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Henceforth, the essential problem in statistical thermodynamics has been to determine the distribution of a given amount of energy E over N identical systems. Constantin Carathéodory, a Greek mathematician, linked entropy with a mathematical definition of irreversibility, in terms of trajectories and integrability.
Boltzmann's equation—carved on his gravestone. [1]In statistical mechanics, Boltzmann's equation (also known as the Boltzmann–Planck equation) is a probability equation relating the entropy, also written as , of an ideal gas to the multiplicity (commonly denoted as or ), the number of real microstates corresponding to the gas's macrostate:
The concept of thermodynamic entropy arises from the second law of thermodynamics.This law of entropy increase quantifies the reduction in the capacity of an isolated compound thermodynamic system to do thermodynamic work on its surroundings, or indicates whether a thermodynamic process may occur.
The von Neumann entropy formula is an extension of the Gibbs entropy formula to the quantum mechanical case. It has been shown [ 1 ] that the Gibbs Entropy is equal to the classical "heat engine" entropy characterized by d S = δ Q T {\displaystyle dS={\frac {\delta Q}{T}}\!} , and the generalized Boltzmann distribution is a sufficient and ...
The entropy is thus a measure of the uncertainty about exactly which quantum state the system is in, given that we know its energy to be in some interval of size . Deriving the fundamental thermodynamic relation from first principles thus amounts to proving that the above definition of entropy implies that for reversible processes we have:
The maximum entropy principle: For a closed system with fixed internal energy (i.e. an isolated system), the entropy is maximized at equilibrium. The minimum energy principle: For a closed system with fixed entropy, the total energy is minimized at equilibrium.
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 relationship between entropy, order, and disorder in the Boltzmann equation is so clear among physicists that according to the views of thermodynamic ecologists Sven Jorgensen and Yuri Svirezhev, "it is obvious that entropy is a measure of order or, most likely, disorder in the system."