( )

= ( )
:
T P
dZ P, T
Z Z X, Y
Z
Chapter 5
General Procedure
Derivation of the General Proce-
dure
In this chapter we will develop a general method for determining the
relationship between thermodynamic variables. If your independent
variables of choice happen to be and , then you can just look
at the six expressions in the Summary of Thermodynamic functions
for and write down the various relationships that result by
applying coecient and Maxwell relations to the exact dierentials.
This is the trivial case. If on the other hand; however, you are inter-
ested in relationships that involve variables other than temperature
and pressure then you need to do a bit more work. Lets proceed to
develop a strategy for deriving these relationships.
1. The rst step is to identify the variables of interest. If you have a
system with only two degrees of freedom then you will have three
variables, one dependent and two independent. Write down
the dependent variable as a function of the two independent
variables;
2. Write the total dierential of
59
60
_ _
_ _
_ _ _ _
_ _ _ _
_ _ _ _
General Procedure
= +
=
=
= +
= +
= =
= ( + ) + ( + )
= ( + ) + ( + )
= +
Z
X Y
Z
Y X
X
P T
X
T P
Y
P T
Y
T P
P
X
P T
P
Y
P T
T P T P
T T P P
T P
Summary of Thermo-
dynamic State Functions in terms of T and P
not
dZ MdX NdY
M
N
X Y, P T.
dX dY
dX dY
dX dP dT
dY dP dT
X , Y ,
dZ
dZ M X dT X dP N Y dT Y dP
dZ MX NY dT MX NY dP
dZ Z dT Z dP
where we know that the coecients are just the partials
and
3. The third step is to convert the total dierential from the in-
dependent variables of and to and We do this by
substituting in for and from the
in the previous
section. and are themselves exact dierentials and so
they are of the form
and
where we write etc. as shorthand
for the partial derivatives. Notice that here that the subscripts
in this notation refer to the independent variables that are
constant.
Then on substitution into we obtain:
4. The fourth step is to collect like terms:
5. The fth step involves writing
61

( )
= +
= +
=
=
=
=
T P P T
T P P T
P T T P
T P P T
General Procedure
T T T
P P P
T T
P P
T T
P P
T T
P P
T T
P P
Z Y Z Y
X Y X Y
Z X Z X
X Y X Y

Summary of Thermody-
namic State Functions in terms of T and P.
dZ T, P T P
dZ
dT
dP dZ
Z MX NY
Z MX NY
M
N.
M N
M N
M
Z Y
Z Y
X Y
X Y
N
X Z
X Z
X Y
X Y
M
N .
from the now obviously very useful
We now have two
dierent expressions for . Since the variables and
are both independent variables we can vary each one indepen-
dent of the other and since the two expressions for dont
depend on the variation we know that the coecients of and
from the two expressions for are equal to each other.
and
6. The Sixth step involves solving these two equations for and
Solving a system of two linear equations in two unknowns
can be done by elimination of or and then solving for the
other or by using the Jacobians of the system. For the two linear
equations in the two unknowns and above the Jacobians
are:
and
which of course gives you
and
Now that we have outlined this procedure, lets apply it to several
problems as examples (these examples are taken from DeHo section
4.3.3).
p
p
62

_ _
_ _
Example 3
C
T
C
T

S
V T
General Procedure
= ( )
= +
( )
= + ( )
= ( + )
( )
=
= +
=
= =
General Procedure Examples
T or P as an Independent Variable
T P
T
S S T, V
dS MdT NdV
dV dV P, T
dS MdT N V dT V dP
dS M NV dT NV dP
dS P, T dS
dS dT V dP
M NV
V NV
N.
N
The following three examples involve using the General Procedure to
nd the thermodynamic relationship between three variables where
one of the independent variables is either or . In the rst example
is one of the independent variables.
Write the entropy of a system as a function of its tem-
perature and volume.
Step 1. Identify variables:
Step 2. Write the dierential form:
Step 3. Convert using from the summary:
Step 4. Collect terms:
Step 5. Obtain from the summary and compare to we
just derived:
The coecients are equal to each other so:
and
Step 6. Since the algebra is simple we can just use elimination of
and
2
2
63
p
p
p
p
p
p
Example 4

_ _
_ _
_ _
_ _
_ _
General Procedure
=
= =
= +
= ( )
= +
( )
= + ( )
= ( ) +
( )
=
=
=
= =
C
T

C
T

S
T V
C
T

C
T
C
T
C
V T
S
V P
This next example is very similar, however rather than is one
of the independent variables.
M V
M V
dS V dT dV
T, P
S S P, V
dS MdP NdV
dV dV P, T
dS MdP N V dT V dP
dS M NV dP NV dT
dS P, T dS
dS dT V dP
NV
V M NV
N.
N
and nally
Write the entropy of a system in terms of its pressure
and volume
Step 1. Identify variables:
Step 2. Write the dierential form:
Step 3. Convert using from the summary:
Step 4. Collect terms:
Step 5. Obtain from the summary and compare to we
just derived:
The coecients are equal to each other so:
and
Step 6. Since the algebra is simple again we can just use elimination
of
and
64
p
p p
Example 5
_ _
_ _
_ _
_ _ _ _

General Procedure
C
T
S
P V
C
T
C
V T
S
V
F
V P
S
V
S

F
P V
S

S
V
=
= =
= +
= ( )
= +
( )
= + ( )
= ( ) +
( )
= ( + ) +
( + ) =
=
= ( + ) =
= ( + )
= = =
= ( + )
M NV V
M V
dS V dP dV
P T
dP dT
F F P, V
dF MdP NdV
dV dV P, T
dF MdP N V dT V dP
dF M NV dP NV dT
dF P, T dF
dF S PV dT PV dP
S PV NV
PV M NV
N.
N P
M N P V
M P P V
dF dP P dV
From the above two examples we can see that if either or is
one of the independent variables then we do not have to substitute
in for or in step 3. This results in simple algebra in step 5.
Notice this again in the next example.
and nally
Find the relationship needed to compute the change in
Helmholtz free energy when the initial and nal states are specied by
their pressure and volume.
Step 1. Identify variables:
Step 2. Write the dierential form:
Step 3. Convert using from the summary:
Step 4. Collect terms:
Step 5. Obtain from the summary and compare to we
just derived:
The coecients are equal to each other so:
and
Step 6. Since the algebra is simple again we can just use elimination
of
and
and nally
65
P
P
P

_ _
_ _
_ _
C
T
C
T
P
P
C
T
Example 6
General Procedure
Independent Variables Not T or P
= ( )
= +
( ) ( )
= + ( )
= ( + ) + +
( )
= + (1 )
(1 ) = ( + )
= +
H H S, V
dH MdS NdV
dS dV dS P, T dV P, T
dH M dT V dP N V dT V dP
dH MV NV dP M NV dT
dH P, T dH
dH C dT V T dP
V T MV NV
C M NV

Write the enthalpy as a function of volume and entropy.

Step 1. Identify variables:
Step 2. Write the dierential form:
Step 3. Convert and using and from the
summary:
Step 4. Collect terms:
Step 5. Obtain from the summary and compare to
we just derived:
The coecients are equal to each other so:
and
Step 6. Here we can multiply the top equation by and the bottom
equation by and add the two equations or use the Jacobians. Well
use the Jacobians in this case just to illustrate their use.
In the above three examples we solved for the thermodynamic rela-
tionship between three variables where one of the independent vari-
ables was either temperature or pressure. A slightly more complicated
case involves solving for the relationship using the exact same steps
of the General Procedure, but where neither of the independent vari-
ables are pressure nor temperature. The slight complication involves
primarily the extra algebra of solving the two linear equations. Lets
look at an example of this type.
66

(1 )
+
+
+
+
2
2
2
2
2
2
2
2
2
_ _
_ _
_ _
_ _
_ _
_ _
General Procedure

= =
=
=
( )
=
=
= +
=
=
=
= + =
= =
=
M
H V
H V
S V
S V
M
C C .
dS V dT dV
dT
V
C C .
M C
N
S H
S H
S V
S V
M
N .

_ _
_ _
_ _
_ _

T P P T
T P P T
P
C
P
T
P
C
P
T
P
V

TV

T
P
TV

P
V

TV

P
TV

p
p
V
V
T P P T
T P P T
P
V
T T
P P
T T
P P
H V H V
S V S V
C V V T V
V V V
C V TV
V
C
C
T C
C
V P
C
T

S
T V
C
T

S
T V
C
T
V p
TV

T
C
V
V

H
S V
T T
P P
T T
P P
S H S H
S V S V
C
C
Now although this is a perfectly valid equation, it is not in its simplest
form. If one of the independent variables is volume it is usually the
case that a simpler form results if we express the coecients in terms
of rather than To do this we note that from the rst example
of using the General Procedure we found that
which has a coecient relation of which states that
We also know from the section in this chapter on denitions that
So we nd that
Substituting this into our expression for M gives us a simpler look-
ing form:
and
which can be expanded as was to obtain
67
0 1
0 1
0 1
Example 7

_ _
_ _
_ _
_ _
_ _
General Procedure
S
P F
S
F P
S
P F
S
P T
S
F P
T or P as the Dependent Variable
T P.
P S, F
P P S, F
F F P, S S S P, F
S F dP.
P P S, F
P.
S S P, F
M N,
dS MdP NdF
( )?
= ( )
= ( ) = ( )
= ( )
= ( )
=
( ) ( ) ( ) ( )
( ) ( ) ( ) ( )
=
( ) ( ) ( ) ( )
( ) ( ) ( ) ( )
=
( ) ( ) ( ) ( )
( ) ( )
=
( ) ( )
( )
+
=
( ) ( )
( ) ( )
=
( )
( )
= +
S
T
P
F
P
T
S
P
T
F
T
P
P
T
P
F
P
T
P
P
T
F
T
P
P
T
P
S
P
T
P
P
T
S
T
P
P
T
P
F
P
T
P
P
T
F
T
P
S
T
P
F
P
T
S
P
T
F
T
P
F
P
T
F
T
P
S
T
P
F
P
T
F
T
P
S
P
T
S
T
P
F
P
T
F
T
P
S
T
P
F
T
P
The next example of using the General Procedure involves cases where
the dependent variable is either temperature or pressure For ex-
ample, how would one go about solving for the relationship
In this case we would just rewrite the equation as either
or and then use the General Procedure to
determine this relationship. The nal step would then be to rearrange
the total dierentials of either or to the total dierential
Write an expression that shows the dependence of pres-
sure on entropy and Helmholtz free energy.
First we identify variables:
Next we rewrite our master equation since in this case the depen-
dent variable is pressure
We can then write the Jacobians for the partials directly:
and
Which are just and respectively. Well start with simpli-
fying the rst expression. Notice that the partial derivatives of the
pressure with respect to the temperature and pressure are zero and
one, respectively:
The second partial simplies even further:
Now that we have general expressions for the partials (we could
substitute in for the various partials from the summary of thermody-
namic relations, but well refrain from that here) we can write our
total dierential:
2
68

1 1
0 1
0 1
1 1 ( )
1
1 ( )
1
General Procedure
dP
dP dS dF
T P
PV RT

and rearranging gives

Applications to Ideal Gases
__ _ __ _
_ _
_ _
_ _
_ _
_ _
_ _
_ _
_ _
_ _
=
=
( )
( )
=
( ) ( ) ( ) ( )
( ) ( ) ( ) ( )
=
( ) ( )
( ) ( )
=
( )
( )
=
= = =
=
= = =
=
dS
M
NdF
M
S
P F
S
P F
X
Y P
X
Y P
X
Y P
V
V
T P V
RT/P
T
P
R
PV
T
V
V
P T
P
RT
RT/P
P
T
P
RT
RT
P
P
S
T
P
F
T
P
P
T
P
X
P
T
P
P
T
X
T
P
P
T
P
Y
P
T
P
P
T
Y
T
P
X
P
T
X
T
P
Y
P
T
Y
T
P
X
T
P
Y
T
P
Notice that when I have the partials of one state function with
respect to another at either a constant temperature or constant pres-
sure that this partial becomes just the ratio of the two partials with
respect to or (which ever is not held constant). That is
which simplies by
so that
The above General Procedure is useful and as the name implies Gen-
eral. That is, we dont have to specify any materials properties in
order to apply the General Procedure to derive thermodynamic rela-
tionships. On the other hand, the general relationships we derive can
be applied to specic cases when we have some measured property for
the specic case. The ideal gas is the most trivial case. Remember
that for one mole of an ideal gas
The thermal expansion coecient then becomes
and the compressibility for an ideal gas becomes
1
P
P
69
2
2
2
1
2
1
Example 8
_ _
_ _
_ _
_
_ _

General Procedure
= =
=
=
=
=
=
=
= + +
= +
= ( )
=
= = =
= =
= = ln
V
P
V P
TV

P
TV P
T
V P
PV
T
V P
C
T
V
T
V
T
V
P
V
P
PV
T
C
T
V
T
T
V
T
T
RT
P T
T
R
P
T
T,rev T
RT
P
T
T,rev
P
P
RT
P
T
P
P
C
C
C C C
C C
C C R

dS dT dP
dV dT dP
dU C dT
dH C dT
dF S dT V dP
dG SdT V dP
S S T, P
dS dT dP
dS dP dP dP
q TdS dP
q dP RT
What is the heat absorbed by one mole of an ideal gas
for a reversible isothermal change in pressure? The relationship that
describes this process is and from the above we write
and since the process is isothermal this becomes
Using the relationship between the heat ow in a reversible process
and the change in entropy we can write
which on integration becomes
Applying these results to the general relationship between and
we get
which is the same relationship we had derived earlier while discussing
ideal gases. Also note that we can apply the ideal gas equation of state
to any of the six state functions written as functions of temperature
and pressure. The following summarizes the results of substituting in
the explicit forms of and into our six state functions:
Using these expressions we can then nd the changes in the various
thermodynamic quantities for a particular change of state. Lets look
at an example that does just this.
If instead we were interested in the heat absorbed by an ideal
gas during an isobaric expansion we would need to nd a dierent
thermodynamic relationship to describe the process. Lets look at
this case as another example.
2
1
70

_ _
_
2 1
2 1
Example 9
P P
P
P
P P
p
P
Example 15
General Procedure
= 0
= ( )
= +
=
= 1
=
= = =
= = ( )
= ( )
( )
dP
S S P, V
dS V dP dV
dS dV
T
dS dV
q TdS dV dV
q dV V V
q C T T
C T.
T
C T
C
T
C
V T
P
C
V T
P
P
C
V
P
P,rev P
TC
V
P
PC
R
P
P,rev
V
V
PC
R
P
PC
R
P,rev P
P
P
Note that we implicitly assumed that is independent of This
is not necessarily the case. In cases where there is a signicant change
in this assumption might not hold and an explicit description of
should be included in the more complicated integral.
What is the heat adsorbed by an ideal gas during an
expansion at constant pressure?
The variables for this case are entropy (because we are interested
in heat), volume (because the gas expands) and pressure (because the
process is done with ). So
We found this expression previously in using the
General Procedure:
and for an isobaric expansion this becomes
Since we have for an ideal gas we obtain
To calculate the heat absorbed we multiply by temperature
which we integrate to get
and
71
_ _ _ _
Example 10
P
S
P U
S
U P
= 0
= 0
= ( )
= +
= 0
General Procedure
Applications to Solids
, ,
C
dU
dU
S S P, U
dS dP dU
dU
Solid State Thermodynamics
In the processing of a mole of nickel at 100,000 atm of
pressure you suddenly reduce the pressure down to 1atm. You realize
that similar to the expansion of an ideal gas you are going to cre-
ate entropy during this irreversible process of expanding your ingot.
Although the change in pressure is signicant, we showed previously
that the work done by expanding condensed phases is very small (the
change in enthalpy and internal energies are almost identical). If you
allow this expansion to take place in a thermally insulating vessel we
know that there is no entropy associated with heat transfer with the
surroundings. Since the ingot does negligible work and absorbs no
heat from the surroundings this is approximately a constant internal
energy process:
Since we are interested in the entropy change during a pressure
change with we can write our master equation as
and
Now since we know that
Although ideal gases make for simple examples to demonstrate the
use of the various strategies we have been developing, and although
we can often times approximate the thermodynamic behavior of real
gases by assuming that a gas behaves like an ideal gas, we are most
interested in the thermodynamics of solids. In fact this course is titled
and the thermodynamics of materials is
what we ultimately hope to learn in this course. So lets take a look
at the application of our newly developed thermodynamic tools to the
analysis of solid state thermodynamics.
We know from experience that in contrast to gases, solids and liq-
uids are not very compressible, nor do they expand a great deal on
heating. We also know from experiment that also unlike gases, the
heat capacity of condensed phases is not a strong function of temper-
ature. However, in many cases materials processing involves heating
a material over a large temperature range. So while it is still true
that the compressibility thermal expansion coecient and heat
capacity are not strong functions of temperature, the tempera-
ture changes enough so that we cannot assume these properties to be
constant without having a signicant error.
_ _
72
2
2
2

_ _
_ _
_ _
_ _
_ _
_
_
General Procedure
( )+ ( )
( )
( )
( )
5 1
6 1
2
2 5 1
2
2 6
2 6 1
5

dS dP
dS dP
dS
dS U
K ,
. atm
C . . T J/mol K
V . cc/mol , T K
V T . K K
V T .
C . . x K .
C .
S
T
P
U
P
T
S
P
T
U
T
P
P
T
P
U
P
T
P
P
T
U
T
P
S
T
P
U
P
T
S
P
T
U
T
P
U
T
P
C
P
T
P
P
P
P
P
P
U
S
P U
U
S
P U
S
P U
S
P U
V P T V C PV
C PV
S
P U
PV C V T
T C PV
U
PV C V T
T C PV
P
cc
mol
cc
mol K
P
J
mol K
J
mol K atm
P
J
mol atm K
=
=
( ) ( ) ( ) ( )
( ) ( ) ( ) ( )
=
( ) ( ) ( ) ( )
( )
=
=
( )
=
( )
)
= 4 10 ( )
= 1 5 10 ( )
= 16 99 + 2 95 10 ( )
= 6 6( ) = 300( )
= 6 6( ) 300( ) [4 10 ( )]
= 3 2 10 ( )
= 16 99( ) + 2 95 10 ( )(300 ) 1 5 10 ( )
= 3 876 10
The Jacobian for the partial derivative coecient is just
and so
Now to nd the change in entropy of this process we just need
to integrate over the changes in pressure and temperature etc.
The typical strategy one uses in solving for the change in a state
function for some irreversible process is to nd a simpler reversible
process which connects the same two end points. In this case the
simplest process (which we have already implicitly chosen since we
derived for constant internal energy is an expansion of our
solid at constant internal energy.
In addition to determining the best specic process to use for the
integration, we also need to know the dependence of the various ma-
terials properties over the range of pressures in the integration. Un-
fortunately we dont have this information. What we do know is that
A good approach here is to look at the integrand and see if some
terms are negligible:
and
Converting units gives

P
P
73
_ _
_
2
2
1
6 1

Example 11

General Procedure
5
4
2
2
( )
2
2
1
2
2
(6 6 ) 1 5 10 ( )
2(300 )
2
C . .
C .
C V T C
C V T .
dS dP
PV .
C K
S dP P P
, atm
S J/K
T K P atm T K
P atm
U P,
T. P T
= 3 876 10 9 869
= 3 8 10
=
=
( )
= 26 4 ( )
(@300 ) = 255( )
= = ( )
=
[ ]
(100 000 )
= 170 17
= 300 = 1 = 350
= 1000
P
J
mol atm K
cc atm
J
P
cc
mol K
P P
P
U
PV C V T
T C PV
atm CC
K
P
atm CC
K
U
P
P
PV
T
V
T
. cc . atm
K
U
cc atm
K
So
since is more than a hundred times larger than Comparing
terms in the denominator of
shows that even at the maximum pressure of 100,000 atmospheres
is still 10 times smaller than
With these comparisons we then make the approximation that
or
where we have assumed that the temperature is nearly constant.
A student studying electromigration problems in alu-
minum (Al) interconnects processes a mole of Al by increasing the
temperature and pressure from and to
and in a pressurized furnace.
independent dependent
The above example is representative of the way the General Pro-
cedure can be used to determine the thermodynamics of a system.
Although we made some assumptions because we didnt know the de-
tails of how the materials properties depended on temperature, this
strategy lead to an explicit answer in a straightforward way. Lets
look at one more example which is even more straightforward than
the last.
a) Estimate the change in internal energy per mole of Al for this
process?
The variable is and the variables are
and Since the independent variables are and we can just use
the table of the summary of thermodynamic functions in the course
notes:
74
2
2
2 2 2
2
2 2
3 3 3
_
_ _
_
_ _
_ _
_ _
_ _
General Procedure

state function
two
not

| |

| |

=0
=0
=0
1000
1
=0
1000
1
1000
1
=0
2
1000
1
1000
1
=0
=0
350
300
=0
350
300
350
300
=0
2
350
300
350
300
=0
6 1
(1000) 1
2
5 1
=0
=0
(350 ) (300 )
2
5 1
=0
=0 =0
dU C PV dT V P T dP
U
dU V P T dP
dU C PV dT
U V P T dP
U V PdP V T dP
U V V TP
dU
U C PV dT
U a bT dT PV dT
U aT PV T
U . atm
K K atm
U .
T K, P atm
U K K .
atm K K K
U
U U U
U .
= ( ) + ( )
= ( )
= ( )
= ( )
=
=
= ( )
= ( + )
= +
= 10 (1 2 10 )
[ ]
(10 ) (300 ) (7 10 ) (1000 1)
= 203 79
= 300 = 1000
= 206 (350 300 ) + 0 12
[ ]
(1000 )(10 ) (7 10 ) (350 300 )
= 12215
= +
= 12215 203 79 = 12011
P
dT
dP P
dT
atm
atm
dT
atm
atm
atm
atm
dT
P atm
atm
atm
atm
dP
dP
K
K
P
dP
K
K
K
K
dP
bT K
K
K
K
dT
cc
mole
atm
cc
mole
dT
atm cc
mole
dP
cc atm
mole K
cc atm
mole K
K K
cc
mole
dP
atm cc
mole
dP dT
atm cm
mole
atm cm
mole
atm cm
mole
Since is a I can break the process of getting the
temperature and pressure changes into steps; a) one isothermal,
and b) the other isobaric and get the same change in internal energy.
For the isothermal step
Here I assume that the compressibility is pressure dependent,
and that the volume change on pressurization is also negligible. I
then get:
To integrate Ill assume volume and the thermal expansion
coecient are approximately temperature independent.
If the isothermal step is rst:
If the isobaric step is carried out second ( )
75
_ _
_ _
_ _
_ _
NOTE
NOTE:
2
2 2
3
2 2 2
3
3 3 3
0
0
General Procedure

=0
(350 ) (300 )
2
5 1
=0
=0
6 1
(1000) 1
2
5 1
=0
=0 =0
0
0
0
0
6 1 5 1
0
=0
1000
1
1000
1
=0
1000
1
0
1000
1
0
U K K .
atm K K K
U .
U . atm
K K atm
U .
U U U
U .
V V T
V V P
V
V
V V P T
. atm atm K K
.
.
dV V dT V dP
V V P T .
U V PdP T V dP
U V P PdP T V P dP
dP
CC atm
mole K
CC atm
mole K
K K
cc
mole
dP
atm cm
mole
dT
cc
mole
atm
cc
mole
dT
atm cm
mole
dP dT
atm cm
mole
atm cm
mole
atm cm
mole
V
V
V
V
dT
atm
atm
atm
atm
dT
atm
atm
atm
atm
= 206 (350 300 ) + 0 12
[ ]
(1 )(10 ) (7 10 ) (350 300 )
= 12250 0
= 10 (1 2 10 )
[ ]
(10 ) (350 ) (7 10 ) (1000 1)
= 238 76
= +
= 12250 238 76 = 12011
= (1 + )
= (1 )
= (1 ) (1 + )
= [1 (1 2 10 ) (999 )] [1 + (7 10 )(50 )]
= 1 0023
0 23%
=
= (1 ) (1 + )
=
= (1 ) (1 )
: If I would have reversed the order of the steps Id get
(hold your breath!):
and
Excellent! This is the same result as we obtained when we had
the isothermal step followed by the isobaric step so we can continue
to believe in the power of state functions.
b) Estimate the percentage change in volume of the Al?
Now if the process occurs by two steps the for the second step
is the at the end of the rst step. So we nd that:
The volume change is approximately
We could have also used
and broken the process up into two steps to get the equation
Check the constant volume approximation: If I would not have
assumed the volume was pressure independent then
76
3 2 2
3
2
3
3

_ _
_ _ _ _ __
_ _
_ _
General Procedure
Chapter 5 Main Points

|

dT
atm
atm
atm
atm
dT
P P P atm
atm
dT
atm cm
mole
dT
atm cm
mole
U
U V P P P dP T V P P dP
U V P TV P P
U .
. U .
U .
. V
T P,
T P
dT dP,

= ( ) ( )
=
= 10(1 2 10 )
300(7 10 ) 10(1 2 10 ) 999 = 1 2095 10
= 203 79
0 023
=0
1000
1
0 0
1000
1
0 0
=0
0
2
3
0
2
0
2
0
1000
1
=0
6
2 (1000)
3
(999)
2
2
5 6 1000
2
1
=0
0
The is dierent from the constant volume assumption by the
integral
which is much smaller than
so the constant volume approximation works well in this case. A
similar treatment can show that the approximation is also good for
the isobaric step. In either case, the result of part (b) that the volume
change is only justies our approximation.
Now although the General Procedure proves very useful and sim-
ple to use, it does not by itself allow us to determine the special state
variable relationships that occur when a material is in equilibrium.
Those relationships are derived in the next section.
The General Procedure can be used to derive the thermody-
namic relationship between any three thermodynamic variables.
The process can be followed step by step, or by using the Jaco-
bian expressions for the necessary partial derivatives.
Often times the partial derivatives that can be derived using
the General Procedure are more easily obtained by using the
Coecient Relations or Maxwell Relations.
In cases were the dependent variable is either or rewrite
the function so that neither or are the independent vari-
able, then use the General Procedure and nally rearrange the
resulting expression for or whichever is the dependent
variable.