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A microstate is the arrangement of the molecules in a sample, or the various ways the molecules can be distributed differently over the available energy levels. "W" measures the number of microstates than a particular atom/molecules has. Essentially, the more microstates that a particular atom has, the greater the entropy because there is more disorder. This greater disorder comes from the greater number of microstates because there are more ways to achieve the same energy. Essentially, this means that the more ways that an atom/molecule can be positioned (microstates), the greater the disorder (entropy).
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