Classical phase space
The description of a classical system of F degrees of freedom may be stated in terms of a 2F dimensional phase space, whose coordinate axes consist of the F generalized coordinates qi of the system, and its F generalized momenta pi. The microstate of such a system will be specified by a single point in the phase space. But for a system with a huge number of degrees of freedom its exact microstate usually is not important. So the phase space can be divided into cells of the size h0 = ΔqiΔpi, each treated as a microstate. Now the microstates are discrete and countable[5] and the internal energy U has no longer an exact value but is between U and U+δU, with .
The number of microstates Ω that a closed system can occupy is proportional to its phase space volume:
where is an Indicator function. It is 1 if the Hamilton function H(x) at the point x = (q,p) in phase space is between U and U+ δU and 0 if not. The constant makes Ω(U) dimensionless. For an ideal gas is .[6]
In this description, the particles are distinguishable. If the position and momentum of two particles are exchanged, the new state will be represented by a different point in phase space. In this case a single point will represent a microstate. If a subset of M particles are indistinguishable from each other, then the M! possible permutations or possible exchanges of these particles will be counted as part of a single microstate. The set of possible microstates are also reflected in the constraints upon the thermodynamic system.
For example, in the case of a simple gas of N particles with total energy U contained in a cube of volume V, in which a sample of the gas cannot be distinguished from any other sample by experimental means, a microstate will consist of the above-mentioned N! points in phase space, and the set of microstates will be constrained to have all position coordinates to lie inside the box, and the momenta to lie on a hyperspherical surface in momentum coordinates of radius U. If on the other hand, the system consists of a mixture of two different gases, samples of which can be distinguished from each other, say A and B, then the number of microstates is increased, since two points in which an A and B particle are exchanged in phase space are no longer part of the same microstate. Two particles that are identical may nevertheless be distinguishable based on, for example, their location. (See configurational entropy.) If the box contains identical particles, and is at equilibrium, and a partition is inserted, dividing the volume in half, particles in one box are now distinguishable from those in the second box. In phase space, the N/2 particles in each box are now restricted to a volume V/2, and their energy restricted to U/2, and the number of points describing a single microstate will change: the phase space description is not the same.
This has implications in both the Gibbs paradox and correct Boltzmann counting. With regard to Boltzmann counting, it is the multiplicity of points in phase space which effectively reduces the number of microstates and renders the entropy extensive. With regard to Gibbs paradox, the important result is that the increase in the number of microstates (and thus the increase in entropy) resulting from the insertion of the partition is exactly matched by the decrease in the number of microstates (and thus the decrease in entropy) resulting from the reduction in volume available to each particle, yielding a net entropy change of zero.