[Physics] Is the entropy change the same for both closed reversible and irreversible processes

entropyreversibilitystatistical mechanicstemperaturethermodynamics

It is said that entropy is a state function and doesn't depend on path.

Also

$$S_2-S_1=\int \frac{1}{T}dQ$$

for reversible process,

$$S_2-S_1>\int \frac{1}{T}dQ$$

for irreversible process.

  1. If the same amount of heat đQ enters in both reversible and irreversible process, then shouldn't $S_2-S_1$ be different in reversible and irreversible processes?

  2. Is $\int dQ/T$ equal in both reversible and irreversible processes since the same amount of heat is transferred at same boundary temperature? Please explain this.

Also,

$$dS=d_eS+d_iS=\frac{dQ}{T}+d_iS$$

"dS" for a reversible process is only equal to "đQ/T" and no entropy generation.
But an irreversible process, working between same conditions(heat supplied at same T) is accompanied by entropy generation.

  1. So shouldn't "$\int dS$" for an irreversible process greater than "$\int dS$" in a reversible process? Or, is $\int dQ/T$ for an irreversible process less than $\int dQ/T$ for a reversible process and together with entropy generation in an irreversible process, the total entropy change is the same in both an reversible and irreversible process? Please clarify.

Best Answer

Let me start by saying I agree with what both @Barbaud Julien and @Chester Miller said. So my answer is only intended to provide a different perspective.

First, it is true that the entropy is a state function of a system, and therefore the change of entropy of the system between any two given equilibrium states will be the same whether or not the process between the states is reversible. However, the change in entropy of the system plus surroundings will depend on the process. It will be zero if the process is reversible, and greater than zero if irreversible.

Consider a cycle consisting of two isothermal and two adiabatic processes. If the processes were all reversible, we would obviously have a Carnot cycle. Since your question focuses on the effect of heat transfer on entropy, let’s assume the adiabatic processes are reversible adiabatic (isentropic) and consider only the impact of the heat transfer processes being reversible or irreversible.

Let’s take the example of a heat addition expansion process of an ideal gas between two equilibrium states. Let the initial and final temperatures be equal. Consequently, from the ideal gas law, the initial and final pressure-volume products are equal. Clearly the process between the states may be a reversible isothermal process. However, it also need not be. We’ll consider both.

Let the temperature of the system be $T_{sys}$ and the temperature of the surroundings be $T_{sys}+dT$. Consider the system and surroundings as thermal reservoirs, i.e., heat transfer between them does not alter their temperatures so that the heat transfer occurs isothermally.

Let a specific quantity of heat, $Q$, transfer from the surroundings to the system. The resulting entropy changes are:

$$\Delta S_{sys}=\frac{+Q}{T_{sys}}$$

$$\Delta S_{surr}=\frac{-Q}{T_{sys}+dT}$$

The net change in entropy (system + surroundings) is thus:

$$\Delta S_{net}=\frac{+Q}{T_{sys}}+\frac{-Q}{T_{sys}+dT}$$

Now, note that if $dT\to 0$, then $\Delta S_{net}\to 0$ and the process is a reversible isothermal process.

However, for any finite temperature difference, $dT>0$, $\Delta S_{net}>0$ and the process is irreversible.

For both the reversible and irreversible processes, the change in entropy of the system is the same. However, for the irreversible process the change in entropy of the system is greater than the change in entropy of the surroundings. The excess entropy that is created in the irreversible expansion process means more heat must be rejected to the cold temperature reservoir (surroundings) during the isothermal compression in order for the cycle entropy to be zero. That results in less energy to do work in the cycle.

Although in this example the same amount of heat is transferred reversibly and irreversibly, clearly the rate of heat transfer will be greater for the irreversible than the reversible process owing to the finite temperature differential for the irreversible process. So for the amount of heat transfer to be the same, the product of the very slow heat transfer rate times the very long time for the reversible process would need to equal the product of the higher heat transfer rate times the shorter time duration for the irreversible process.

Hope this helps.

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