View Full Version : How they got this Identity
pivoxa15
Mar18-07, 02:09 AM
1. The problem statement, all variables and given/known data
If dU=TdS-PdV then
(dS/dV)T=(dP/dT)V
the T and V at the end means that T and V are constant
How did they get this identity? It came from a thermodynamics hence for their notations.
I have tried ways like rearranging but it dosen't seem to work. I think it has something to do with exact differentials.
Hootenanny
Mar18-07, 08:08 AM
Are you familiar with the Helmholtz function?
tim_lou
Mar18-07, 10:37 AM
by Clairaut's theorem,
let [itex]z=z(x,y)[/tex]
\left ( \frac{\partial^2 z}{\partial x\partial y}\right )=\left ( \frac{\partial^2 z}{\partial y\partial x}\right )
or more explicitly, using "thermodynamic notations":
\left [\frac{\partial}{\partial y}\left ( \frac{\partial z}{\partial x}\right )_y\right ]_x=\left [\frac{\partial}{\partial x}\left ( \frac{\partial z}{\partial y}\right )_x\right ]_y
then look at:
F=U-TS
dF=-SdT-PdV
so F is a function of T and V, ie. [itex]F=F(T,V)[/tex] (when N is treated as a constant)
pivoxa15
Mar18-07, 04:59 PM
I see. The Clairaut's theorem is a formal way of stating exact differentials isn't it?
Helmholtz function is F=U-TS and sub dU=TdS-PdV and apply Clairaut's theorem.
Using F=U-TS was the important bit. The sheet didn't mention Helmoholtz anywhere so it would have been hard to know what to use in order to derive the relation. Wouldn't you say?
tim_lou
Mar18-07, 05:38 PM
not really.. hehe, looking at the derivatives you posted. One easily notice that the variables involved are V and T.
so you should know the one thermodynamic potential that is a function of V and T. (which is F)
in general, you have
U(S,V)
H(S,P)
F(T,V)
G(T,P)
H=U+PV
F=U-TS
G=U-TS+PV
so when you see an identity, check what variables it involves and use the appropriate thermodynamic functions.
There's a neat calculation involving differential forms.
0=d(dU)=d(TdS-PdV)=dT \wedge dS+Td(dS) - dP\wedge dV-Pd(dV)=dT\wedge dS-dP\wedge dV
Then write
dS=\left(\frac{\partial S}{\partial T}\right)_V dT + \left(\frac{\partial S}{\partial V}\right)_T dV
and
dP=\left(\frac{\partial P}{\partial T}\right)_V dT + \left(\frac{\partial P}{\partial V}\right)_T dV .
Note that dT\wedge dT=0 and dT\wedge dV= - dV\wedge dT.
pivoxa15
Mar18-07, 09:44 PM
not really.. hehe, looking at the derivatives you posted. One easily notice that the variables involved are V and T.
so you should know the one thermodynamic potential that is a function of V and T. (which is F)
in general, you have
U(S,V)
H(S,P)
F(T,V)
G(T,P)
H=U+PV
F=U-TS
G=U-TS+PV
so when you see an identity, check what variables it involves and use the appropriate thermodynamic functions.
OK. But you could interchange these functions couldn't you to get them into different variables intermingled together.
There's a neat calculation involving differential forms.
0=d(dU)=d(TdS-PdV)=dT \wedge dS+Td(dS) - dP\wedge dV-Pd(dU)=dT\wedge dS-dP\wedge dV
Then write
dS=\left(\frac{\partial S}{\partial T}\right)_V dT + \left(\frac{\partial S}{\partial V}\right)_T dV
and
dP=\left(\frac{\partial P}{\partial T}\right)_V dT + \left(\frac{\partial P}{\partial V}\right)_T dV .
Note that dT\wedge dT=0 and dT\wedge dV= - dV\wedge dT.
What is the upside down V in the equations?
What is the upside down V in the equations?
It's called the "wedge product". http://mathworld.wolfram.com/WedgeProduct.html
tim_lou
Mar18-07, 10:44 PM
the notation looks insane.
just one question, why does d(dU)=0??
and I am very confused by the info from mathworld...
so
dT\wedge dS
equals what in terms of partial derivatives???
is it like a vector cross product or something like that???
suppose a=a(x,y), b=b(x,y)
what would
da\wedge db
be?
the notation looks insane.
just one question, why does d(dU)=0??
This comes from the definition of the exterior derivative (http://mathworld.wolfram.com/ExteriorDerivative.html)
and I am very confused by the info from mathworld...
so
dT\wedge dS
equals what in terms of partial derivatives???
Plug dS and dP into the first equation in robphy's post.
is it like a vector cross product or something like that???
suppose a=a(x,y), b=b(x,y)
what would
da\wedge db
be?
Look up the exterior derivative above.
tim_lou
Mar19-07, 09:58 AM
wow.. thanks for the info. differential forms are awesome! time for me to pick up a book on such topic.
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