Thermodynamics – Understanding the Relation ?S?/?E? = -?S?/?E? in Entropy Derivation

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My course guide gives the following derivation for change in entropy w.r.t. energy, where I don't understand a step:

\begin{align}
E & = E_1 + E_2 \\
S & = S_1 + S_2 \\
S(E,E_1 ) & = S_1 (E_1) + S_2(E-E_1)
\end{align}

Then the question is asked, which $E_1$ the new S wouldn't change. I don't truly understand what the premise is of this question. But I understand that it is a maximum, thus you can find it with setting a derivative to zero as follows:

$$\frac{\partial S}{\partial E_1} = 0 =\frac{\partial S_1}{\partial E_1} + \frac{\partial S_2 }{\partial E_1} \tag{ chain rule}$$

Then the guide just says: "Use the following relation". I don't get how to find this relation?

$$ \frac{\partial S_2}{\partial E_1} = -\frac{\partial S_2}{\partial E_2} $$

Where then this follows:

$$ \frac{\partial S_1}{\partial E_1} = \frac{\partial S_2}{\partial E_2} $$

Central question:
$$ \frac{\partial S_2}{\partial E_1} = -\frac{\partial S_2}{\partial E_2} $$
How to find this. When I differentiate $S$ to $E_2$ I just get:

$$\frac{\partial S}{\partial E_2} = 0 =\frac{\partial S_1}{\partial E_2} + \frac{\partial S_2 }{\partial E_2} \tag{ chain rule}$$

Best Answer

It's not unreasonable to be confused about this. Let's say you have a function $f$ of one variable and $f'$ is its derivative. Then we have $$\frac{d}{dx} f(c-x) = \color{red}{-}f'(c-x)$$ via the chain rule. If we have a function $g$ of two variables, then we might similarly write $$\frac{\partial}{\partial x} g(c-x,y) = \color{red}{-} \big(\partial_1 g\big)(c-x,y)$$ where $\partial_1g$ is the function obtained by differentiating $g$ with respect to its first entry. It is extremely common to simply call $\partial_1 g$ the same thing as $\frac{\partial g}{\partial x}$, but that only works when we assume that $x$ is the thing which we plug into the first slot of $g$. When that isn't the case - e.g. here - that notation is bad in my opinion.


In our case, we have the following expression: $$S(E,E_1) := S_1(E_1) + S_2(E - E_1)$$ $S_1(\epsilon)$ is the entropy of the first system when it has energy $\epsilon$. $S_2(\epsilon)$ is the entropy of the second system when it has energy $\epsilon$. $S(E,E_1)$ is the entropy of both systems together when they have total energy $E$, and when the first system has energy $E_1$ (so the second system has energy $E_2= E-E_1$).

If we wish to maximize this with respect to $E_1$, we would differentiate and set the result to zero: $$\frac{d}{dE_1} \big(S_1(E_1) + S_2(E-E_1)\big) = S_1'(E_1) \color{red}{-} S_2'(E-E_1) = 0$$ $$\implies S_1'(E_1) = S_2'(\underbrace{E-E_1}_{=E_2})$$

This is what your course guide is trying to say.

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