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Enthalpy (/ ˈ ɛ n θ əl p i / ⓘ) is the sum of a thermodynamic system's internal energy and the product of its pressure and volume. [1] It is a state function in thermodynamics used in many measurements in chemical, biological, and physical systems at a constant external pressure, which is conveniently provided by the large ambient atmosphere.
The definition of the Gibbs function is = + where H is the enthalpy defined by: = +. Taking differentials of each definition to find dH and dG, then using the fundamental thermodynamic relation (always true for reversible or irreversible processes): = where S is the entropy, V is volume, (minus sign due to reversibility, in which dU = 0: work other than pressure-volume may be done and is equal ...
Enthalpy and isochoric specific heat capacity are very useful mathematical constructs, since when analyzing a process in an open system, the situation of zero work occurs when the fluid flows at constant pressure. In an open system, enthalpy is the quantity which is useful to use to keep track of energy content of the fluid.
Thus, they are essentially equations of state, and using the fundamental equations, experimental data can be used to determine sought-after quantities like G (Gibbs free energy) or H . [1] The relation is generally expressed as a microscopic change in internal energy in terms of microscopic changes in entropy , and volume for a closed system in ...
Entropy cannot be measured directly. The change in entropy with respect to pressure at a constant temperature is the same as the negative change in specific volume with respect to temperature at a constant pressure, for a simple compressible system. Maxwell relations in thermodynamics are often used to derive thermodynamic relations. [2]
Many thermodynamic equations are expressed in terms of partial derivatives. For example, the expression for the heat capacity at constant pressure is: = which is the partial derivative of the enthalpy with respect to temperature while holding pressure constant.
At present, there is no single equation of state that accurately predicts the properties of all substances under all conditions. An example of an equation of state correlates densities of gases and liquids to temperatures and pressures, known as the ideal gas law, which is roughly accurate for weakly polar gases at low pressures and moderate temperatures.
Substituting from the ideal gas equation gives finally: = where n = number of moles of gas in the thermodynamic system under consideration and R = universal gas constant. On a per mole basis, the expression for difference in molar heat capacities becomes simply R for ideal gases as follows: