UPME ME 267 ENQ 6/2010 1

THERMODYNAMIC RELATIONS



A LITTLE MATHPARTIAL DERIVATIVES AND ASSOCIATED
RELATIONS


For a function z that depends on two independent variables (x,y) such that

( , ) z z x y = (1.1)

its partial derivative
0 0
( , ) ( , )
lim lim
x x
y y
z z z x x y z x y
x x x

+
| | | |
= =
| |

\ . \ .
represents the variation of z with respect to one variable while
holding the other variable constant.

The partial derivative of z with respect to x at constant y is

(1.2)

and the partial derivative of z with respect to y at constant x is


0 0
( , ) ( , )
lim lim
y y
x x
z z z x y y z x y
y y y

| | | | +
= =
| |

\ . \ .
(1.3)



represents the partial differential change
due to the variation of a

single variable

Also note that the value of the partial
derivative

y
z
x

| |
|

\ .


in general, is different at different y values.












UPME ME 267 ENQ 6/2010 2

The total differential

change of a function reflects the influence of all variables.
Specifically, the total differential change in z(x, y) for simultaneous changes in x and y,
is given by




y
x
z z
dz dx dy
x y
| |
| |
= +
| |

\ .
\ .
(1.4)


This is the fundamental relation for the total
differential of a dependent variable in
terms of its partial derivatives with respect to
the independent variables















Note:
The changes indicated by d and are identical for independent variables

, but
not for dependent variables.
For example,
(x)
y
but
= dx
(z)
y
dz = (z)
x
+ (z)
y





UPME ME 267 ENQ 6/2010 3

Partial Differential Relations


If
( , ) z z x y =


is a continuously variable function of (x,y), then its total differential

is

dz M dx N dy = +
(1.5)
where


,
y
x
z z
M N
x y
| |
| |
= =
| |

\ .
\ .
(1.6)

Also, dz is an

exact differential if

2 2
y
x
M z N z
y x y x y x
| |
| |
= = =
| |

\ .
\ .
(1.7)



Reciprocity Relation

( )
1
/
y
y
z
x x z

| |
=
|

\ .
(1.8)



Cyclic Relation

1
y x
z
z x y
x y z
| |
| | | |
=
| | |

\ . \ .
\ .
(1.9)



UPME ME 267 ENQ 6/2010 4


Maxwell Relations


These are equations that relate the partial derivatives of properties P, v, T, and s
of a simple compressible system to each other



s v
T P
v s

| | | |
=
| |

\ . \ .
(1.10)


s P
T v
P s

| | | |
=
| |

\ . \ .
(1.11)


T v
s P
v T

| | | |
=
| |

\ . \ .
(1.12)


T P
s v
P T

| | | |
=
| |

\ . \ .
(1.13)


These are called the Maxwell relations (Fig. 128). They are extremely valuable
in thermodynamics because they provide a means of determining the change in
entropy in terms of changes in properties P, v, and T.

Note that the Maxwell relations given above are limited to

simple compressible
systems.


UPME ME 267 ENQ 6/2010 5

THE CLAPEYRON EQUATION


Enables us to determine the enthalpy change associated with a phase change (such
as the enthalpy of vaporization h
fg

) from a knowledge of P, v, and T data alone.
Example: Vaporization Process at constant pressure and temperature

The development of the enthalpy change relation starts with the 3
rd

Maxwell relation

T v
s P
v T

| | | |
=
| |

\ . \ .
(1.12)

In the case of liquid-vapor phase change or vaporization process,

1. P = P
sat
is a function of T = T
sat
only P
sat
= f(T
sat

)
2. Then

v sat
P P
T T

| | | |
=
| |

\ . \ .
(1.14)

which represents the slope of the saturation line
For the vaporization process (sat. liquid to sat.
vapor, or f g) at a given or constant
temperature,
on a P-T diagram

.
sat
P
const
T
| |
=
|

\ .


so that combining (1.12) and (1.14) gives


g f fg
g f fg sat
s s s
P
T v v v

| |
= =
|

\ .


or




fg fg
sat
P
s v
T

| |
=
|

\ .
(1.15)


The entropy change during vaporization is the product of the change in specific volume
and the slope (P/T) of the vaporization curve at the vaporization temperature T
sat

.


UPME ME 267 ENQ 6/2010 6

The enthalpy change for the process is obtained using the relation

dh = T ds + v dP (1.16)

Since the pressure is constant during vaporization, dP = 0.

Integrating eq. (1.16) noting that T = const. = T
sat

during vaporization,

fg fg
sat
P
h T v
T

| |
=
|

\ .
(1.17)


The Clapeyron equation is applicable to any phase-change process that occurs at
constant temperature and pressure. It can be expressed in a general form as



12
12 sat
h
P
T T v

| |
=
|

\ .
(1.18)


where the subscripts 1 and 2 indicate the two phases.



Some Simplifications:
If all the following conditions exist,

1. At Low Pressures, v
g
>>v
f
so that v
fg
v
g

,
2. and treating the vapor as an ideal gas, v
g

RT/P
3. and for small temperature intervals, h
fg
)
T1
h
fg
)
T2
h
fg

const. ,
then



for liquid-vapor and solid-vapor phase changes.




UPME ME 267 ENQ 6/2010 7


GENERAL RELATIONS FOR du, dh, ds, c
v
, & c
p

IN
TERMS OF P, v, and T

The following discussion presents the development of relations for
calculating changes in internal energy, enthalpy, and entropy

in terms of
the measurable properties pressure, specific volume, temperature, and
specific heats.
Once the state of a system is defined by two independent properties (i.e.,
the state postulate), the other properties may be calculated using the
relations developed here

An expression relating c
p
and c
v

will be developed so that only one of the
specific heats need to be measured the other specific heat is calculated
Property values at specified states can be determined after the selection
of an arbitrary reference state (which has assigned values of properties)


I nt er nal Ener gy Change - du

From the state postulate, let

( , ) u u T v = (1.1)

Its total differential is then

v T
u u
du dT dv
T v

| | | |
= +
| |

\ . \ .
(1.2)

Recall that the definition of the specific heat at constant volume is


v
v
u
c
T

| |

\ .
(1.3)

Substituting (1.3) into (1.2),

v
T
u
du c dT dv
v

| |
= +
|

\ .
(1.4)

In this expression, we want to express
T
u
v
| |
|

\ .
in terms of P, v, T so that we can finally
calculate du in terms of measurable parameters.


Another relationship for du in terms of P, v, T, and s which can be invoked comes
from one of the Gibbs equations:

du T dS P dv = (1.5)

UPME ME 267 ENQ 6/2010 8


We now express dS in terms of P, v, T by letting (using the state postulate)
entropy be a function of the same variables (T, v) as internal energy. Thus

( , ) s s T v = (1.6)

and its total differential is then


v T
s s
ds dT dv
T v

| | | |
= +
| |

\ . \ .
(1.7)

Substituting (1.7) into (1.5) to eliminate ds ,


v T
s s
du T dT dv Pdv
T v
(

| | | |
= +
( | |

\ . \ .


Or

v T
s s
du T dT T P dv
T v
(

| | | |
= +
( | |

\ . \ .

(1.8)

Between eqs. (1.4) and (1.8), the former looks easier to express in terms of P, v, T.
Note that both eqs. (1.8) and (1.4) can independently calculate du which implies that
their RHS are equal. Specifically, the coefficients of dT should be equal; the same is
true for the coefficients of dv . Therefore,


v
v
s
c T
T

| |
=
|

\ .
(1.9)
and

T T
u s
T P
v v

| | | |
=
| |

\ . \ .
(1.10)

Eq. (1.10) is now substituted in eq.(1.4) to obtain


v
T
s
du c dT T P dv
v
| |

| |
= +
| |

\ .
\ .
(1.11)

The partial derivative of entropy in the above equation is then replaced by the Maxwell
relation


T v
s P
v T

| | | |
=
| |

\ . \ .
(1.12)

To finally obtain du in terms of measurable properties P, v, T and c
v

as

UPME ME 267 ENQ 6/2010 9


v
v
P
du c dT T P dv
T
| |

| |
= +
|
|

\ .
\ .
(1.13)

This can be integrated between two states at (T
1
, v
1
) and (T
2
, v
2
) to determine (u
2

u
1

):

2 2
1 1
2 1
T v
v
T v
v
P
u u c dT T P dv
T
(

| |
= +
( |

\ .


(1.14)



UPME ME 267 ENQ 6/2010 10

Ent hal py Change - dh

From the state postulate, let

( , ) h h T P = (1.15)

Its total differential is then

P T
h h
dh dT dP
T P

| | | |
= +
| |

\ . \ .
(1.16)

Recall that the definition of the specific heat at constant pressure is


p
P
h
c
T

| |

\ .
(1.17)

Substituting (1.17) into (1.16),

p
T
h
dh c dT dP
P

| |
= +
|

\ .
(1.18)

In this expression, we want to express
T
h
P
| |
|

\ .
in terms of P, v, T so that we can finally
calculate dh in terms of measurable parameters.


Another relationship for dh in terms of P, v, T, and s which can be invoked comes
from one of the Gibbs equations:

dh T ds v dP = + (1.19)

We now express dS in terms of P, v, T by letting (using the state postulate)
entropy be a function of the same variables (T, P) as enthalpy. Thus

( , ) s s T P = (1.20)

and its total differential is then


P T
s s
ds dT dP
T P

| | | |
= +
| |

\ . \ .
(1.21)

Substituting (1.21) into (1.19) to eliminate ds ,


P T
s s
dh T dT v T dP
T P
(

| | | |
= + +
( | |

\ . \ .

(1.22)




UPME ME 267 ENQ 6/2010 11

Between eqs. (1.18) and (1.22), the former looks easier to express in terms of P, v, T.
Note that both eqs. (1.22) and (1.18) can independently calculate dh which implies
that their RHS are equal. Specifically, the coefficients of dT should be equal; the same
is true for the coefficients of dP . Therefore,


p
P
s
c T
T

| |
=
|

\ .
(1.23)
and

T T
h s
v T
P P

| | | |
= +
| |

\ . \ .
(1.24)

Eq. (1.24) is now substituted into eq.(1.18) to obtain


p
T
s
dh c dT v T dP
P
(

| |
= + +
( |

\ .

(1.25)

The partial derivative of entropy in the above equation is then replaced by the 4
th


Maxwell relation

T P
s v
P T

| | | |
=
| |

\ . \ .
(1.26)

To finally obtain dh in terms of the measurable properties P, v, T and c
p

as

p
P
v
dh c dT v T dP
T
(

| |
= +
( |

\ .

(1.27)

This can be integrated between two states at (T
1
, P
1
) and (T
2
, P
2
) to determine (h
2

h
1

):

2 2
1 1
2 1
T P
p
T P
P
v
h h c dT v T dP
T
(

| |
= +
( |

\ .


(1.28)




UPME ME 267 ENQ 6/2010 12


Ent r opy Change - ds

Two general relations for entropy change of a simple compressible system can be
developed: one in terms of T and v, another in terms of T and P.

1
st

Relation In terms of ( T, v )
Let
( , ) s s T v = (1.29)

its total differential is then


v T
s s
ds dT dv
T v

| | | |
= +
| |

\ . \ .
(1.30)

From the development of a general relation for du, where u = u(T,v), it has been shown
that

v
v
c s
T T

| |
=
|

\ .
(1.31)
Also from the 3
rd

Maxwell relation

T v
s P
v T

| | | |
=
| |

\ . \ .
(1.32)

Substituting (1.31) and (1.32) into (1.30) yields


v
v
c
P
ds dT dv
T T

| |
= +
|

\ .
(1.33)
or


2 2
1 1
2 1
T
T
v
v
v
v
P
T
c
s dT dv
T
s

| |
=
|
\ .
+

(1.34)



UPME ME 267 ENQ 6/2010 13

2
nd

Relation In terms of ( T, P )
Let
( , ) s s T P = (1.35)

its total differential is then


P T
s s
ds dT dP
T P

| | | |
= +
| |

\ . \ .
(1.36)

From the development of a general relation for dh, where h = h(T,P), it has been
shown that

P
P
c s
T T

| |
=
|

\ .
(1.37)
Also from the 4
th

Maxwell relation

P P
s v
T T

| | | |
=
| |

\ . \ .
(1.38)

Substituting (1.37) and (1.38) into (1.36) yields


P
P
c
v
ds dT dP
T T

| |
=
|

\ .
(1.39)
or


2 2
1 1
2 1
T P
T P
P
P
v
T
c
s dT dP
T
s

| |
=
|
\ .

(1.40)




UPME ME 267 ENQ 6/2010 14

Rel at i ons f or Spec i f i c Heat s c
v
and c
p


For a general pure substance the specific heats depend on pressure or specific volume
as well as temperature.

Relation Between Zero Pressure (or Ideal Gas) Specific Heats and Higher
Pressure

Specific Heats
Recall that ideal gas specific heats c
v0
and c
p0

, which are easier to determine, are
valid for low pressures or high specific volume
A relation for relating ideal gas specific heats to those at higher pressures can be
developed as follows:

Consider the two relations for entropy change derived previously which contain
specific heats in the equations,

v
v
c
P
ds dT dv
T T

| |
= +
|

\ .
(1.33)

P
P
c
v
ds dT dP
T T

| |
=
|

\ .
(1.39)
Applying the test for exactness

y
x
M N
y x
| |
| |
=
| |

\ .
\ .

for a differential
dz M dx N dy = +
on eqs. (1.33) and (1.39) give


2
2
v
v T
c
P
T
v T

| | | |
=
| |

\ . \ .
(1.41)
and

2
2
p
P
T
c
v
T
P T

| |
| |
=
|
|
|

\ .
\ .
(1.42)

The deviation of c
p
from c
p0
with increasing pressure can be determined by
integrating eq.(1.42) from zero pressure to any pressure P along a constant-
temperature process

. Thus

( )
2
2
0
0
P
p p
T
P
v
T
c dP c T

| |
=
|
\ .

(1.43)

The P-v-T behavior of the substance is necessary to integrate the RHS of the above
equation.

UPME ME 267 ENQ 6/2010 15


Relation Between c
p
and c
v


A relation between c
p
and c
v
will be advantageous since only one of the two specific
heats needs to be measured (usually c
p

) and the other just calculated.
The relation between c
p
and c
v

is developed by equating the two entropy change
relations derived earlier
v
v
c
P
ds dT dv
T T

| |
= +
|

\ .
(1.33)

P
P
c
v
ds dT dP
T T

| |
=
|

\ .
(1.39)
and solved for dT so that

( ) ( )
/ /
v P
p v p v
T P T T v T
dT dv dP
c c c c

= +

(1.44)

This suggests that
( , ) T T v P = (1.45)
and

P v
T T
dT dv dP
v P

| | | |
= +
| |

\ . \ .
(1.46)

Equating the coefficients of dv or dP of eqs.(1.44) and (1.46) gives


p v
P v
v P
c c T
T T

| | | |
=
| |

\ . \ .
(1.47)


Another version of this equation which can be expressed in terms of the thermodynamic
properties volume expansivity and isothermal compressibility is obtained using
the cyclic relation applied to the P-v-T behavior of a substance:


1
v P T
P T v
T v P

| | | | | |
=
| | |

\ . \ . \ .

or

v P T
P v P
T T v
| | | | | |
=
| | |

\ . \ . \ .
(1.48)

Substituting eq. (1.48) into (1.47),


2
p v
P T
v P
c c T
T v

| | | |
=
| |

\ . \ .
(1.49)


UPME ME 267 ENQ 6/2010 16

Recalling the definitions
Volume Expansivity
1
P
v
v T

| |
=
|

\ .
(1.50)
and
Isothermal Compressibilty
1
T
v
v P

| |
=
|

\ .
(1.51)
and substituting these into eq.(1.49) gives


2
p v
vT
c c

=
(1.52)


Notes:
1. Since is positive for all substances in all phases and
2

is also always
positive, then
p v
c c
(1.53)

2. c
p
approaches c
v

as the temperature approaches absolute zero.
3. For incompressible substances, i.e., v = const., c
p
c
v

. The differences
are usually neglected for solids and liquids.



UPME ME 267 ENQ 6/2010 17

THE JOULE-THOMPSON COEFFICIENT

The J oule-Thomson coefficient is a measure of the change in temperature
with pressure during a constant-enthalpy process.


h
T
P

| |
=
|

\ .
(1.54)


A careful look at its defining equation reveals that
the J oule-Thomson coefficient represents the
slope of h =constant lines on a T-P diagram



A throttling process proceeds along a constant-
enthalpy line in the direction of decreasing
pressure, that is, from right to left.




Only some
a point of zero slope or zero J oule-Thomson
of the constant-enthalpy lines have
coefficient.

The line that passes through these points is
called the Inversion Line, and the temperature at a
point where a constant-enthalpy line intersects the
inversion line is called the inversion temperature.

During a throttling process, the temperature
increases on the right-hand side of the inversion
line, decreases on the left-hand side of the
inversion line.

It is clear from this diagram that a cooling effect
cannot be achieved by throttling unless the fluid is
below its Maximum inversion temperature.








UPME ME 267 ENQ 6/2010 18


An expression for the J oule-Thompson coefficient in terms of P-v-T can be developed
from the relation for dh


p
P
v
dh c dT v T dP
T
(

| |
= +
( |

\ .

(1.55)

Noting that dh = 0 for a throttling process, this equation after re-arrangement becomes


1
JT
P h
v
v T
v T
c T P

(

| | | |
= =
( | |

\ . \ .

(1.56)



UPME ME 267 ENQ 6/2010 19

GENERAL RELATIONS FOR du, dh, & ds OF REAL
GASES

Real gas behavior deviates significantly from ideal gas behavior at higher pressures.
The deviation from ideal gas behavior should be accounted for in the calculation of dh,
du, & ds for real (non-ideal) gases. The approach taken to accomplish this is the use of
the relations developed earlier for ideal gases together with the compressibility factor Z
to account for the real gas (or deviation from ideal gas) behavior.


Real Gas Ent hal py Change - dh

For a real gas actual process 1 2, the
calculation of dh is carried out along a series
of imaginary processes 1 1* - 2* - 2
starting and ending at the same states as the
actual process.

These processes are:

1 1* isothermal process from actual
initial pressure to zero pressure

1* - 2* isobaric process with change in
temperature, ideal gas behavior

2* - 2 isothermal process from zero
pressure to actual final pressure




Although these series of processes is more complicated than the actual process, the
calculations are greatly simplified because one property remains constant in any
segment of the entire process.

The general relation


2 2
1 1
2 1
T P
p
P T P
v
h h c dT v T dP
T
(
| |
= +
| (

\ .


(1.57)


is applied to process 1 1* - 2* - 2 .


UPME ME 267 ENQ 6/2010 20

Thus,

( ) ( ) ( )
* * * *
2 1 2 2 2 1 1 1
h h h h h h h h = + +
(1.58)

where


2 2
2 0
2
2
*
*
2 2
0
P P
P P P P
T T
T T
v v
h h v T dP v T dP
T T
=
=
( (
| | | |
= + =
| | ( (

\ . \ .


(1.59)

2 2
1 1
* *
2 1 0
0 ( )
T T
p p
T T
h h c dT c T dT = + =

(1.60)


1 1
1 0
1
1
*
*
1 1
0
P P
P P P P
T T
T T
v v
h h v T dP v T dP
T T
=
=
( (
| | | |
= + =
| | ( (

\ . \ .


(1.61)


Now define

Enthalpy Departure = ( h* - h )
T


= the difference in enthalpy of a real gas at ( P, T ) and ideal
gas at ( P
0
, T ) , where P
0

zero pressure
For a real gas with compressibility factor Z ,


/ v ZRT P =


The enthalpy departure at any temperature T and pressure P can be expressed as

( )
* 2
0
P
T
P
Z dP
h h RT
T P

| |
=
|

\ .

(1.62)



By expressing the pressure and temperature P and T in terms of the reduced properties

P = P
cr
P
R
and T = T
cr
T
R




UPME ME 267 ENQ 6/2010 21

the enthalpy departure can be expressed in non-dimensional form called

Enthalpy Departure Factor


( )
( )
*
2
0
ln
R
R
P
h R R
u cr R
P
h h
Z
Z T d P
R T T

| |
= =
|

\ .

(1.63)

The integral on the RHS of the above equation can be evaluated graphically or
numerically using data from the compressibility charts.

A plot of Z
h
=Z
h
( P
R
, T
R

) is known as the Generalized Enthalpy Departure
Chart and is used to evaluate enthalpy departure of a real gas at an actual
temperature T and pressure P.
The enthalpy change of a real gas from (T
1
, P
1
) to (T
2
, P
2

) on a molar basis is then

( )
( )
2 1 2 1 2 1 u cr h h
ideal
h h h h R T Z Z =
(1.64)

or on a mass basis,

( )
( )
2 1 2 1 2 1 cr h h
ideal
h h h h RT Z Z =
(1.65)

where

(h
2
h
1
)
ideal
is evaluated using ideal gas behavior from T
1
to T
2

.



Real Gas I nt er nal Ener gy Change - du

The change in internal energy of a real gas is calculated from the change in enthalpy.
Thus,

( )
( )
2 1 2 1 2 2 1 1 u
u u h h R Z T Z T =
(1.66)



UPME ME 267 ENQ 6/2010 22






UPME ME 267 ENQ 6/2010 23

Real Gas Ent r opy Change - ds

Because of the dependence of ideal gas entropy change on both pressure and
temperature, a pathway similar to enthalpy change calculation cannot be applied for
entropy change because it involves the value of entropy at zero pressure, which is
infinity.

The pathway chosen for calculating entropy
change from (P
1
, T
1
) to (P
2
, T
2

) is shown
in the figure.
1 a* - 1* - 2* - b* - 2 .

where

* indicates ideal gas state

P
*
1
= P
1
T
*
1
= T
1
P

*
2
= P
2
T
*
2
= T
2
P

0

zero pressure (ideal gas conditions)
1 1* , isothermal process
2 2* , isothermal process
1* - 2* , ideal gas behavior




The entropy change from (P
1
, T
1
) to (P
2
, T
2

) is then


The entropy difference (s s

) between the actual state at (P, T) and the

corresponding ideal gas state at the same pressure and temperature (P

=P, T

=T)
is called the Entropy Departure at (P, T) which can be expressed as


If the specific volume for the real gas and ideal gas are respectively


ZRT
v
P
= and
RT
v
P
=



UPME ME 267 ENQ 6/2010 24

the entropy departure can be expressed as


By expressing temperature and pressure in terms of reduced properties

T =T
cr
T
R
and P =P
cr
P
R


the entropy departure can be expressed in non-dimensional form called the Entropy
Departure Factor as



Values of Z
s
as a function of P
R
and T
R
are shown in the Generalized Entropy
Departure Chart. Note that Z
s

=1 for an ideal gas.
The entropy change of a real gas from state (P
1
, T
1
) to (P
2
, T
2

) on a molal or mass
basis respectively is therefore






UPME ME 267 ENQ 6/2010 25