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The basic thermodynamic potential is internal energy.In a simple fluid system, neglecting the effects of viscosity, the fundamental thermodynamic equation is written: = + where U is the internal energy, T is temperature, S is entropy, P is the hydrostatic pressure, V is the volume, is the chemical potential, and M mass.
Hess's law states that the change of enthalpy in a chemical reaction is the same regardless of whether the reaction takes place in one step or several steps, provided the initial and final states of the reactants and products are the same. Enthalpy is an extensive property, meaning that its value is proportional to the system size. [4]
For quasi-static and reversible processes, the first law of thermodynamics is: d U = δ Q − δ W {\displaystyle dU=\delta Q-\delta W} where δQ is the heat supplied to the system and δW is the work done by the system.
The first and second law of thermodynamics are the most fundamental equations of thermodynamics. They may be combined into what is known as fundamental thermodynamic relation which describes all of the changes of thermodynamic state functions of a system of uniform temperature and pressure.
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 second was the 1933 book Modern Thermodynamics by the methods of Willard Gibbs written by E. A. Guggenheim. In this manner, Lewis, Randall, and Guggenheim are considered as the founders of modern chemical thermodynamics because of the major contribution of these two books in unifying the application of thermodynamics to chemistry. [1]
This equation shows that in thermodynamics intensive properties are not independent but related, making it a mathematical statement of the state postulate. When pressure and temperature are variable, only of components have independent values for chemical potential and Gibbs' phase rule follows. The Gibbs−Duhem equation cannot be used for ...
The concept of free energy was developed by Hermann von Helmholtz, a German physicist, and first presented in 1882 in a lecture called "On the thermodynamics of chemical processes". [1] From the German word Arbeit (work), the International Union of Pure and Applied Chemistry (IUPAC) recommends the symbol A and the name Helmholtz energy. [2]