[Physics] Why can’t we plot irreversible processes on a $T$-$S$ diagram

entropyreversibilitytemperaturethermodynamics

In the book "Heat and Thermodynamics" by Zemanky, It is stated that

"only reversible processes can be plotted on a $T$-$S$ diagram. Since the definition of entropy involves a reversible change in heat."

But, As $T$ and $S$ are state variables, We should be able to plot the process despite the fact that it is irreversible. If the process is quasi-static we can have the precise set of values of $T$ and $S$ at every instant of the process.

Best Answer

When we plot a process as a continuous line, curve, etc., of states using thermodynamic variables we are assuming that each point on the chart represents an equilibrium state, i.e., the process taking place is a series of “quasi-static” or “quasi-equilibrium” states. For example, refer to the T-S diagram below for a Rankine refrigeration cycle. The compressor, condenser, and evaporator processes are each reversible. The expansion valve (throttling) process is not. Note how it is represented by a series of hashed lines implying that the states between 3 and 4 are not equilibrium states. The enthalpy at state 3 and state 4 are the same but it is not a constant enthalpy process. Although Zemansky singles out the T-S diagram, the same holds true for other graphs of processes. The following is from an MIT web course on thermodynamics concerning processes.

“…properties define a state only when a system is in equilibrium. If a process involves finite, unbalanced forces, the system can pass through non-equilibrium states, which we cannot treat. An extremely useful idealization, however, is that only infinitesimal unbalanced forces exist, so that the process can be viewed as taking place in a series of quasi-equilibrium states”.

Hope this helps enter image description here

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