Thermodynamic databases for pure substances

Thermodynamic databases contain information about thermodynamic properties for substances, the most important being enthalpy, entropy, and Gibbs free energy. Numerical values of these thermodynamic properties are collected as tables or are calculated from thermodynamic datafiles. Data is expressed as temperature-dependent values for one mole of substance at the standard pressure of 101.325 kPa (1 atm), or 100 kPa (1 bar). Unfortunately, both of these definitions for the standard condition for pressure are in use. Thermodynamic databases contain information about thermodynamic properties for substances, the most important being enthalpy, entropy, and Gibbs free energy. Numerical values of these thermodynamic properties are collected as tables or are calculated from thermodynamic datafiles. Data is expressed as temperature-dependent values for one mole of substance at the standard pressure of 101.325 kPa (1 atm), or 100 kPa (1 bar). Unfortunately, both of these definitions for the standard condition for pressure are in use. Thermodynamic data is usually presented as a table or chart of function values for one mole of a substance (or in the case of the steam tables, one kg). A thermodynamic datafile is a set of equation parameters from which the numerical data values can be calculated. Tables and datafiles are usually presented at a standard pressure of 1 bar or 1 atm, but in the case of steam and other industrially important gases, pressure may be included as a variable. Function values depend on the state of aggregation of the substance, which must be defined for the value to have any meaning. The state of aggregation for thermodynamic purposes is the standard state, sometimes called the reference state, and defined by specifying certain conditions. The normal standard state is commonly defined as the most stable physical form of the substance at the specified temperature and a pressure of 1 bar or 1 atm. However, since any non-normal condition could be chosen as a standard state, it must be defined in the context of use. A physical standard state is one that exists for a time sufficient to allow measurements of its properties. The most common physical standard state is one that is stable thermodynamically (i.e., the normal one). It has no tendency to transform into any other physical state. If a substance can exist but is not thermodynamically stable (for example, a supercooled liquid), it is called a metastable state. A non-physical standard state is one whose properties are obtained by extrapolation from a physical state (for example, a solid superheated above the normal melting point, or an ideal gas at a condition where the real gas is non-ideal). Metastable liquids and solids are important because some substances can persist and be used in that state indefinitely. Thermodynamic functions that refer to conditions in the normal standard state are designated with a small superscript °. The relationship between certain physical and thermodynamic properties may be described by an equation of state. It is very difficult to measure the absolute amount of any thermodynamic quantity involving the internal energy (e.g. enthalpy), since the internal energy of a substance can take many forms, each of which has its own typical temperature at which it begins to become important in thermodynamic reactions. It is therefore the change in these functions that is of most interest. The isobaric change in enthalpy H above the common reference temperature of 298.15 K (25 °C) is called the high temperature heat content, the sensible heat, or the relative high-temperature enthalpy, and called henceforth the heat content. Different databases designate this term in different ways; for example HT-H298, H°-H°298, H°T-H°298 or H°-H°(Tr), where Tr means the reference temperature (usually 298.15 K, but abbreviated in heat content symbols as 298). All of these terms mean the molar heat content for a substance in its normal standard state above a reference temperature of 298.15 K. Data for gases is for the hypothetical ideal gas at the designated standard pressure. The SI unit for enthalpy is J/mol, and is a positive number above the reference temperature. The heat content has been measured and tabulated for virtually all known substances, and is commonly expressed as a polynomial function of temperature. The heat content of an ideal gas is independent of pressure (or volume), but the heat content of real gases varies with pressure, hence the need to define the state for the gas (real or ideal) and the pressure. Note that for some thermodynamic databases such as for steam, the reference temperature is 273.15 K (0 °C). The heat capacity C is the ratio of heat added to the temperature increase. For an incremental isobaric addition of heat: Cp is therefore the slope of a plot of temperature vs. isobaric heat content (or the derivative of a temperature/heat content equation). The SI units for heat capacity are J/(mol·K). When heat is added to a condensed-phase substance, its temperature increases until a phase change temperature is reached. With further addition of heat, the temperature remains constant while the phase transition takes place. The amount of substance that transforms is a function of the amount of heat added. After the transition is complete, adding more heat increases the temperature. In other words, the enthalpy of a substance changes isothermally as it undergoes a physical change. The enthalpy change resulting from a phase transition is designated ΔH. There are four types of enthalpy changes resulting from a phase transition. To wit: Cp is infinite at phase transition temperatures because the enthalpy changes isothermally. At the Curie temperature, Cp shows a sharp discontinuity while the enthalpy has a change in slope. Values of ΔH are usually given for the transition at the normal standard state temperature for the two states, and if so, are designated with a superscript °. ΔH for a phase transition is a weak function of temperature. In some texts, the heats of phase transitions are called latent heats (for example, latent heat of fusion). An enthalpy change occurs during a chemical reaction. For the special case of the formation of a compound from the elements, the change is designated ΔHform and is a weak function of temperature. Values of ΔHform are usually given where the elements and compound are in their normal standard states, and as such are designated standard heats of formation, as designated by a superscript °. The ΔH°form undergoes discontinuities at a phase transition temperatures of the constituent element(s) and the compound. The enthalpy change for any standard reaction is designated ΔH°rx.