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Non-equilibrium thermodynamics is a branch of thermodynamics that deals with systems that are not in thermodynamic equilibrium. Most systems found in nature are not in thermodynamic equilibrium because they are not in stationary states, and are continuously and discontinuously subject to flux of matter and energy to and from other systems.
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 laws of thermodynamics are the result of progress made in this field over the nineteenth and early twentieth centuries. The first established thermodynamic principle, which eventually became the second law of thermodynamics, was formulated by Sadi Carnot in 1824 in his book Reflections on the Motive Power of Fire.
Examples are internal energy, enthalpy, Helmholtz free energy, Gibbs free energy, thermodynamic temperature, and entropy. For a given body, of a given chemical constitution, when its thermodynamic state has been fully defined by its pressure and volume, then its temperature is uniquely determined.
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. However, the second law of thermodynamics is not a defining relation for the entropy.
Thus, a negative value of the change in free energy (G or A) is a necessary condition for a process to be spontaneous. 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.
Entropy is a state function and is defined in an absolute sense through the Third Law of Thermodynamics as S = ∫ 0 T d Q r e v T {\displaystyle S=\int _{0}^{T}{dQ_{rev} \over T}} where a reversible path is chosen from absolute zero to the final state, so that for an isothermal reversible process
For thermodynamics, a natural process is a transfer between systems that increases the sum of their entropies, and is irreversible. [2] Natural processes may occur spontaneously upon the removal of a constraint, or upon some other thermodynamic operation , or may be triggered in a metastable or unstable system, as for example in the ...