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NCERT Exemplar · Q27

Q.Given that ΔH = 0 for mixing of two gases. Explain whether the diffusion of these gases into each other in a closed container is a spontaneous process or not?

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For an ideal gas mixture, ΔH=0\Delta H = 0 but the process is spontaneous because the entropy increases (ΔS>0\Delta S > 0), making ΔG=−TΔS<0\Delta G = -T\Delta S < 0 — the second law of thermodynamics drives mixing even without any heat change.

The key insight here is that spontaneity is not decided by enthalpy change alone. Many students instinctively think "no heat change means no driving force" — but that's a trap. The real master of spontaneity is Gibbs free energy: ΔG=ΔH−TΔS\Delta G = \Delta H - T\Delta S. When ΔH=0\Delta H = 0, the sign of ΔG\Delta G depends entirely on entropy.

For two gases diffusing into each other, the process is fundamentally about disorder. Before mixing, each gas is confined to its own volume — the molecules of gas A are segregated from those of gas B. After mixing, both gases occupy the entire container, intermingling freely. This is a classic example of increased randomness.

  1. Entropy change is the driver. For an ideal gas mixture at constant temperature and pressure, the entropy of mixing is always positive. The formula for two gases is:

ΔSmix=−nR(xAln⁡xA+xBln⁡xB)\Delta S_{\text{mix}} = -nR(x_A \ln x_A + x_B \ln x_B)

where xAx_A and xBx_B are mole fractions. Since xAx_A and xBx_B are less than 1, their logarithms are negative, making the sum inside negative — and the negative sign outside gives a positive ΔS\Delta S.

  1. Apply the Gibbs free energy criterion. With ΔH=0\Delta H = 0:

ΔG=ΔH−TΔS=0−TΔS=−TΔS\Delta G = \Delta H - T\Delta S = 0 - T\Delta S = -T\Delta S

Since ΔS>0\Delta S > 0, we get ΔG<0\Delta G < 0. A negative ΔG\Delta G is the thermodynamic condition for a spontaneous process at constant temperature and pressure.

  1. Physical intuition. Imagine a box divided by a removable partition, with nitrogen on one side and oxygen on the other. When you remove the partition, the gases spontaneously mix — you don't need to push them. This happens because the mixed state has more possible arrangements of molecules (microstates) than the separated state. Nature always moves toward higher probability, which is higher entropy. …

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