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I am trying to prove $(1)$ below for irreversible processes, but I have a significant doubt. I will first lay out my attempt, and then explain my issue.

Let $\mathcal{Z}$ be any irreversible process which transforms a system between two states. Then $$\Delta_{\mathcal{Z}}S>\int_{\mathcal{Z}}\frac{\delta Q}{T} \tag{1}$$

where $\Delta_{\mathcal{Z}} S$ is the change in entropy of the system over the curve $\mathcal{Z}$.

I start by noting the Clausius inequality. For any irreversible, cyclic process $\mathcal{C}$, we have $(2)$ $$\oint_{\mathcal{C}}\frac{\delta Q}{T}\lt 0 \tag{2}$$

Let $\mathcal{P}:=\mathcal{R}\cup \mathcal{I}$ be a cyclic transformation where $\mathcal{R}$ transforms the system reversibly from state $A$ to $B$, and $\mathcal{I}$ transforms the system irreversibly from $B$ to $A$. By additivity of the line integral, we have $$\oint_\mathcal{P}\frac{\delta Q}{T}=\int_{\mathcal{R}}\frac{\delta Q}{T}+\int_{\mathcal{I}}\frac{\delta Q}{T}<0\tag{3}$$

The first term is simply the change in entropy, $\displaystyle \Delta _{\mathcal{R}}S=S(B)-S(A)$. Rearranging gives us equation $(4)$ $$\displaystyle \Delta_{\mathcal{R}}S<-\int_{\mathcal{I}}\frac{\delta Q}{T}\tag{4}$$

Here is where I don't really understand what is going on. If we divide by $-1$ and flip the inequality sign, then we have proven $(1)$ (since the LHS will give $S(A)-S(B)$). However, if we try to use another property of line integrals, that "flipping the sign" changes the order of the limits, then we should get $$\Delta_{\mathcal{R}}S<\int_{-\mathcal{I}}\frac{\delta Q}{T}$$

since $\mathcal{I}$ transforms our system from $B$ to $A$, $-\mathcal{I}$ should transform it from $A$ to $B$. But the inequality sign has the wrong direction here. I suspect what is happening is that I am applying a property of line integrals which is illegal, since this property of reversing the curve is typically proven for exact differentials, which $\delta Q/T$ for the process $\mathcal{I}$ is not.

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    $\begingroup$ Your suspicion is right. The whole point of "irreversible" processes is that their reverses are impossible. The path $- \mathcal{I}$ would involve physically impossible things like heat spontaneously flowing from cold to hot, or a cake spontaneously unbaking itself. If you allow such processes, then various thermodynamic inequalities can be flipped, and entropy can decrease. But these arguments start from the observational fact that such processes don't occur. $\endgroup$ Commented Sep 20 at 23:57
  • $\begingroup$ Are you being careful to distinguish the temperatures of the environment and the system? The temperature showing up in the Clausius inequality is the temperature of the environment in contact with the system, whereas the temperature in the definition of $\Delta S$ is the temperature of the system. $\endgroup$ Commented Sep 21 at 3:07
  • $\begingroup$ You need to put subscripts of I and R on the dQ's and the T's. That is, they are not the same for the irreversible path as for the reversible path. Note also that the T's are not the system temperature along the path; the are the temperatures at the interface between the system and its surroundings. $\endgroup$ Commented Sep 21 at 10:35
  • $\begingroup$ Thank you for the comments about making sure to keep the temperatures separate, I will keep this in mind. I have a tangentially related question. Is there any mathematical reason why we cannot use this property of line integrals here? I have only studied line integrals for "normal" (exact) differentials, so I suspect it is perhaps the case that this property is not true for inexact differentials. Is this the case? $\endgroup$ Commented Sep 21 at 12:02
  • $\begingroup$ Accessibility between pairs of states is an equivalence class of states and these can be connected by reversible paths but not all conceivable "connection" is integrable unless it is reversible. This is why the measurement of whatever being integrated is measured relative to or within the environment, here in the thermal energy source itself, because in it any and all processes are reversible by its very own definition. $\endgroup$ Commented Sep 21 at 12:34

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