenfrost used the arrangement to measure the specific heat of nickel up to 500C and the specific heat of liquids. When the measurements on nickel were carried out to determine the exact temperature of the Curie point, the system was so sensitive that another kind of transition was noticed at about 230C. The system was also tested for measuring simultaneously the thermal conductivity of poor-conducting fluids by following the transient technique discussed in the previous sections. A number of problems must be solved in order to attain precision in adiabatic calorimetry. First, it is difficult to achieve complete adiabacy. Resulting from this there will be heat leakages to the surrounding shield. Lead-in losses also are present and so are the effects of nonuniformity and several other influences already discussed in the previous section and by West [99]. A quasi-adiabatic calorimeter was developed by Krischer [100] especially for the measurements of specific heat of poor-conducting solids and for samples of high moisture content. Equally thick layers of the sample are sandwiched together with a foil-type heater in between as shown on the left side of Fig. 11.17. If the samples are large enough and unwanted effects are avoided, the uniformly generated heat will cause, after an initial period of time, a quasi-stationary condition within the sample. The conditions are described by equidistant parabolic isotherms shown in the right-hand side of the figure. The temperature of the heating foil Tf is measured and that of a center location Tc. Observing the time period At necessary for Tc to reach Tf allows one to evaluate the specific heat from the equation where L is half thickness of the layer. The equation is valid because every point of the sample undergoes the same temperature change during the time At. The arrangement obviously can also be used for thermal conductivity. Adiabatic calorimeters can produce specific heat data with an accuracy which equals in certain ranges that of the drop-type calorimeter. In other ranges they have in addition the advantage that the specific heat can be evaluated at any temperature covered in one run and that measurements will detect influences of transitions or other changes which might occur within the sample during the test. In the drop-type calorimeter many drops must be performed in order to establish the specific heat values at regions of transition-or the transition might be similarly frozen during the rapid cooling process in the calorimeter. The drop-type calorimeter technique heats a sample to a known temperature, usually in a furnace, which is then dropped into a calorimeter where the sample cools rapidly and heat it evolves is measured. This procedure essentially measures the enthalpy of the sample at the higher temperature relative to that at the lower temperature. The heat exchanged from the sample

to the calorimeter can be measured by observing the temperature change in a liquid or a solid calorimeter body or by determining isothermally the amount of ice melted, or of liquid evaporated or condensed. Of very high precision is the so-called "ice calorimeter," a very simple, very accurate, best tested, and most commonly applied device. The calorimeter consists of an inner tube open at the upper end to receive the sample and closed at the bottom. The tube is completely surrounded by a wider vessel. The space between the tube and the vessel is filled with pure, air-free water and some pure mercury at the bottom. Some of the water is frozen. There is only one opening to the outside-by a mercury-filled tube connecting the pool of pure mercury to the outside. The heat evolved by the sample when it cools to the ice point melts a corresponding amount of ice which is very precisely measured by the mass of mercury drawn in (from a weighed outside supply) to compensate for the volume shrinkage. A bath of ice water serves as a heat shield making the heat losses of the calorimeter very small and highly constant. A detailed description of the operation and performance of drop-type calorimeter was given by Douglas [101]. Taylor [102] determined specific heat by a pulse-heating method. The small sample in the form of a wire is heated rapidly by the passage of large currents of the order of several thousand amperes and causing heating rates of 103 to 105 degrees per second. Taylor lists as advantages: heat losses small, no furnace required, chemical interaction and preferential vaporization of specimen is limited, the upper temperature limit is the melting point. The disadvantages are that the sample must be an electrical conductor and it is difficult to measure the temperature. (Cezairliyan [87] used tubes and measured temperature by optical and fast-recording devices. It appears that he did overcome those difficulties; see also [103].) In Taylor's experiment a dual oscilloscope was used to measure voltage and current simultaneously as a function of time and at discrete time intervals. The specific resistance at each time interval is calculated from the relationship where A is the cross-sectional area of the wire, L the distance between voltage probes, and E and / the voltage and current, respectively. The specific resistance as a function of time is then determined. The specific heat at any temperature is given by the expression where m is the mass of the sample between the voltage probes and E I the power dissipated in the region. dpfdT is the temperature coefficient of the resistance at T and dp/dt the time rate of change of the resistivity at T. The accuracy of the specific-heat data measured by that method agreed well with those observed in drop-type calorimeters operating with samples heated to the same temperature. The adiabatic and drop-type calorimeter can also be used for liquids by providing suitable containers. Some other measurement techniques for liquids are shown in the following figures. Figure 11.18 represents a differential calorimeter. One of the calorimeter containers is filled with the test sample, the other with a liquid of known specific heat. The specific heat is evaluated from measuring the heat necessary to produce in each calorimeter the same temperature increase, from the masses contained in the calorimeters and the known specific heat. Due to the symmetry of the arrangement it is not necessary to evaluate the heat capacities of the container itself and the heat losses. Specific heat of liquids quite often is measured by determining the temperature change in a liquid flowing through an insulated tube under constant heat input. A calorimeter of this type is shown in Fig. 11.19 representing a device originally used by Callendar and Barnes [104]. H

represents the heater wire (normally made of platinum) placed in the center of tube Q which is insulated by a vacuum chamber M, kept at a constant temperature by a circulating thermostat fluid. The temperature change is measured by two thermocouples or resistance thermometers located at proper places close to the ends of the tube. The heat losses qL in the system can be determined by varying the mass flow rate and heat input under constant T Flow calorimeters have been used with success at high pressures and temperatures and also for gases. Another calorimeter system of interest for reasons of its simplicity and accuracy is that of Schlesinger [105] shown in Fig. 11.20. The calorimeter C is filled completely with the test fluid by means of valves a and b and placed in a thermostat. When equilibrium is established valve b is closed and some mercury is forced to enter the capillary k by slight increase in pressure through a which then is also closed. The liquid is heated H by a small amount and for a short time (Q). If the thermal expansion and specific heat can be assumed constant the displacement of the mercury in the capillary immediately will yield the change of volume even when the liquid is heated only in the neighborhood of the heater H. The liquid next to the walls of C remains practically at the temperature of the surroundings and no heat losses are encountered. The specific heat, therefore, is determined not only quickly but also very accurately. where V is the volume change and v the specific volume change of one unit of mass of liquid under a temperature change of 1 degree. 11.6.2 Measurements of the Specific Heat of Gases The flow-type and the mixing calorimeters can be used for gases as well as heating a gas enclosed in a large vessel by an electrical heater of large surface area. The specific heat of gases furthermore can be determined by means of techniques to observe heating values of gas reaction (i.e., H2 + &02) but adding the gas of unknown specific heat. Measurements also can be carried out by the differential method and by many other methods. Of more interest are the indirect methods. The adiabatic change of a gas from a state v0, p0, T0 to another state ul5 pl9 T1, is given by the thermodynamic relationship for ideal gases: The measurements of two of the related quotients yield K = cp/cv and with the molar heats cp and cv can be evaluated for ideal gases. For real gases Eq. (11.50) is not valid and an equation of state must be introduced making Eq. (11.49) quite complex. However, the difficulties can be overcome by special differentiating techniques [106] and with the aid of highspeed computers. Furthermore K can be computed from the velocity of sound. The following process under constant enthalpy yields the Joule-Thompson coefficient: and cp can be calculated when T(dv/dp)p v can be computed from an equation of state.