vapour of Vol
g
T
g
liquid of Vol
f
T
f
T
mixture
T
vapour of Vol
g g
liquid of Vol
f f mixture
v
m
m
v
m
m
v
m
V
gives m by and
v m v m V
,
,
+ = =
+ =
fg
v
f g f
g f
v v x v
xv v x v or
) (
) 1 (
+ =
+ =
(3.3)
Chapter3ME2121/E,August2013,KCNg Page4
Thus,
fg fg
v to compared small
f
v
v
v
v v
x ~
= (3.4)
For example, at low pressure, v =1.2 m
3
/kg
and v
f
=0.001 m
3
/kg (density of water is 1000
kg/m
3
), thus, v
f
<<<v.
However, the same argument cannot be applied
to the other properties such as internal energy,
enthalpy or entropy. In a mixture, h
f
,
may not
significantly smaller than h
g,
i.e.,
fg f g f
xh h xh h x h + = + = ) 1 ( (3.5)
The internal energy and entropy of a mixture
are respectively given by
fg f g f
xu u xu u x u + = + = ) 1 (
And the entropy (s) is given by
fg f g f
xs s xs s x s + = + = ) 1 ( (3.6)
Using the linear rule, the quality (x), can also
be obtained from other given values of u, or h
or s., e.g.,
fg
f
fg
f
fg
f
u
u u
h
h h
s
s s
x
=
= (3.7)
Example 3.1
Find the states of watersteam mixture for the
following given conditions:
(a) t =34
o
C, v =26.6 m
3
/kg,
(b) P =0.8 bar, t =100
o
C
(c) P =2.7 bar, x =0.5.
Solutions
 Referring to the Table of saturated
steam and water (pg.2), the column 1 is
the temperature of mixtures in
o
C, and
column 3 is the specific volume at dry
saturated vapour.
 At v =26.6 m
3
/kg, we note that t of
steam/water is 34
o
C. Thus, we conclude
that the state point sits on the dry
saturated vapour line or the g line,
shown below.
(b)
At P =0.8 bar, t =100
o
C,
 Look up page 3 of Table where column
1 is the saturated pressure, and at 0.8
bar, the corresponding temperature is
only 93.5
o
C.
 This temperature is found to be less
than 100
o
C (given), thus, we conclude
that the steam is superheated (that is,
temperature of state higher than the
saturated temperature).
(d) At P =2.7 bar,
 v
f
=0.00107 m
3
/kg (pg. 10 of Table).,
v
g
=0.6686 m
3
/kg (pg.4),
 we note that 2.7 bar is very much lower
than P
cr
=221 bar, thus, v
f
<<<v
g.,
and
T
sat
=130
o
C.
t
v
V=26 m
3
/kg
34
o
C
gline fline
Critical pt
t
v=2.087m
3
/kg
100
o
C
gline
fline
Critical pt P=0.8 bar
T
sat
=93.5
o
C
Superheated state
Chapter3ME2121/E,August2013,KCNg Page5
 by definition, any other properties could
be found;

fg f
fg
f
fg
f
fg
f
fg
f
u u u
u
u u
u
u u
h
h h
s
s s
x
5 . 0 5 . 0 + =
=
 In this region (L+V), P & T are no
longer independent.
Interpolation
When the states of a point fall outside the
tabulated values in the Tables, an interpolation
technique may be needed. For example,
 To interpolate for v at pressure (P)
when values of v
1
and v
2
are available
from the Tables at P
1
and P
2
.
 ( )
1 2
1 2
1
1
) ( v v
P P
P P
v P at v


.

\

+ =
Sometimes, a double interpolation may be
needed when values on P
1
and P
2
are not
readily available from the tables.
Example 3.2
Find the specific volume of steam for P =2.5
MPa, and t = 275
o
C.
Solution
 The state of the steam is superheated.
Use superheated tables on page 7.
 Values of specific volumes at P =20
and t=250
o
C, 300
o
C are available and
also at 30 bars (t=250 and 300
o
C).
 It is easier to make a tabulation
containing the boundary values as
shown below.
v (m
3
/kg) P=20
bar
P=25 bar P=30
bar
t = 250
o
C
0.1115
m
3
/kg
0.0706
m
3
/kg
t =275
o
C 0.1185
Values to be
determined
=(0.1185+0.0759)/2
=0.0972
0.0759
t =300
o
C 0.1255 0.0812
Gaseous Phase
The state of a gas can be determined from the
key properties such as pressure (P),
temperature (T), specific volume (v) and the
amount of gas (mass (m) or moles (n)) in a
defined volume (V).
 The equation relating these properties
of a gas is called the equation of state
(EOS),
 Experiments have been conducted to
evaluate how these variables are related.
For an ideal gas, the EOS is
) tan (
lim
t cons a R
Tm
PV
=

.

\

(3.8)
where m is the mass in kg, R= 8314.5/M,
(8314.5) is the universal gas constant (R
o
) in
J /kmol.K, M is the molecular mass (kg/kmol).
Note: kg is the basic mass units. Equation 3.8
is also known as the ideal gas behaviour.
t
v
V=26 m
3
/kg
130
o
C
gline fline
Critical pt
P=2.7 bar
X=0.5
L+V
Sp volume to be obtained
gline
fline
Critical pt
P
2
L+V
P
1
P
v
v
2
v
1
t
Chapter3ME2121/E,August2013,KCNg Page6
 If the amount of substance for a gas in a
defined volume is measured in moles,
K kmol kJ or K mol J
t cons gas universal R
Tn
PV
o
. / 314 . 8 ) . / 314 . 8
tan (
lim
=

.

\

(3.9)
Note the right hand side is R
o
. You recalled that
a mol is the basic quantity of substance whose
mass is equivalent to its molecular mass. E.g.,
1 mol of carbon has a mass of 12 gm or 1 kmol
of carbon has 12 kg.
For ideal gas at STP (standard temperature and
pressure), the Avogadros number gives the
number of gas molecules per kmol , i.e.,
N
o
=6.02205 10
26
molecules / kmol
or 6.02205 10
23
molecules per mol.
Thus, the mass of a substance is related to the
mols by multiplying it with the molar mass,
m =nM (3.10)
whilst the mass of one molecule (m
*
) will be
given by
m
*
=M / N
o.
(3.11)
Working forms of Ideal Gas equation
The ideal gas equation (EOS) can have the
following forms:
 PV =mRT mass or gravimetric
basis
 PV =nR
o
T molar basis,
 Pv =R
o
T molar volume v =V/n,
In reality, no gas behaves like an ideal gas (it is
only a convenient approximation). A measure
of the deviation of a real gas from the ideal gas
is given by another property, called gas
compressibility, Z
RT
Pv
Z = (3.12)
At low pressures (with respect tp critical
pressure) and high temperatures, Z tends to
1(unity). A graphical depiction of how Z varies
with T and P is shown below.
For the behaviour of real gases, several
methods are available. The compressibility Z
can be expanded in a power series in density
(the reciprocal of specific volume v) to give
 +  + + + + = =
3 2
1
v
D
v
C
v
B
RT
Pv
Z (3.13)
where B,C, D are called the second, third
virialcoefficients that are function of
temperature (as well as the composition for
mixtures). An alternative expression for the
virial equation is a power series expansion in
pressure:
( )  +  + + +

.

\

=
2
/ ) ( / ) ( 1 v T C v T B
v
R
T
P
(3.13a)
Z=Pv/RT
1.0
P
r
=P/ P
cr
T
r
=1.0
T
r
=1.5
T
r
=10
5 10
T
r
=T/T
cr
Chapter3ME2121/E,August2013,KCNg Page7
Comparing term for term for 3.13 and 3.13a, it
is noted that B and C are function of
temperature (T).
Van der Waals Model:
A more widely used equation for real gas is the
correlation given by van del Waals (in 1837),
where the intermolecular forces or attractions,
(
2
/v a ), and the presence or effect of gas
molecules on (b)  the free volume, are both
accounted for and the correlation is
( ) T R b v
v
a
P
o
= 
.

\

+
2
(3.14)
where
2
/v a adds to the pressure P due to
molecular interactions from per mole of
molecules, and ( ) b v represents the free
volume available to each mole of the
substance. However, these empirical equations
do have short comings when depicting the
behaviour of condensable fluids, as shown
below.
In the liquid+vapor (L+V) region, such a
correlation does not fit well with under
prediction on the f line and over predicting
nearer to the gline. At the critical point, there
is an inflection point at the isotherm (T
c
) where
the following mathematical conditions apply:
0
2
2
=


.

\

c
c
= 
.

\

c
c
C
C T
T v
P
v
P
Thus, at the critical point, equation 3.14 can
also be arranged as
( )
2
c c
c o
c
v
a
b v
T R
P
=
Differentiating,
( )
3 2
2
0
c
c
c o
T
c
v
a
b v
T R
v
P
C
+
= = 
.

\

c
c
and
( )
4 3 2
2
6 2
0
c
c
c o
T
c
v
a
b v
T R
v
P
C
= =


.

\

c
c
If we multiply the former by 2 and the latter by
( ) b v and then add together, we have
( )
4 3
) ( 6 4
0
c
c
c
v
b v a
v
a
=
( )
3
) ( 6
4
c
c
c v
b or
v
b v
=
= .
Substitute back, we solve for a:
c o
c T R v a
8
9
= .
Rewriting the van der Waals equation at
critical point,
( )
2
c c
c o
c
v
a
b v
T R
P
= or
( )
.
8
3
)
8
9
8
12
(
.
8
9
2
3
= =
=
=
c o
c
c
c
c o
c
c o
c
v
c
c o
c
T R
v P
z
v
T R
v
T R v
v
T R
P
c
which is the compressibility factor (z) of the
real gas at its critical state (P
c
,
T
c
).
P
2
v
L+V
( ) ( ) 0
2
2
=
c
c
=
c
c
C
T V
P
C
T V
P
T
T
C
Chapter3ME2121/E,August2013,KCNg Page8
Example 3.3
Calculate the van der Waals parameters (a and
b) for the following gases with the
experimental values at the critical point:
Gases P
c
(bar) T
c
(K)
Benzene 49.1 562
Water 221.2 647.3
Take R
o
=8.3144 J /mol.K.
We write the van der Waals equation in another
form (i.e., as a cubic equation):
0
2
3
= +
(
+
P
ab
v
P
a
v b
P
T R
v
o
And at the critical point,
0
2
3
= +
(
+
c c c
c o
P
ab
v
P
a
v b
P
T R
v
(3.15)
At the critical point, the three roots (solutions)
of the cubic equation must converge, that is
( ) 0
3
=
c
v v
And expanding the cubic equation, we have
0 3 3
3 2
2
3
= +
c c c
v v v v v v (3.16)
Comparing equations (3.15) and (3.16) for the
roots (solution) of v,
The root of zero order: ( )
3
c
c
v
P
ab
= , (3.17)
The root of 1
st
order : ( )
2
3
c
c
v
P
a
= , (3.18)
The root of 2
nd
order: ( )
c
c
c
v b
P
RT
3 = + (3.19)
From (3.18), we have
( )
c c
P v a
2
3 = ,
and from (3,17) we have
( )
( )
( )
3
3
2
3
c
c c
c c
v
P v
P v
b = = .
Also, from 3.19, substitute for a, b and obtain
( )
c
c o
c
P
T R
v
8
3
= . Now, substitute v
c
into a and b
gives
( )
c
c o
P
T R
a
2
64
27
= , and
( )
c
c o
P
T R
b
8
= .
Now, substitute into the tables for a and b gives
Gases P
c
(bar)
or 10
5
Pa
T
c
(K)
( )
c
P
c
T
o
R
a
2
64
27
=
[J m
3
/ mol
2
].
( )
c
c o
P
T R
b
8
=
[m
3
/mol]
Benzene 49.1 562 ( )
5
10 1 . 49
2
562 314 . 8
64
27
x
x
a =
=1.875
( )
5
10 1 . 49 8
562 314 . 8
x x
x
b =
1.19 x10
4
Water 221.2 647.3 =0.552 3.04 x10
5
Note: Parameter a indicates the dispersion interactions,
and parameter b is affected by size of molecules or the
occupied volume per mol.
Example 3.4
A virial equation of state of a gas is given by
( )  +  + + +

.

\

=
2
/ ) ( / ) ( 1 v T C v T B
v
R
T
P
where B(T), C(T) etc., are functions of
temperature only.
Find the expressions for the virial coefficients
for gases that obey
(a) the ideal gas relation, and
(b) the van der Waals equation.
Solution:
(a) For the ideal gas, P/T =R/v, thus B(T)
=0, and C(T)=0 for the equation to
revert to ideal gas.
(b) For the van der Waals equation, the
relation is
( ) v
a
v
b
RT Pv or
T v
a
b v
R
T
P

.

\

=
=
1
2
1
Expanding using the binomial series,
  + 
.

\

+ + = 
.

\

2 1
1 1
v
b
v
b
v
b
Chapter3ME2121/E,August2013,KCNg Page9
Substitute and rearranging, we have




.

\

 +




.

\

+


.

\


.

\

+ =


.

\

 + 
.

\



.

\

+ + =
2
) (
2
) (
2
2
1
1
1
1
v
b
RT
a
b
v v
R
RT v
a
v
b
v
b
v
R
T
P
T C
T B
Thus, the equivalent coefficients of the virial
equation of van der Waals become
B(T) = 
.

\

RT
a
b and C(T) =b
2
.
Home assignment #2 (Submit to your Tutor in
two weeks.)
The functional forms of the van der Waals
equation can be expressed as follows:
1) ( )
( )
2 2
v
a
b v
T R
P or T R b v
v
a
P
o
o
= =


.

\

+ ,
2)
( )
o
R
b v
v
a
P T


.

\

+ =
2
3) 0
2
3
= +
(
+
P
ab
v
P
a
v b
P
T R
v
o
Using mathematics, show that the variables
used in the van der Waals equation of real gas
satisfying requirements of thermodynamic
properties, i.e., the exactness and independency
tests.
Tutorial no. 2 (Chapter 3 2011)
Q1. The table gives the properties of water
under five sets of conditions. Use the steam
tables to compute for the missing properties as
per tabulation.
State P
(bar)
T
(C)
v
(m3/kg)
Dryness
Fraction,
x, ()
1 26 226 0.05 ??
2 ?? 300 ?? 0.8
3 15 325 ?? ??
4 ?? 275 0.2 ??
5 128 ?? ?? 0.6
(You steam tables to find the answer and some state may
require double interpolation)
[1: x
1
=0.6447; 2:P=85.9 bar, v=0.0176 m
3
/kg; 3: v=0.1787
m
3
/kg, x =1; 4:P=12.68 bar, x=1; 5: T=329.6
o
C, v=0.00847
m
3
/kg]
Q2. An industrial boiler is fitted with a sight
glass device to indicate its level of liquid and
the boiler contains saturated steam at 200C.
During the routine "blowdown" procedure,
liquid water is purged from the bottom (mud
drum) at a slow rate, and the temperature in the
boiler remains constant during this process. If
the crosssectional area of the boiler is 2.5 m2
(assumed constant), and the level of the liquid
drops by 150 mm, determine the mass of liquid
withdrawn.
(You may decouple the blowdown process
first consider the amount of water removed
(v
f
dV), and then the void left behind is filled
with vapour (steam). The amount of vapour is
obtained from the water removed).
Liquid
Steam
blowdown
T
sat
=200
o
C
Chapter3ME2121/E,August2013,KCNg Page10
[Ans: m
liquid
removed =(324.12.945) =321.15 kg]
Q3. Water is contained in a cylinder fitted with
a frictionless piston. The mass of water is 1.05
kg and the area of piston is 0.5 m
2
. At the initial
stage, the water is at 110C with a quality
(dryness fraction) of 0.90, and the spring just
touches the piston (exerts no force).
Now heat is transferred to the water and the
piston begins to rise. During this process, the
resisting force on the spring is proportional to
the distance moved, with a force (stiffness) of k
=10 N/mm.
(a) Sketch this heating process on a Pv
diagram for water,
(b) Obtain expressions for P and V of the
contents in the cylinder when the piston moves
by z meters,
(c) Calculate the pressure in the cylinder when
the temperature reaches 200C.
(This problem coupled the pistoncylinder to a mechanical
spring. The spring provides a resisting force on the piston).
[Ans: P
2
P
1
=km (v
2
v
1
)/A
2
; P =1.56 bar, v
=1.391 m
3
/kg]
{ideal gas problem]
Q4. A rigid vessel (A) is connected to a
spherical elastic balloon (B). Both the vessel
and balloon contain air at the ambient
temperature of 25C. The volume of vessel A
is 0.1 m
3
and the initial pressure is 300 kPa.
The initial diameter of the balloon B is 0.5 m
and the pressure inside is 100 kPa. The valve
connecting A and B is now opened and remains
open, and the final temperature of air is
uniform at 25C.
Determine the final pressure in the system, the
final volume and the mass of air in the balloon.
It may be assumed that the pressure inside the
balloon is directly proportional to its diameter.
[Ans: k
B
=200 kN/m; P
B
=200 D
B,2
(kN); D
B,2
=0.683 m, V
B,2
=0.167
m
3
].
Q5. One kg of air is trapped in a cylinder
behind a frictionless piston. The initial
temperature of air is 50C and the density of air
is 1.08 kg/m
3
. The air is compressed until the
volume is 1/6 of the initial volume and the
absolute pressure at the end of compression is
700 kPa.
Calculate the initial volume and pressure of the
air, and the final temperature of the air.
If the volume is held fixed and temperature of
the air reduced to 50C by cooling, find the
final pressure of the air.
Indicate these processes on a Pv diagram.
Assume that the molecular mass of air is 29
kg/kmol and R
0
=8.3143 kJ /kmol.K.
[Ans: P
1
=1 bar; T
2
=376.7 K, P
3
=6 bar]

Explanatory notes for Q2.:
This question tests on the definition of specific
volume, i.e., ). (
3
kg
m
m
V
v = The drop in water
level in the boiler represents the spaces to be
occupied by steam that has to be evaporated at
the same pressure and temperature from the
liquid. It also trains you how to read steam
tables.
Explanatory notes for Q3.:
Area of piston (A) =0.5 m
2
.,
Spring stiffness, k =10 N/mm or kN/m (SI
units), Mass of piston =M (kg).
Final state
Z
2
Vapor +liquid
Completely
Vapor
Initial states
Heat
addition
Piston, Mass=
M
Z
1
Spring is
compressed
Chapter3ME2121/E,August2013,KCNg Page11
This problem involves a real fluid such as
steam, and thus one must use the tables for
accurate computation of fluid properties.
(should you use the ideal gas equation for the
equation of state, errors would be larger.)
Initial states (1): T
1
=110
o
C, m
1
=1.05 kg,
No force exerted by spring at the initial
condition, P
1
= P
sat
., x
1
=0.9, v
1
~x
1
(v
g1
)
valid for low steam pressure.
Final states (2): T
2
=200
o
C,
Solution steps:
Taking aforce balance on the piston;
force Spring
SF A
o
P Mg A P + + =
1
(E1)
After the addition of heat to the vapour+liquid
mixtures, the piston expands and all liquid
evaporated with increasing pressure within the
cylinder (P
2
) and temperature (T
2
). Taking a
force balance again on the piston, noting that
volume change from the initial state
) (
1 2 1 2
Z Z A V V V = = A and using the
definition of specific volume, i.e.,
( ) ) (
1 2 1 2 1 2
Z Z A v v m V V = = , gives
mx C y or
v
A
km
A
v km
P P
or
A
v v km
P P
A
v v km
A P A P
Z k A
o
P Mg A P
force Spring
force Spring
A P
+ =

.

\

+ 
.

\

=
+ =
+ =
A + + =
) (
) (
2
) (
2
) (
2
2
2
2 2
1
1
2
1 2
1
1 2
1
1
(E2)
Thus, we obtain a straight line relation for P
2
in
terms of P
1,
A, k, m and v, which are properties
of the pistoncylinder assembly. Note that v
1
can be read off the steam tables at the initial
conditions. As only the final temperature (T
2
) is
known, one has to use the superheated tables to
plot out an isotherm (T=200
o
C) in a P versus v
graphical plot. Using the P
2
equation (as in
equation (E2)) and using the same range of v
2
,
the two lines (isotherm and the straight line of
P
2
) to intersect for the roots (solutions, as
shown below using a graphical method).
Alternatively, we can approach from
mechanics point of view:
( ) ( )
diagram PV under WD
gravity against WD
o
spring by WD
V V
P P
Z A P Mg Z k ) (
2
) (
2
1
1 2
1 2
2
+
= A + + A
And
( ) ) (
1 2 1 2 1 2
Z Z A v v m V V = =
A P
A
o
P Mg A P
1
1
+ = .
From which we get
2
1 2
1
) (
2
A
v v km
P P
=
Explanatory notes for Q4
The balloon has a certain amount of stiffness
(like a spring of stiffness k) where it is stated
that the pressure in the balloon is proportional
to the diameter:
m
Pa
D
P
k or D P ) 10 ( 2
5 . 0
) 10 ( 100
5
3
= = = .
=0
1.56 bar
Intersection of two lines gives the answer.
1.391 m
3
/kg
Equation E2
P
V
Values taken from steam
tables at 200
o
C
Chapter3ME2121/E,August2013,KCNg Page12
The total mass in the system remains
unchanged before (state 1) and after (state 2)
the valve was opened.
state final
B A total
state Initial
B A
m m m m m
2 2 1 1
+ = = +
where A and B denotes the vessel and the
balloon, respectively, and the subscripts 1 and
2 refer to the initial and final states.
(iii) Note the ideal gas equation for mass of
matter, m =PV/RT.
(iv) Volume of a sphere is give by
3
6
D V
t
= .
Explanatory notes for Q5
Applying the Equation of state (EOS):
State 1: V
1
is determined.
15 . 323 287 1
1
??
1
T R m V P
bar
=
State 2: V
2
=V
1
/6, P
2
=7 bar,
T
2 =
P
2
V
2
/mR
=(7x10
5
x 0.9274/6)/(287x1)=376.9 K.
State 3: an isochoric process (V=constant) and
T
3
=323.15 K.
P
2
/T
2
=(mR/V)=P
3
/T
3
P
3
=6 x10
5
Pa or 6 bar.

P
V
2
1
V
2
/V
1
=1/6
7bar
1 bar
3
T=50 C
T
2
Chapter3ME2121/E,August2013,KCNg Page13
The Steam Tables (PARTIAL LISTING ONLY) can be obtained from the booklet (recommend to
buy one copy): Thermodynamic and Transport Properties of Fluids, (SI Units) by GFC Rogers &
YR Mayhew, Blackwell.
Page 2 of tables (partial)
Page 3 of Tables (partial)
Chapter3ME2121/E,August2013,KCNg Page14
page 4 of Tables (partial)
Page 7 of Tables (partial)
Chapter3ME2121/E,August2013,KCNg Page15
Page 10 of Tables (partial)
Page 11 of Tables (partial)
Chapter3ME2121/E,August2013,KCNg Page16