Experimentally Determining Entropy

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To experimentally determine the entropy of a substance at standard state, one begins with the Third Law of Thermodynamics, which states that the entropy of a pure crystalline substance is zero at absolute zero. The entropy change can be calculated using the formula ΔS = ∫(dQ_rev/T). To find the entropy at standard state, this integral must be evaluated along a path from absolute zero to the standard state, often by heating at constant pressure. The resulting expression for entropy involves the heat capacity at constant pressure, S = ∫(c_P dT/T), which necessitates measuring the heat capacity as a function of temperature. A significant challenge arises in accurately measuring the heat capacity near absolute zero. To address this, researchers typically measure the heat capacity as closely as possible to absolute zero and apply the Debye approximation to refine their estimates of heat capacity in that region.
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Out of curiosity, how would one experimentally determine the entropy of a substance at standard state?
 
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Starting with the Third Law of Thermodynamics, you take the entropy of the pure crystalline form of the substance to be 0 at absolute 0. The definition of entropy is
\Delta S = \int\frac{dQ_{rev}}{T}
You need to integrate this to get the entropy in the standard state by choosing a path that leads from absolute 0 and any pressure to the standard state. You can do this, for instance by heating at constant pressure, then the expression for the entropy would be
S = \int_{0}^{T}\frac{c_{P}dT}{T}
So the problem reduces to measuring the heat capacity as a function of T. The main experimental difficulty would be measuring cp near absolute 0. In practice, you measure as close as you can and then use the Debye approximation (http://en.wikipedia.org/wiki/Debye_model) to get the best approximation you can of the heat capacity near absolute 0.
 
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