Review of Thermodynamics

The equations of stellar structure involve derivatives of thermodynamic variables such as pressure, temperature, and density.
To express these derivatives in a useful form, we will need to review the basic thermodynamic relations. First, lets define the
variables:
:
P:
T:
:

the
the
the
the

gas density
gas pressure
gas temperature
mean molecular weight

q:
u:
s:
V:

the
the
the
the

specific
specific
specific
specific

heat content
internal energy
entropy
volume (1/)

Note that q, u, s, and V are all per unit mass. From these
variables come the specific heats

dq
s
cV =
=T
(1.1)
dT V
T V

dq
s
cP =
=T
(1.2)
dT P
T P
the ratio of the specific heats
=

cP
cV

the adiabatic temperature gradient

ln T
ad =
ln P s
an isothermal compressibility coefficient

P V
ln
=
=
V P T,
ln P T,

(1.3)

(1.4)

(1.5)

a volume coefficient of expansion

T
=
V

V
T

=
P,

ln
ln T

ln
ln

(1.6)
P,

and a chemical potential coefficient

=
V

=
P,T

(1.7)
P,T

(For the following, we will assume the chemical composition is

fixed.)
We will also need the first law of thermodynamics:
dq = T ds = du + P dV

(1.8)

Note that although there are four variables in this equation (s,
T , P , and V ), only two are independent.

To derive the relationships between the various thermodynamic

variables, first take s and V as independent, and re-write (1.8)
as
du = T ds P dV
(1.9)
However, when written in terms of s and V , du is formally
du =

u
s

ds +
V

which means that

u
=T
s V

u
V

and

u
V

dV
s

= P

(1.10)

Now, mathematically
2u
2u
=
V s
sV
so

u
V

u
s

=
V

u
s

u
V

or

T
V

=
s

P
s

(1.11)
V

Similarly, if we choose s and P as the independent variables, and

add d(P V ) to each side of (1.9), then the first law of thermodynamics becomes
dH = d(u + P V ) = T ds P dV + P dV + V dP = T ds + V dP

The total first derivative of H is then

H
H
ds +
dP
dH =
s P
P s
which implies that

H
=T
s P
and

T
P

and

=
s

V
s

H
P

=V
s

(1.12)
P

If we subtract d(T s) from each side of the first law of thermodynamics, then T and V are the free parameters, via
dF = d(u T s) = T ds P dV T ds sdT = P dV sdT
We then get the relations

F
= s
T V

and

F
V

which leads via the second derivatives to

s
P
=
V T
T V

= P
T

(1.13)

Finally, if T and P are chosen to be independent, and d(P V T s)

are added to (1.8), then we can derive the relation

s
V
=
(1.14)
P T
T P

Thus, we have Maxwells relations

T
V

T
P

=
s

=
s

P
s

V
s

(1.11)
V

(1.12)
P

s
P
=
V T
T V

s
V
=
P T
T P

(1.13)
(1.14)

To derive a relation between the specific heats, start by letting

T and P be independent, and write the specific heat content as
dq = T ds = T
and dP as
dP =

P
T

s
T

dT +
P

dT +
V

P
V

s
P

dV

dP
T

This gives
dq = T

s
T

dT + T
P

s
P

P
T

dT +
V

P
V

dV
T

We can now evaluate (dq/dT ) while holding V constant, i.e.,

with dV = 0

dq
s
s
P
=T
+T
dT V
T P
P T T V
The term on the left side of the equation is cV , the first term
on the right is cP , and (ds/dP )T = (dV /dT )P by a Maxwell
relation (1.14). Thus,
cP cV = T

V
T

P
T

The first partial differential can immediately be written in terms

of the volume coefficient of expansion (1.6)

V
T

=
P

V
T

(1.15)

The second partial differential can also be re-written, if one first

notes that the total derivative for dV is

V
V
dV =
dT +
dP
T P
P T
Thus, when V is held constant, dV = 0, and

P
T

=
V

V
T

V
P

The numerator on the right side is again (/T ), while the denominator is related to the compressibility coefficient by

Thus

and

V
P

P
T

=
T

=
V

V
P

P
T

P V 2
P 2
cP cV =
=
T
T

Note that this reduces to R = k/mA for an ideal gas.

(1.16)

(1.17)

Finally, to express the change in the heat content of a system,

dq, in terms of the intensive parameters only, choose V and T as
the independent variables, and write the change in entropy as

s
s
ds =
dT +
dV
T V
V T
Using the definition of heat capacity (1.1) and the Maxwell relation (1.13), this becomes

P
cV
dT +
dV
ds =
T
T V
If we now substitude (1.16) for (P/T )V , and convert dV to d
using dV = 1/2 d, we get an expression for dq
dq = T ds = cV dT

P d

This can then be further simplified by noting that

d
ln
ln
dP
dT
=
d ln P +
d ln T =

ln P T
ln T P
P
T
Thus

P 2

dq = cV dT +
dT dP
T

or

dq = cP dT dP

(1.18)

This equation also leads directly to an expression for the adiabatic temperature gradient. If dq = 0, then
cP dT =

dP

which implies that

and
ad =

T
P

cP

ln T
ln P

P
T cP

(1.19)

Note that for an ideal gas, the definition of an adiabat implies

that

P
P
= T P (1)/
T
Hence for a monotonic gas with = 5/3,
ad

= (2/3) (5/3) = 0.4

(1.20)

Note also that (1.19) can then be substituted back into (1.18)
to yield an equation for dq in terms of P , T , cP , and adiabatic
temperature gradient

dT
dP
T cP ad
dP = cP T
ad
dq = cP dT
P
T
P

(1.21)