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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:
Ludwig Boltzmann defined entropy as a measure of the number of possible microscopic states (microstates) of a system in thermodynamic equilibrium, consistent with its macroscopic thermodynamic properties, which constitute the macrostate of the system. A useful illustration is the example of a sample of gas contained in a container.
The collisionless Boltzmann equation, where individual collisions are replaced with long-range aggregated interactions, e.g. Coulomb interactions, is often called the Vlasov equation. This equation is more useful than the principal one above, yet still incomplete, since f cannot be solved unless the collision term in f is known.
Despite the foregoing, there is a difference between the two quantities. The information entropy Η can be calculated for any probability distribution (if the "message" is taken to be that the event i which had probability p i occurred, out of the space of the events possible), while the thermodynamic entropy S refers to thermodynamic probabilities p i specifically.
The H-theorem is a natural consequence of the kinetic equation derived by Boltzmann that has come to be known as Boltzmann's equation. The H-theorem has led to considerable discussion about its actual implications, [6] with major themes being: What is entropy? In what sense does Boltzmann's quantity H correspond to the thermodynamic entropy?
When these probabilities are substituted into the above expression for the Gibbs entropy (or equivalently k B times the Shannon entropy), Boltzmann's equation results. In information theoretic terms, the information entropy of a system is the amount of "missing" information needed to determine a microstate, given the macrostate.
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."
Although Boltzmann first linked entropy and probability in 1877, the relation was never expressed with a specific constant until Max Planck first introduced k, and gave a more precise value for it (1.346 × 10 −23 J/K, about 2.5% lower than today's figure), in his derivation of the law of black-body radiation in 1900–1901. [11]