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Deriv
Deriv
In this section we will establish some generic relations between partial derivatives of thermodynamic
quantities, which follow just from the multiple-variable calculus. We will also showby the analysis of
intensive and extensive variablesthat there are three types of special partial derivatives that either
(i) reduce to ratios, or (ii) identically equal to zeros, or (iii) identically equal to infinity. Finally, we
will introduce the so-called Jacobian technique, which is a mathematical tool for re-expressing partial
derivatives with respect to a given set of variables in terms of some other set of variables.
Maxwell Relations
Consider the derivative
S
V
(1)
[At the moment we assume that the total number of particles, N , is either an internal observable,
like in the systems with non-conserving N (photons, phonons), or kept fixed. The situation with
conserving but variable N will be discussed later.] Recalling that
F
S=
T
we have
S
V
=
T
(2)
2 F (V, T )
.
V T
(3)
The function F (V, T ) normally is a regular function of its two variables, and we can swap the partial
derivatives:
2 F (V, T )
2 F (V, T )
=
.
(4)
V T
T V
Then, taking into account
F
= P ,
(5)
V T
we see that
S
P
=
.
(6)
V T
T V
This equality and analogous equalities following just from swapping variables in the mixed secondorder partial derivatives are called Maxwell relations. These are general thermodynamic relations
valid for all systems.
To obtain all the Maxwell relations, consider the following abstract mathematical situation. Some
quantity A is a function of two variables, B and C (just for the sake of briefnessthe actual number
of variables can be arbitrarily large). The differential of A is written as
dA = X dB + Y dC ,
where
X=
Then we have
X
C
A
B
Y =
(7)
A
C
2 A(B, C)
2 A(B, C)
=
=
=
C B
B C
1
(8)
Y
B
.
C
(9)
So far, we have obtained just a direct analog of (6). But now we do the following trick. We introduce
the quantity
A = A XB ,
(10)
and note that
dA = d(A XB) = B dX + Y dC .
Hence,
B
C
=
X
2 A(X,
C)
2 A(X,
C)
Y
=
=
.
C X
C X
X C
(11)
(12)
B
C
=
X
Y
X
(13)
(14)
dE = T dS P dV .
(15)
and
And the corresponding Maxwell relation is
T
V
=
S
P
S
(16)
dH = T dS + V dP
dG = S dT + V dP
(Enthalpy) ,
(Gibbs Free Energy) .
(17)
(18)
Problem 43. (a) Find two Maxwell relations corresponding to Eqs. (17) and (18).
(b) Derive the relation
CP =
H
T
(19)
P
that establishes an important physical meaning of enthalpy as a function describing the heat absorbed/released
by a system at fixed pressure and varying temperature: Q = H.
In the case of variable number of particles, we can produce all Maxwell-type relations starting from
either of the two previously established differential forms,
d = S dT P dV N d ,
2
(20)
dE = T dS P dV + dN ,
(21)
and performing all possible Legendre transformations. The starting point is not important, since the
two forms are related to each other by two Legendre steps.
How many relations are we going to obtain? It is a good idea to count all different Maxwell
relations generated by a differential form
dA = Y1 dX1 + Y2 dX2 + + Ym dXm .
(22)
Special Relations
= + PV
(24)
= S dT + V dP N d .
d
0, and
But we have established earlier that P V , and thus
S dT + V dP N d = 0 .
(25)
(26)
(27)
(28)
[Reminder: A quantity is called intensive if it does not directly depend on the system size. A
quantity which is proportional to the system volume is called extensive. In other words, if we take
two identical systems and combine them into one, all the intensive quantities remain the same, while
all the extensive quantities become factor two larger.]
What we see from Eq. (28) is that any three intensive thermodynamic quantities are not independent. For example, Eq. (28) explicitly states that P is always a function of T and : P = P (T, ),
and, more over
P (T, )
= n,
(29)
P (T, )
= s.
(30)
T
[The fact that P = P (T, ) and Eq. (29) are already known to us from the Grand canonical formalism.]
Similarly, = (T, P ), and
(T, P )
= 1/n ,
(31)
P
(T, P )
= s/n ,
(32)
T
as well as T = T (, P ) and
T (, P )
= n/s ,
(33)
T (, P )
= 1/s .
P
(34)
Trivial relations. What happens if we formally use Eq. (25) to produce Maxwell relations? We will
get relations in terms of pathological expressions of the form
A
B
(35)
x,y
where A is an extensive variable, while B, x, and y are intensive. By fixing x and y we actually fix all
the other intensive quantities, including B, so that the partial derivative is ill defined. Mathematically,
it is convenient to treat it as infinity, in view of the fact that its inverse
B
A
(36)
x,y
S
P
= ,
= 0.
P ,T
S ,T
(37)
It is also worth noting that if x and y are intensive, while A and B are extensive, then
A
B
=
x,y
A
,
B
(38)
since the only consistent way to represent the function A(x, y, B) is A = Bf (x, y). We have already
met an example of such a situation. Namely,
P =
V
=
T,
.
V
(39)
Problem 44. Establish all 24 Maxwell-type relations following from the differential form (20). Among the
relations found, identify pathological ones, as well as the ones which reduce to Eqs. (29)-(34).
Jacobian Technique
Suppose we are looking for the heat capacity at constant volume (and total number of particles) of a
quantum gas:
S
CV = T
.
(40)
T V,N
To explicitly do the partial derivative (40) we have to know an analytic expression for S as a function
of N , V , and T . [Alternatively, we might do the derivative numerically, which is however rather
cumbersome.] Our results for quantum gases are obtained in the grand canonical formalism where
the natural variables are (T, , V ), rather than (T, N, V ). In Multi-Variable Calculus, there is a
generic technique for solving problems like that based on the properties of Jacobians.
Suppose we have m functions, y1 , y2 , . . . , ym , of m variables, x1 , x2 , . . . , xm . If we introduce the
matrix M as
yi
Mij =
,
(41)
xj
then, by definition, the Jacobian of the given set of functions and arguments is the determinant of
M:
(y1 , y2 , . . . , ym )
= det M .
(42)
(x1 , x2 , . . . , xm )
The left-hand side of (42) is just a convenient symbol for corresponding Jacobian.
Jacobians feature some generic properties which we will be utilizing below. The first property
immediately follows from the definition:
(x1 , x2 , . . . , xm )
1.
(x1 , x2 , . . . , xm )
(43)
(y1 , y2 , . . . , ym ) (z1 , z2 , . . . , zm )
(y1 , y2 , . . . , ym )
=
.
(z1 , z2 , . . . , zm ) (x1 , x2 , . . . , xm )
(x1 , x2 , . . . , xm )
(44)
One readily gets Eq. (44) from the chain rule for partial derivatives,
m
X
yi
yi zk
=
,
xj
zk xj
k=1
(45)
and the theorem that the determinant of a product of matricesthe right-hand side of Eq. (45) is
nothing else than the product of matricesis equal to the product of their determinants.
With (43) and (44), we obtain
(y1 , y2 , . . . , ym ) (x1 , x2 , . . . , xm )
= 1,
(x1 , x2 , . . . , xm ) (y1 , y2 , . . . , ym )
that is
(x1 , x2 , . . . , xm )
=
(y1 , y2 , . . . , ym )
(y1 , y2 , . . . , ym )
(x1 , x2 , . . . , xm )
(46)
(47)
Why Jacobians are good for our purposes? Because of the following formula (readily seen from
the definition):
(u, x2 , . . . , xm )
u
=
.
(48)
(x1 , x2 , . . . , xm )
x1 x2 ,...,xm
Example. Consider Eq. (40). We can write it as
CV = T
(S, N )
.
(T, N )
(49)
Note that we do not include V in this Jacobian, since with respect to the quantity and variables of
interest, the variable V plays a role of a fixed external parameter which does not participate in the
transformation of variables.The situation with CP would be different.
We write
(S, N )
(S, N ) (T, )
(S, N )
(T, N )
=
(T, N )
(T, ) (T, N )
(T, )
(T, )
By definition,
(S, N )
=
(T, )
S
T
V,
V,T
N
T
(S, N )
=
(T, )
V,
(50)
T,V
(51)
V,T
Finally, we get
CV = T
S
T
N
T
=
V,
"
T
V,
N
T
V,
(52)
V,T
#2 ,
(53)
T,V
Problem 45. Express the heat capacity at constant pressure (and the total number of particles), CP , in
terms of partial derivatives of S, P , and N as functions of the three grand-canonical variables (T, , V ). Try
to maximally simplify your final answer by utilizing Maxwell relations.