1 Thermodynamic Relations

1.1 Relations for Energy Properties

1.1.1 Internal Energy Change dU
From rst law of thermodynamics
dU = dQ+dW (1.1)
For a reversible process
dW = PdV
From second law of thermodynamics for a reversible process
dQ = TdS
Therefore Eqn.(1.1) becomes
dU = TdS PdV (1.2)
1.1.2 Enthapy Change dH
From the denition of enthalpy
H = U +PV (1.3)
Dierentiating
dH = dU +PdV +V dP
Substituting for dU from Eqn.(1.2)
dH = V dP +TdS (1.4)
1.1.3 Gibbs Free Energy Change dG
From the denition of Gibbs free energy
G = H TS
Dierentiating
dG = dH TdS SdT
Substituting for dH from Eqn.(1.4)
dG = V dP SdT (1.5)
1
1.1.4 Helmholtz Free Energy Change dA
From the denition of Helmholtz free energy
A = U TS
Dierentiating
dA = dU TdS SdT
Substituting for dU from Eqn.(1.2)
dA = PdV SdT (1.6)
1.2 Mathamatical Concepts
1.2.1 Exact Dierential Equations
If F = F(x, y) then
dF = Mdx +Ndy
Exactness Criteria:
_
M
y
_
x
=
_
N
x
_
y
If F = F(x, y, z) then
dF = Mdx +Ndy +Pdz
Exactness Criteria:
_
M
y
_
x,z
=
_
N
x
_
y,z
_
M
z
_
x,y
=
_
P
x
_
y,z
_
N
z
_
x,y
=
_
P
y
_
x,z
1.2.2 Cyclic Relation Rule
For the function in the variables x, y & z
_
x
y
_
z
_
y
z
_
x
_
z
x
_
y
= 1
2
1.2.3 Other Relations of Importance
_
z
x
_
y
=
_
z
w
_
y
_
w
x
_
y
_
x
y
_
z
=
1
_
y
x
_
z
1.3 Maxwell Relations
For the fundamental property relations:
dU = TdS PdV
dA = PdV SdT
dG = SdT +V dP
dH = V dP +TdS
Applying exactness criteria of dierential equation:
T V
P S
U G
H
A

d
d
d
d
d
d
ds
PASGVHTU
_
T
V
_
S
=
_
P
S
_
V
_
P
T
_
V
=
_
S
V
_
T
_
S
P
_
T
=
_
V
T
_
P
_
V
S
_
P
=
_
T
P
_
S
1.4 Relations for Thermodynamic Properties in terms
of PV T and Specic heats
1.4.1 Denitions
_
U
T
_
V
= C
V
_
H
T
_
P
= C
P
3
Volume expansivity
=
1
V
_
V
T
_
P
Isothermal compressibility
=
1
V
_
V
P
_
T
1.4.2 Relations for dU
_
U
V
_
T
= T
_
P
T
_
V
P
Considering U = U(T, V )
dU = C
V
dT +
_
T
_
P
T
_
V
P
_
dV
For van der Waals gas,
dU = C
V
dT +
a
V
2
dV
1.4.3 Relations for dH
_
H
P
_
T
= V T
_
V
T
_
P
Considering H = H(T, P)
dH = C
P
dT +
_
V T
_
V
T
_
P
_
dP
1.4.4 Relations for dS
_
S
T
_
V
=
C
V
T
_
S
T
_
P
=
C
P
T
4
Considering S = S(T, V )
dS =
C
V
T
dT +
_
P
T
_
V
dV
For van der Waals gas,
dS =
C
V
T
dT
R
V b
dV
Considering S = S(T, P)
dS =
C
P
T
dT
_
V
T
_
P
dP
1.4.5 Relations for Specic heats
C
P
= T
_
P
T
_
S
_
V
T
_
P
C
V
= T
_
P
T
_
V
_
V
T
_
S
Specic heat dierences:
C
P
C
V
= T
_
P
V
_
T
_
V
T
_
2
P
For van der Waals gas,
C
P
C
V
= T
V
2

Specic heat ratio:

C
P
C
V
=
(P/V )
S
(P/V )
T
Specic heat variations:
_
C
P
P
_
T
= T
_

2
V
T
2
_
P
_
C
V
V
_
T
= T
_

2
P
T
2
_
V
5
1.5 Two-phase Systems
Equilibrium in a closed system of constant composition:
d(nG) = (nV )dP (nS)dT
During phase change T and P remains constant. Therefore, d(nG) = 0.
Since dn = 0, dG = 0.
For two phases and of a pure species coexisting at equilibrium:
G

= G

where G

and G

are the molar Gibbs free energies of the individual phases.

dG

= dG

dP
sat
dT
=
S

1.5.1 Clapeyon equation

dP
sat
dT
=
H

TV

1.5.2 Clausius-Clapeyron equation

ln
P
sat
2
P
sat
1
=
H
R
_
1
T
1

1
T
2
_
1.5.3 Vapor Pressure vs. Temperature
From Clausius-Clapeyron equation
ln P
sat
= A
B
T
A satisfactory relation given by Antoine is of the form
ln P
sat
= A
B
T +C
The values of the constants A, B and C are readily available for many
species.
6
1.6 Gibbs Free Energy as a Generating Function
d
_
G
RT
_
=
1
RT
dG
G
RT
2
dT
Substituting for dG from fundamental property relation, and from the de-
nition of G:
d
_
G
RT
_
=
V
RT
dP
H
RT
2
dT
This is a dimensionless equation.
V
RT
=
_
(G/RT)
P
_
T
H
RT
= T
_
(G/RT)
T
_
P
When G/RT is known as a function of T and P, V/RT and H/RT fol-
low by simple dierentiation. The remaining properties are given by dening
equations.
S
R
=
H
RT

G
RT
U
RT
=
H
RT

PV
RT
1.7 Residual Properties
Any extensive property M is given by:
M = M
ig
+M
R
where M
ig
is ideal gas value of the property, and M
R
is the residual value
of the property.
For example for the extensive property V :
V = V
ig
+V
R
=
RT
P
+V
R
Since V = ZRT/P
V
R
=
RT
P
(Z 1)
7
For Gibbs free enrgy
d
_
G
R
RT
_
=
V
R
RT
dP
H
R
RT
2
dT (1.7)
V
R
RT
=
_
(G
R
/RT)
P
_
T
(1.8)
H
R
RT
= T
_
(G
R
/RT)
T
_
P
(1.9)
From the denition of G:
G
R
= H
R
TS
R
S
R
R
=
H
R
RT

G
R
RT
(1.10)
At constant T Eqn.(1.7) becomes
d
_
G
R
RT
_
=
V
R
RT
dP
Integration from zero pressure to the arbitrary pressure P gives
G
R
RT
=
_
P
0
V
R
RT
dP (const. T) (1.11)
where at the lower limit, we have set G
R
/RT equal to zero on the basis that
the zero-pressure state is an ideal-gas state. (V
R
= 0)
Since V
R
= (RT/P)(Z 1) Eqn.(1.11) becomes
G
R
RT
=
_
P
0
(Z 1)
dP
P
(const. T) (1.12)
Dierentiating Eqn.(1.12) at with respect to T at constant P
_
(G
R
/RT)
T
_
P
=
_
P
0
_
Z
T
_
P
dP
P
H
R
RT
= T
_
P
0
_
Z
T
_
P
dP
P
(const. T) (1.13)
Combining Eqn.(1.12) and (1.13) and from Eqn.(1.10)
S
R
R
= T
_
P
0
_
Z
T
_
P
dP
P

_
P
0
(Z 1)
dP
P
(const. T) (1.14)
8
1.8 Generalized Correlations of Thermodynamic Prop-
erties for Gases
Of the two hinds of data needed for the evaluation of thermodynamic proper-
ties, heat capacities and PV T data, the latter are most frequently missing.
Fortunately, the generalized methods developed for compressibility factor Z
are also applicable to residual properties.
Substituting for P = P
c
P
r
and T = T
c
T
r
,
dP = P
c
dP
r
and dT = T
c
dT
r
H
R
RT
c
= T
2
r
_
Pr
0
_
Z
T
r
_
Pr
dP
r
P
r
(const. T
r
) (1.15)
S
R
R
= T
r
_
Pr
0
_
Z
T
r
_
Pr
dP
r
P
r

_
Pr
0
(Z 1)
dP
r
P
r
(const. T
r
)
(1.16)
1.8.1 Three Parameter Models
From three-parameter corresponding states principle developed by Pitzer
Z = Z
0
+Z
1
Similar equations for H
R
and S
R
are:
H
R
RT
c
=
(H
R
)
0
RT
c
+
(H
R
)
1
RT
c
S
R
R
=
(S
R
)
0
R
+
(S
R
)
1
R
Calculated values of the quantities
(H
R
)
0
RT
c
,
(H
R
)
1
RT
c
,
(S
R
)
0
R
and
(S
R
)
1
R
are shown by plots of these quantities vs. P
r
for various values of T
r
.
(H
R
)
0
RT
c
and
(S
R
)
0
R
used alone provide two-parameter corresponding states
correlations that quickly yield coarse estimates of the residual properties.
9
1.8.2 Correlations from Redlich/Kwong Equation of State
Z =
1
1 h

4.934
T
1.5
r
_
h
1 +h
_
where
h =
0.08664P
r
ZT
r
and
T
r
=
T
T
c
P
r
=
P
P
c
1.9 Developing Tables of Thermodynamic Properties
from Experimental Data
Experimental Data:
(a) Vapor pressure data.
(b) Pressure, specic volume, temperature (PV T) data in the vapor re-
gion.
(c) Density of saturated liquid and the critical pressure and temperature.
(d) Zero pressure specic heat data for the vapor.
From these data, a complete set of thermodynamic tables for the saturated
liquid, saturated vapor, and super-heated vapor can be calculated as per the
steps below:
1. Relation for ln P
sat
vs. T such as
ln P
sat
= A
B
T +C
2. Equation of state for the vapor that accurately represents the PV T
data.
3. State: 1
Fix values for H and S of saturated-liquid at a reference state.
10
4. State: 2
Enthalpy and entropy changes during vaporization are calculated from
Clapeyron equation using the ln P
sat
vs. T data as:
dP
sat
dT
=
H
lv
T(V
v
V
l
)
and
S
lv
=
H
lv
T
Here V
l
shall be measured, and V
v
is calculated from the relation ob-
tained in step-2.
From these values of H
vl
and S
vl
obtaine the values of H and S
at state: 2
11
5. State: 3 Follow the constant pressure line.
dH = C
P
dT +
_
V T
_
V
T
_
P
_
dP
dS = C
P
dT
T

_
V
T
_
P
dP
Here for the specic heat of vapor corresponding to the pressure at
state: 2 is obtained from the relation:
_
C
P
P
_
T
= T
_

2
V
T
2
_
and from the zero pressure specic heat data.
With the value of C
P
for this state as calculated above, S and H
values at state: 3 are calculated.
6. State: 4, 5 & 6 The above calculation can be done along con-
stant temperature lineand the values at states 4, 5 and 6 can be ob-
tained.
7. State: 7 The calculations made for state: 2 can de done for the tem-
perature at state: 6.
12
1.10 Thermodynamic Diagrams of Importance
1.10.1 T S diagram
13
1.10.2 P H diagram
14
1.10.3 H S diagram
15
2 Thermodynamics of Flow Processes
2.1 Conservation of Mass
dm
dt
+ (uA) = 0 (2.1)
where the symbol denotes the dierence between exit and entrance streams.
For steady ow process
(uA)
fs
= 0 (2.2)
Since specic volume is the reciprocal of density,
m =
uA
V
= constant. (2.3)
This is the equation of continuity.
16
2.2 Conservation of Energy
d(mU)
dt
+ [(U +
1
2
u
2
+zg) m] =

Q

W (2.4)
W = W
s
+ [(PV ) m] (2.5)
d(mU)
dt
+ [(H +
1
2
u
2
+zg) m] =

Q

W
s
(2.6)
For most applications, kinetic- and potential-energy changes are negligi-
ble. Therefore
d(mU)
dt
+ (H m) =

Q

W
s
(2.7)
Energy balances for steady state ow processes:
[(H +
1
2
u
2
+zg) m] =

Q

W
s
(2.8)
Bernoullis equation:
P

+
u
2
2
+gz = 0 (2.9)
2.3 Flow in Pipes of Constant Cross-section
H +
u
2
2
= 0 (2.10)
In dierential form
dH = udu (2.11)
Equation of continuity in dierential form:
d(uA/V ) = 0 (2.12)
Since A is a constant, d(u/V ) = 0. Therefore
du
V

udV
V
2
= 0
17
or
du =
udV
V
(const. A) (2.13)
Substituting this in Eqn.(2.11)
dH =
u
2
dV
V
(2.14)
From the fundamental property relations
TdS = dH V dP
Therefore
TdS =
u
2
dV
V
V dP (2.15)
As gas ows along a pipe in the direction of decreasing pressure, its specic
volume increases, and also the velocity (as m = uA/V ). Thus in the
direction of increasing velocity, dP is negative, dV is positive, and the two
terms of Eqn.(2.15) contribute in opposite directions to the entropy change.
According to second law dS 0.
u
2
max
dV
V
+V dP = 0 (const. S)
Rearranging
u
2
max
= V
2
_
P
V
_
S
(2.16)
This is the speed of sound in uid.
2.4 General Relationship between Velocity and Cross-
sectional Area
d(uA/V ) = 0
1
V
(udA+Adu) uA
dV
V
2
= 0
18
or
udA+Adu
uA
=
V dV
V
2
From the fundamental property relation for dH and from steady ow energy
equation
V dP = udu (const. S)
i.e., V = udu/dP at constant S. Therefore
dA
A
+
du
d
=
udu
V
2
(P/V )
S
From the relation for velocity of sound, the above equation becomes
dA
A
+
du
u
=
udu
u
2
sonic
Therefore
dA
A
=
udu
u
2
sonic

du
u
=
_
u
2
u
2
sonic
1
_
du
u
The ratio of actual velocity to the velocity of sound is called the Mach Number
M.
dA
A
= (M
2
1)
du
u
(2.17)
Depending on whether M is greater than unity (supersonic) or less than
unity (subsonic), the cross sectional area increases or decreases with velocity
increase.
includegraphicssupersonic.eps
includegraphicssubsonic.eps
includegraphicsconvergdiverg.eps
2.5 Nozzles
u
2
2
u
2
1
= 2
_
P
2
P
1
V dP =
2P
1
V
1
1
_
1
_
P
2
P
1
_
(1)/
_
(2.18)
19
From the denition of sound velocity
u
2
max
= V
2
_
P
V
_
S
and from the evaluation of the derivative (P/V )
S
for the isentropic ex-
pansion of ideal gas with constant heat capacities from the relation PV

=
const,
u
2
throat
= P
2
V
2
(2.19)
Substituting this value of the throat velocity for u
2
in Eqn.(2.18) and solving
for the pressure ratio with u
1
= 0 gives
P
2
P
1
=
_
2
+ 1
_
/(1)
(2.20)
The speed of sound is attained at the throat of a conerging/diverging nozzle
only when the pressure at the throat is low enough that the critical value
of P
2
/P
1
is reached. If insucient pressure drop is available in the nozzle
for the velocity to become sonic, the diverging section of the nozzle acts as
a diuser.
2.6 Turbines

W
s
= mH (2.21)
20
and
W
s
= H (2.22)
W
s
(isentropic) = (H)
S
(2.23)
=
W
s
W
s
(isentropic)
=
H
(H)
S
(2.24)
2.7 Throttling Processes
H = 0
Joule-Thomson Coecient:

J
=
_
T
P
_
H
=
T(V/T)
P
V
C
P
21
For ideal gases
J
= 0. For a real gas u
J
can be positive, zero or negative.
Any gas for which volume is linear with temperature along an isobar will
have a zero Joule-Thomson coecient. i.e., if V/T = constant = (P),

J
= 0.
Inversion curve: T P diagram. The points in the curve correspond
to
J
= 0. In the region inside the curve
J
is positive.
2.8 Compression
W =
_
P
2
P
1
V dP
For reversible-adiabatic compression
W =
P
1
V
1
1
_
1
_
P
2
P
1
_
1

_
Eect of clearance on work of compression:
W =
P
1
V
I
1
_
1
_
P
2
P
1
_
1

_
22
Multistage compression:
Optimum compression ratio per stage =
_
P
2
P
1
_
1/n
W =
nP
1
V
I
1
_
1
_
P
2
P
1
_
1
n
_
Relation between V
D
and V
I
:
V
I
= V
D
_
1 +C C
_
P
2
P
1
_
1/
_
where C = V
C
/V
D
For compression in multistages,
V
I
= V
D
_
1 +C
1
C
1
_
P
2
P
1
_ 1
n
_
where C
1
is the clearance in the rst stage.
23
2.9 Ejectors
24