2
$\begingroup$

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?

$\endgroup$
4
  • 3
    $\begingroup$ "All these processes are clearly irreversible. " Who says? $\endgroup$ Commented Nov 1, 2016 at 0:23
  • $\begingroup$ Well, by the computations we see that $\Delta S > 0$, which is the same as saying that the processes are irreversible right? Furthermore, I admit can't see how can a melting process be naturally reversed, that's what I meant by "these processes are clearly irreversible". $\endgroup$
    – Gold
    Commented Nov 1, 2016 at 0:32
  • 2
    $\begingroup$ $\Delta S>0$ for the system does not mean that a process is irreversible. Melting can be reversed by putting the system in contact with a reservoir that is at a slightly lower temperature, rather than a slightly higher temperature (and waiting long enough). A reversible path is one in which the system passes through a continuous sequence of thermodynamic equilibrium states. Did they not cover this in your thermodynamics course? $\endgroup$ Commented Nov 1, 2016 at 1:39
  • $\begingroup$ Related physics.stackexchange.com/q/677501/226902 $\endgroup$
    – Quillo
    Commented Mar 14, 2023 at 0:45

2 Answers 2

2
$\begingroup$

Entropy $S$ is a state function.

It only depends on the final and initial states, and not on how the state was reached.


The Clausius' Inequality states

$$\oint \frac{đQ_\textrm{system}}{T_\textrm{source}}\leqq 0\,.\tag{I }$$

When the cycle is reversible, $T_\textrm{source}~=~ T_\textrm{system}$ and equality of $\rm(I)$ applies i.e.,

$$\oint \frac{đQ_\textrm{system}}{T_\textrm{system}} = 0\tag{I.i}$$

It is a matter of few steps from $\rm(I.i)$ to show that the integral $\displaystyle\int \dfrac{đQ}{T}$ takes the same value for two different reversible paths.

So, we can define $S(\rm A) = \displaystyle\int_{\rm O_\textrm{reference state}}^{\rm A}~ \dfrac{đQ_\textrm{rev}}{T_\textrm{system}}$ i.e., for a reversible transformation.

Now, consider two paths equilibrium states $\rm A$ and $\rm B$ such that $\mathsf I$ connecting $\rm A$and $\rm B$ is arbitrary path (reversible or irreversible) and the second path $\mathsf I^\prime$ connecting $\rm B$ and $\rm A$ is reversible.

So, using $\rm(I),$ we get

$$\begin{align} \oint_{\mathrm A \mathsf I \mathrm B \mathsf{^\prime}\mathrm A } \frac{đQ}{T} & \leqq 0 \\ \implies~~~~~~~~~~~~~~~ \left (\int_{\mathrm A}^{\mathrm B} \frac{đQ}{T}\right)_{\mathsf{I}} + \left (\int_{\mathrm B}^{\mathrm A} \frac{đQ}{T}\right)_{\mathsf{I^\prime}} & \leqq 0\\\implies \left (\int_{\mathrm A}^{\mathrm B} \frac{đQ}{T}\right)_{\mathsf{I}} - \left[\int_{\mathrm O}^{\mathrm B}\frac{đQ}{T}-\int_{\mathrm O}^{\mathrm A} \frac{đQ}{T}\right]&\leqq 0~~~~~~~~~~~~~~~~~~~~~(\mathsf I^\prime~\textrm{is reversible})\\ \implies~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ S(\mathrm B)- S(\mathrm A)&\geqq \left (\int_{\mathrm A}^{\mathrm B} \frac{đQ}{T}\right)_{\mathsf{I}}\tag{II}\end{align}$$

From $\rm (II)$

$$S(\mathrm B)-S(\mathrm A)~=~\left (\int_{\mathrm A}^{\mathrm B} \frac{đQ}{T}\right)_{\mathsf{I}}~~~\textrm{iff}~~~\mathsf I ~\textrm{is a reversible transformation}$$ that is, $$S(\mathrm B)-S(\mathrm A)~=~\int_{\mathrm A}^{\mathrm B} \frac{đQ_\textrm{rev}}{T}\tag{III.i}$$

When $\sf{ I}$ is irreversible, then from $\rm{(II)}$

$$S(\mathrm B)-S(\mathrm A)\gt \int_{\mathrm A}^{\mathrm B} \frac{đQ_\textrm{irrev}}{T}$$

More precisely, using the first law $$\mathrm dS= \dfrac{\textrm{đ} q_\textrm{irrev}}{T}+ \dfrac{\left [ \textrm{đ} w_\textrm{rev}-\textrm{đ} w_\textrm{irrev}\right]}{T}\;.\tag{III.ii}$$

Both $\rm{(III.i)}$ and $\rm{(III.ii)}$ would yield the same entropy change as after-all entropy $S$ is a state function.

But which of $\rm{(III.i)}$ and $\rm{(III.ii)}$ would one use to compute the change in entropy?

Think.


References:

$\bullet$ Thermodynamics by Enrico Fermi.

$\endgroup$
2
  • 1
    $\begingroup$ What is "$đQ$" supposed to be? $\endgroup$
    – Ryan Unger
    Commented Nov 12, 2016 at 3:59
  • 1
    $\begingroup$ It means that $đQ$ is not an exact differential, @0celo7. $\endgroup$
    – user36790
    Commented Nov 12, 2016 at 4:18
0
$\begingroup$

When a system at constant temperature $T$ receives (loses) heat $Q$, the system's gain (loss) of entropy $\textit{due to this particular operation}$ of heating addition (removal) may indeed be written as $\Delta S_{heating/cooling}=\frac{Q}{T}$. Such a situation occurs during phase change. However this is only one mechanism by which a system's entropy may change; entropy of a system can also change due to flux of mass which carries entropy; dissipative processes such as friction generate entropy all on its own.

To show that a process is reversible (irreversible), you must show that entropy of system+surroundings remains the same (increases). Just from knowledge of $\Delta S_{heating/cooling}$ pertaining to the system you cannot conclude anything.

$\endgroup$

Your Answer

By clicking “Post Your Answer”, you agree to our terms of service and acknowledge you have read our privacy policy.

Not the answer you're looking for? Browse other questions tagged or ask your own question.