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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.
where ln denotes the natural logarithm, is the thermodynamic equilibrium constant, and R is the ideal gas constant.This equation is exact at any one temperature and all pressures, derived from the requirement that the Gibbs free energy of reaction be stationary in a state of chemical equilibrium.
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 above derivation uses the first and second laws of thermodynamics. The first law of thermodynamics is essentially a definition of heat, i.e. heat is the change in the internal energy of a system that is not caused by a change of the external parameters of the system.
Understanding this is perhaps a "thought experiment" in chemical kinetics, but actual examples exist. A gas-phase reaction at constant temperature and pressure which results in an increase in the number of molecules will lead to an increase in volume. Inside a cylinder closed with a piston, it can proceed only by doing work on the piston.
which can be further processed to calculate the enthalpy of metal-ligand interaction. [10] [11] Although this example is between a metal and a ligand, it is applicable to any ITC experiment, regarding binding interactions. As a part of the analysis, a number of protons are required to calculate the solvent-independent thermodynamics.
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 ...
The standard enthalpy of reaction (denoted ) for a chemical reaction is the difference between total product and total reactant molar enthalpies, calculated for substances in their standard states. The value can be approximately interpreted in terms of the total of the chemical bond energies for bonds broken and bonds formed.