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[1] [2] [3] A more fundamental statement was later labelled as the zeroth law after the first three laws had been established. The zeroth law of thermodynamics defines thermal equilibrium and forms a basis for the definition of temperature: if two systems are each in thermal equilibrium with a third system, then they are in thermal equilibrium ...
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 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]
The Collected Works of J. Willard Gibbs Thermodynamics. New York: Longmans, Green and Co. Vol. 1, pp. 55–349. Guggenheim E.A. (1933). Modern thermodynamics by the methods of Willard Gibbs. London: Methuen & co. ltd. Denbigh K. (1981). The Principles of Chemical Equilibrium: With Applications in Chemistry and Chemical Engineering. London ...
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 ...
This is the most useful form of the second law of thermodynamics in chemistry, where free-energy changes can be calculated from tabulated enthalpies of formation and standard molar entropies of reactants and products. [19] [15] The chemical equilibrium condition at constant T and p without electrical work is dG = 0.
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 ...
[11] Assume two products B and C form in a reaction: a A + d D → b B, a A + d D → c C. In this case, K eq can be defined as ratio of B to C rather than the equilibrium constant. When B / C > 1, B is the favored product, and the data on the Van 't Hoff plot will be in the positive region.