Metrology, The Measurement of Heat Capacity
The heat capacity of most systems is not a constant. Rather, it depends on the state variables of the thermodynamic system under study. In particular it is dependent on temperature itself, as well as on the pressure and the volume of the system, and the ways in which pressures and volumes have been allowed to change while the system has passed from one temperature to another. The reason for this is that pressure-volume work done to the system raises its temperature by a mechanism other than heating, while pressure-volume work done by the system absorbs heat without raising the system's temperature.
Different measurements of heat capacity can therefore be performed, most commonly at constant pressure and constant volume. The values thus measured are usually subscripted (by p and V, respectively) to indicate the definition. Gases and liquids are typically also measured at constant volume. Measurements under constant pressure produce larger values than those at constant volume because the constant pressure values also include heat energy that is used to do work to expand the substance against the constant pressure as its temperature increases. This difference is particularly notable in gases where values under constant pressure are typically 30% to 66.7% greater than those at constant volume.
The specific heat capacities of substances comprising molecules (as distinct from monatomic gases) are not fixed constants and vary somewhat depending on temperature. Accordingly, the temperature at which the measurement is made is usually also specified. Examples of two common ways to cite the specific heat of a substance are as follows:
- Water (liquid): cp = 4.1855 (15 °C, 101.325 kPa)
- Water (liquid): CvH = 74.539 J/(mol·K) (25 °C)
For liquids and gases, it is important to know the pressure to which given heat-capacity data refer. Most published data are given for standard pressure. However, quite different standard conditions for temperature and pressure have been defined by different organizations. The International Union of Pure and Applied Chemistry (IUPAC) changed its recommendation from one atmosphere to the round value 100 kPa (≈750.062 Torr).
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