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Chemistry · Ch 4 — Chemical Thermodynamics

Entropy and spontaneity (Second law of Thermodynamics)

4.11.3

Entropy and spontaneity (Second law of Thermodynamics)

Look at the following examples:

i. The entropy increases when ice melts above 0 °C and when water vaporizes at 100 °C. Both are spontaneous.

ii. Consider the spontaneous reaction at room temperature:

2H2O2 (l)⟶2H2O (l)+O2 (g),ΔS=+126 J K−12\mathrm{H_2O_2}\,(l) \longrightarrow 2\mathrm{H_2O}\,(l) + \mathrm{O_2}\,\mathrm{(g)}, \quad \Delta S = +126\ \mathrm{J\,K^{-1}}

The entropy increases due to the formation of O2_2 gas.

From the above examples, it is clear that the entropy of the system increases in the spontaneous processes. But consider the reaction

2H2(g)+O2(g)⟶2H2O(l),ΔS=−327 J K−12\mathrm{H_2(g)} + \mathrm{O_2(g)} \longrightarrow 2\mathrm{H_2O}(l), \quad \Delta S = -327\ \mathrm{J\,K^{-1}} …