Thermodynamics – Why Can’t Entropy Decrease in an Adiabatic and Closed System?

adiabaticenergyentropythermodynamics

In equations (10) and (11) of this article by Curzon on the adiabatic piston, Curzon uses that a system which is thermally insulated cannot have its entropy decrease (irrespective of anything else conceivably "doable" to the system). Why is this so, or am I misinterpreting?

The crux of the derivation is that we want a characterization of the (elusive) final equilibrium state. In (10) and (11), Curzon is therefore writing (since this is what is being used in equation (5)) that any virtual, quasistatic process away from the final equilibrium state (to other equilibrium states on the constrained manifold describing the composite system) must obey $dS_i \geq 0$. But why isn't it flatly $dS_i =0$? If we are supposing that the virtual process is quasistatic (since the entire point is to distinguish the final equilibrium state from all the other equilibrium states on the constrained manifold), then $TdS_i = dU_i – PdV_i = dQ – dW – PdV_i = dQ = 0 \implies dS_i = 0$. So why the $\geq$? I ask because I feel like I must surely be missing something.

Best Answer

The only way to decrease the entropy of a system is by transferring heat to its surroundings, which is precluded if the system is adiabatic.

On the other hand entropy can be generated (increase) within the system by means of irreversible adiabatic processes, or there can be no change in entropy for reversible adiabatic (isentropic) processes.

Hope this helps.