Thermodynamics, finding the fundamental equation of ideal gases

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fluidistic
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Homework Statement


An ideal monoatomic gas is characterized by the two equations [itex]PV=NRT[/itex] and [itex]U=\frac{3NRT}{2}[/itex] in which R is a constant.
Find the fundamental equation corresponding to a monoatomic ideal gas.

Homework Equations


[itex]S=\left ( \frac{1}{T} \right ) U+\left ( \frac{P}{T} \right ) V- \left ( \frac{\mu }{T} \right ) N[/itex].


The Attempt at a Solution


I'm given 2 equations of state, one is missing in order to get the fundamental equation. In the entropy representation the variables of the fundamental equation are [itex]\frac{1}{T}[/itex], [itex]\frac{P}{T}[/itex] and [itex]\frac{\mu }{T}[/itex].
The missing one is [itex]\frac{\mu }{T} (U,V,N)=\frac{\mu}{T} (u,v)[/itex] where u and v in lower script are the molar energy and volume respectively.
So I have that [itex]\frac{1}{T}=\frac{3R}{2u}[/itex] and [itex]\frac{P}{T}=\frac{R}{v}[/itex].
I use Gibbs-Duhem's relation [itex]d \left ( \frac{\mu }{T} \right ) =ud \left ( \frac{1 }{T} \right ) +v d \left ( \frac{P }{T} \right )[/itex]. Replacing the variables in parenthesis and integrating both sides, I reach (like the book): [itex]\frac{\mu}{T}=-\frac{3}{2}R \ln \left ( \frac{u}{u_0} \right ) -R \ln \left ( \frac{v}{v_0} \right ) +\left ( \frac{\mu }{\mu _0} \right ) _0[/itex].
When I replace this equation into the expression for S given above and using the fact that u=N/U, [itex]u_0=\frac{N}{U_0}[/itex], I reach that [itex]S =\frac{3U^2 R}{2N}+\frac{RV^2}{N}+ N \left [ \frac{3R}{2} \ln \left ( \frac{U_0}{U} \right ) +R\ln \left ( \frac{V_0}{V} \right ) - \left ( \frac{\mu }{T} \right ) _0 \right ][/itex]. Using some log property this simplifies to [itex]S=\frac{3U^2R}{2N} +\frac{RV^2}{N} +NR \ln \left [ \left ( \frac{U_0}{U} \right ) ^{3/2} \left ( \frac{V_0}{V} \right ) \right ] -N \left ( \frac{\mu }{\mu _0} \right ) _0[/itex].
However this differs from the answer given in the book: [itex]S= \frac {5NR}{2}-N \left ( \frac {\mu }{T} \right ) _0 +NR \ln \left [ \left ( \frac {U}{U_0} \right ) ^{3/2} \left ( \frac{V}{V_0} \right ) \left ( \frac {N}{N_0} \right ) ^{-5/2} \right ][/itex].
I do not see, for the life of me, what I've done wrong.
 
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Hi fluidistic.

Let's start with your integration constant.
It should be ##(\frac{\mu}{T})_0## instead of ##(\frac{\mu}{\mu_0})_0##.

Then you write u=N/U, but that is not right.
Since you defined u to be the molar volume, u=U/N.

Perhaps you can redo it?
 
Thanks a lot for helping me!
You are absolutely right, I've redone everything with more care. I reach however [itex]S=\frac{5RN}{2}-N \left ( \frac{\mu}{T} \right ) _0+NR \ln \left [ \left ( \frac{U}{U_0} \right ) ^{3/2} \left ( \frac{V}{V_0} \right ) \right ][/itex].
Therefore it seems like I'm missing a term in the logarithm.
It seems it comes from the integration of the Gibbs-Duhem relation: [itex]d \left ( \frac{\mu }{T} \right ) =ud \left ( \frac{1 }{T} \right ) +v d \left ( \frac{P }{T} \right )[/itex]. It seems that when I integrate I should get an extra term like "[itex]-R \ln \left ( \frac{N}{N_0} \right )[/itex]. I don't really know how to get that.
 
Maybe it's simpler than you think.
What did you fill in for ##u_0##?
 
Last edited:
I like Serena said:
Maybe it's simpler than you think.
What did you fill in for ##u_0##?
Hmm I still don't see it. I took [itex]u_0=\frac{U_0}{N}[/itex].
 
fluidistic said:
Hmm I still don't see it. I took [itex]u_0=\frac{U_0}{N}[/itex].

Note that N is also a variable that changes.
It has an initial value too, just like ##u_0## and ##U_0##.
 
I like Serena said:
Note that N is also a variable that changes.
It has an initial value too, just like ##u_0## and ##U_0##.

Yes I know this but when should I make use of this?
Here are my steps:
1)[itex]\frac{1}{T}=\frac{3NR}{2U}=\frac{3R}{2u}[/itex]
2)[itex]\frac{P}{T}=\frac{NR}{V}=\frac{R}{v}[/itex]
I use Gibbs-Duhem's relation [itex]d \left ( \frac{\mu }{T} \right ) =ud \left ( \frac{1 }{T} \right ) +v d \left ( \frac{P }{T} \right )[/itex].
3)[itex]ud \left ( \frac{1 }{T} \right ) =-\frac{3Rdu}{2u}[/itex]
4)[itex]v d \left ( \frac{P }{T} \right ) =-R\frac{dv}{v}[/itex].
Integrating the GD relations gives me [itex]\frac{\mu}{T}=-\frac{3}{2}R \ln \left ( \frac{u}{u_0} \right ) -R \ln \left ( \frac{v}{v_0} \right ) +\left ( \frac{\mu }{T} \right ) _0[/itex]. The book (Callen's page 52) reaches exactly the same result so far.
He then says that inserting this into the Euler equation [itex]S=\left ( \frac{1}{T} \right ) U+\left ( \frac{P}{T} \right ) V- \left ( \frac{\mu }{T} \right ) N[/itex] one reaches [itex]S= \frac {5NR}{2}-N \left ( \frac {\mu }{T} \right ) _0 +NR \ln \left [ \left ( \frac {U}{U_0} \right ) ^{3/2} \left ( \frac{V}{V_0} \right ) \left ( \frac {N}{N_0} \right ) ^{-5/2} \right ][/itex].
So my error is when I insert what I obtained into the Euler equation or it's in integrating GD relation (in which case the book would also be wrong) or it's in either of the 4 steps I denoted by 1), etc.?
I really don't see it. :/
 
I got to your book result substituting ##u_0=\frac{U_0}{N_0}## and ##v_0=\frac{V_0}{N_0}## in the integrated GD result.
 
I like Serena said:
I got to your book result substituting ##u_0=\frac{U_0}{N_0}## and ##v_0=\frac{V_0}{N_0}## in the integrated GD result.

Ah! That explains everything :biggrin: In my case those were variables, I didn't even notice. Now I reach the desired result... thank you very much for all.
 
Just out of curiosity, were my previous hints too cryptic?
It is not my intention to make a thread a cryptic puzzle...
Perhaps you have an idea what kind of hint I might have given that would have helped you better?
 
I like Serena said:
Just out of curiosity, were my previous hints too cryptic?
It is not my intention to make a thread a cryptic puzzle...
Perhaps you have an idea what kind of hint I might have given that would have helped you better?

You mean post 6? No, not cryptic. In fact now I understand your "hint" that I should have used N_0 instead of N. I did not realize that with my definition of u_0, it wasn't even a constant.
So in my case pointing out in post 6 that my definition of u_0 was wrong and that it's not even a constant would have made me understand where the problem lies. I did not realize it, because I already knew that N was a variable and I thought that was what you wanted me to know.
But I'm maybe a "weird learner" :) Anyway, thank you very much for having went through all of this with me.