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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 law states that the total enthalpy change during the complete course of a chemical reaction is independent of the sequence of steps taken. [2] [3] Hess's law is now understood as an expression of the fact that the enthalpy of a chemical process is independent of the path taken from the initial to the final state (i.e. enthalpy is a state ...
The concept of internal energy and its relationship to temperature. If a system has a definite temperature, then its total energy has three distinguishable components, termed kinetic energy (energy due to the motion of the system as a whole), potential energy (energy resulting from an externally imposed force field), and internal energy. The ...
At constant temperature, the Helmholtz free energy is minimized at equilibrium. In contrast, the Gibbs free energy or free enthalpy is most commonly used as a measure of thermodynamic potential (especially in chemistry ) when it is convenient for applications that occur at constant pressure .
Here, U is internal energy, T is absolute temperature, S is entropy, P is pressure, and V is volume. This is only one expression of the fundamental thermodynamic relation. It may be expressed in other ways, using different variables (e.g. using thermodynamic potentials). For example, the fundamental relation may be expressed in terms of the ...
Temperature is the driving force, entropy is the associated displacement, and the two form a pair of conjugate variables. The temperature/entropy pair of conjugate variables is the only heat term; the other terms are essentially all various forms of work.
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]
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 ...