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Entropy is a measure related the number of possible configurations that a thermodynamic system, which also means it is a measure related to the number of states the system can be in. The specific relation is given by the Boltzmann equation, S = Kbln(W), but the main point is that it is a related measurement of the number of states, just as meters is a measurement of distance.
Take for example water vapor compared to water as a liquid. In water vapor, the molecules are able to move much more freely and therefore contain a larger number of states than the molecules in the liquid, which are much more constrained and limited in their movements.
As a sample expands to a larger volume, there is more physical space and therefore more possible arrangements of the sample that fit within the space. Entropy is the quantification of this increase in degeneracy, or the number of possible positions.
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