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I have an equation of state as a function of $p$ (pressure), $T$ (temperature) and $V$ (volume) and need to find an expression for the internal energy $U$. If I use the First Law, $$dU=TdS-pdV$$ and set $dS = 0$, then I can find how $U$ depends on $V$, but not how it depends on $S$. Can I then set $dV = 0$ and integrate $T dS$?

Generally, is it possible to integrate $dU$ above given just an equation of state? Can we get a unique answer for $dU$, or is it ambiguous, and if so, how?

Chet Miller
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    Related (possible duplicate as well): http://physics.stackexchange.com/questions/46737/internal-energy-according-to-the-van-der-waals-equation – Kyle Kanos Feb 26 '14 at 14:08
  • You should look at the reference given to you by @KyleKanos and this answer in particular. https://physics.stackexchange.com/a/47097/104696 – Farcher May 09 '17 at 15:59

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Internal Energy $dU$ can be claculated from

\begin{equation} dU=\left(\frac{\partial U}{\partial V}\right)_{T}dV+\left(\frac{\partial U}{\partial T}\right)_{V}dT \end{equation}

We know that \begin{equation} \left(\frac{\partial U}{\partial T}\right)_{V}=C_{V} \end{equation}

One can use Maxwell's equation (which can be seen from $dU=TdS-PdV$):

\begin{equation} \left(\frac{\partial T}{\partial V}\right)_{S}=-\left(\frac{\partial P}{\partial S}\right)_{V} \end{equation}

and can calculate

\begin{equation} \left(\frac{\partial U}{\partial V}\right)_{T}=T\left(\frac{\partial P}{\partial T}\right)_{V}-P \end{equation}

Therefore,

\begin{equation} dU=\left(T\left(\frac{\partial P}{\partial T}\right)_{V}-P\right)dV+C_{V}dT \end{equation}

In the case of ideal gas, equation of state is $PV=nRT$,

\begin{equation} \left(\frac{\partial U}{\partial V}\right)_{T}=T\left(\frac{\partial P}{\partial T}\right)_{V}-P=0 \end{equation}

and internal energy can be integrated which gives \begin{equation} \Delta U=C_{V}(T_{f}-T_{i}) \end{equation} .

In the case of adiabatic expansion $dS=0$, which gives \begin{equation} dU=-PdV \end{equation}

Using, $PV^{\gamma}=\text{constant}$ .If constant is k we can integrate and find \begin{equation} \Delta U=k\left(\frac{V_{f}^{-\gamma-1}-V_{i}^{-\gamma-1}}{\gamma+1}\right) \end{equation}

It was simple in the above two cases because we could reduce integration in one variable.

Now if we consider a toy model \begin{equation} PVT^{3}=k \end{equation}

In this case

\begin{equation} \left(\frac{\partial U}{\partial V}\right)_{T}=\left(T\left(\frac{\partial P}{\partial T}\right)_{V}-P\right)=-4P=-4\frac{k}{VT^{3}} \end{equation}

If we want to integrate $dU$ , $\left(\frac{\partial U}{\partial V}\right)_{T}dV=-4\frac{k}{VT^{3}}dV$ has 2 independent variables and cannot be integrated.

Hence, integration of the internal energy depends on the equation of state. In some cases, it is possible to integrate and in other cases it won't be possible to integrate internal energy.

  • Didn't you exchange $\textrm{d}V$ and $\textrm{d}T$ on your first equation ? – Spirine May 08 '17 at 19:36
  • @Spirine You were right. I edited my answer – Siddharth Dhanpal May 08 '17 at 23:14
  • Perhaps worth clarifying that the heat capacity $C_V$ is not necessarily constant with temperature. An internal molecular degree of freedom may "freeze out" at low temperatures, decreasing the heat capacity. $PV=nkT$ will however continue to hold. The point is that the temperature dependence of the energy is not constrained by the ideal gas law. – creillyucla May 11 '18 at 04:29
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Given a function $U=U(x_1, \dots, x_n)$ of class $\mathcal{C}^1$, for any $a=(a_1,\dots,a_n)$ and $b=(b_1,\dots,b_n)$,

$$\begin{align} U(b) - U(a) &= \sum\limits_{i=1}^{n}U(b_1, \dots, b_{i}, a_{i+1}, \dots, a_n) - U(b_1, \dots, b_{i-1}, a_{i}, \dots, a_n) \\ &= \sum\limits_{i=1}^{n}\int\limits_{a_i}^{b_i}\frac{\partial U}{\partial x_i}(b_1, \dots, b_{i-1}, t_i, a_{i+1}, \dots, a_n)\textrm{d}t_i \end{align}$$

So, in your case $U = U(S, V)$, and let $U_0 = U(S_0, V_0)$ a reference state, then

$$ \begin{align} U(S_f,V_f) &= U_0 + \int\limits_{S_0}^{S_f}\frac{\partial U}{\partial S}(S, V_0)\textrm{d}S + \int\limits_{V_0}^{V_f}\frac{\partial U}{\partial V}(S_f, V)\textrm{d}V \\ &=U_0 + \int\limits_{S_0}^{S_f} T(S, V_0)\textrm{d}S -\int\limits_{V_0}^{V_f}p(S_f,V)\textrm{d}V \end{align}$$

The First Law gives you the partial derivative of $U$, and the equation of state will give you the relation between the useful variables, so it is in fact possible to find the value of $U$ for any state.

Spirine
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  • Can you explain how to find the functions $T(S, V)$ and $p(S, V)$? We are given just $p(T, V)$. – knzhou May 07 '17 at 19:45
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You typically hold one thing constant and get a differential equation in terms of the other quantities. For instance,

$$\left(\frac{dU}{dV}\right)_T=p$$

This is a helpful reference: http://authors.library.caltech.edu/25018/6/TOE05.pdf

  • Don't you want an $S$ subscript, not a $T$ subscript? – knzhou May 02 '17 at 19:58
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    Also, I don't think this answers the question. As stated by the OP, the easy first step is to use this equation; the hard part is whatever comes after. – knzhou May 02 '17 at 19:59
  • I too originally thought $S$, but in the reference I found, on p. 83 you see the equation I gave. Maybe it's a typo. Regardless, in thermodynamics, the hard part is knowing which equation to use, and after that it's just a differential equation, which isn't that hard for anything you'll find in a classroom. – William J. Cunningham May 02 '17 at 20:13
  • i think this would help http://www.harding.edu/lmurray/themo_files/notes/ch04.pdf page 2,3 – Rishi Kakkar May 06 '17 at 12:24