Second Law of Thermodynamics - Derivation From Statistical Mechanics

Derivation From Statistical Mechanics

In statistical mechanics, the Second Law is not a postulate, rather it is a consequence of the fundamental postulate, also known as the equal prior probability postulate, so long as one is clear that simple probability arguments are applied only to the future, while for the past there are auxiliary sources of information which tell us that it was low entropy. The first part of the second law, which states that the entropy of a thermally isolated system can only increase is a trivial consequence of the equal prior probability postulate, if we restrict the notion of the entropy to systems in thermal equilibrium. The entropy of an isolated system in thermal equilibrium containing an amount of energy of is:

where is the number of quantum states in a small interval between and . Here is a macroscopically small energy interval that is kept fixed. Strictly speaking this means that the entropy depends on the choice of . However, in the thermodynamic limit (i.e. in the limit of infinitely large system size), the specific entropy (entropy per unit volume or per unit mass) does not depend on .

Suppose we have an isolated system whose macroscopic state is specified by a number of variables. These macroscopic variables can, e.g., refer to the total volume, the positions of pistons in the system, etc. Then will depend on the values of these variables. If a variable is not fixed, (e.g. we do not clamp a piston in a certain position), then because all the accessible states are equally likely in equilibrium, the free variable in equilibrium will be such that is maximized as that is the most probable situation in equilibrium.

If the variable was initially fixed to some value then upon release and when the new equilibrium has been reached, the fact the variable will adjust itself so that is maximized, implies that the entropy will have increased or it will have stayed the same (if the value at which the variable was fixed happened to be the equilibrium value).

The entropy of a system that is not in equilibrium can be defined as:

see here. Here the is the probabilities for the system to be found in the states labeled by the subscript j. In thermal equilibrium the probabilities for states inside the energy interval are all equal to, and in that case the general definition coincides with the previous definition of S that applies to the case of thermal equilibrium.

Suppose we start from an equilibrium situation and we suddenly remove a constraint on a variable. Then right after we do this, there are a number of accessible microstates, but equilibrium has not yet been reached, so the actual probabilities of the system being in some accessible state are not yet equal to the prior probability of . We have already seen that in the final equilibrium state, the entropy will have increased or have stayed the same relative to the previous equilibrium state. Boltzmann's H-theorem, however, proves that the entropy will increase continuously as a function of time during the intermediate out of equilibrium state.