Wednesday, 7 February 2018

thermodynamics - Why can one use this equation for entropy if this process is irreversible?


The equation


$$dS = \dfrac{dQ}{T}$$


is said do hold only on reversible processes. Indeed this is almost always emphasized by writing


$$dS = \dfrac{dQ_{\mathrm{rev}}}{T},$$


to be clear that this is during one reversible process.


Now there are some irreversible processes on which this is used. For instance, if one mass $m$ of a substance melts at temperature $T_0$ and if it has latent heat of fusion $q_L$ then it is usually computed that


$$\Delta S = \dfrac{mq_L}{T_0}.$$


Another example is when heat enters a system at constant temperature. In that case if the heat is $Q$ we have


$$\Delta S = \dfrac{Q}{T}.$$



All these processes are clearly irreversible. It is intuitively clear, but more than that we have $\Delta S > 0$ in all of them.


Still we are finding $\Delta S$ using


$$\Delta S = \int \dfrac{dQ}{T},$$


and it is obviously that this integral is being carried along irreversible processes in the examples I gave.


In that case, whey can we use this formula to find the change in entropy if the processes are irreversible?




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