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ME2121/ TM1121- Thermodynamics

Chapter 3 1/ 12

Thermodynamic Properties of Pure

Substances
A pure substance is one where its properties
remain invariant (or no change) when it
undergoes state changes, from gaseous to liquid
or to solid phase.
H
Water, H2O

H
O

Ice (Solid)

Water, H2O
liquid

Melting
(NMP)

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ME2121/ TM1121- Thermodynamics

Chapter 3 2/ 12

State Diagrams
Pcr= 221 bar

Water,

Critical point
T

374 o C

Liquid

Isobaric
Process,(A-B-C-D)

Vapour region
Liquid & Vapour

L
100 bar

State A

State B

subcooled
TA <Tsat

State C-D State C

Saturated
(T=Tsat)

State D

T>Tsat
10 bar

100oC

V
L

Qin

Liquid
phase

Two-phase
mixture

A
Gaseous
phase

1 bar

L+V

g-line

f-line
vf = vg
Fig. 3.1

2-D State diagram

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ME2121/ TM1121- Thermodynamics

Chapter 3 3/ 12

3-D state diagrams

load

ice

liquid

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ME2121/ TM1121- Thermodynamics

Chapter 3 3/ 12

Constant pressure

A thermodynamic state on the surface require two independent properties to

locate it, e.g, P=P(v,T).

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ME2121/ TM1121- Thermodynamics

Chapter 3 3/ 12

3-D and 2-D representations of a substance that contracts on freezing

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ME2121/ TM1121- Thermodynamics

Chapter 3 4/ 12

Variables in the liquid+vapour region

Quality or dryness fraction of steam
x

mass of vapour
mass of liquid mass of vapour
mg
mg m f

- Specific volume of a
two-phase mixture
small

vf

compared to v

v fg

v
v fg

Vmixture m f v f m g v g
and by mT gives
m f v f mg vg
V
v

mT
mT
mT
or v (1 x)v f xv g
v

fg

v f x (v g v f )

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ME2121/ TM1121- Thermodynamics

Chapter 3 5/ 12

Other derived properties

h (1 x ) h f xhg h f xh fg

enthalpy

internal energy u (1 x )u f xu g u f xu fg
- Entropy

s (1 x ) s f xs g s f xs fg
At a given P, T, v

- Quality

s sf
s fg

h hf
h fg

uuf
u fg

Example 3.1

Find the states of steam for

the following given
conditions:
(i) t = 34o C, v = 26.6 m3/kg,
(ii) P = 0.8 bar, t = 100o C,
(iii) P = 2.7 bar, x = 0.5.

At P =0.8 bar, t =100o C,

Refer to the Table of saturated

steam and water (pg.2), the
column 1 is the temperature of
mixtures in oC, and column 3 is
the specific volume at dry
saturated vapour.
At v =26.6 m3/kg, note that t of
steam/water is 34oC. Thus, we
conclude that the state point
sits on the dry saturated
vapour line or the g line,
shown below.

Look up page 3 of Table where

column 1 is the saturated
pressure, and at 0.8 bar, the
corresponding temperature is
only 93.5oC.
This temperature is found to be
less than 100oC (given), thus,
we conclude that the steam is
super-heated (that is,
temperature of state higher
than the saturated
temperature).

Tsat
C

t
f-line

g-line

V=26 m3/kg

Note that 2.7 bar is very much lower than

Pcr =221 bar, thus, vf <<< vg., and Tsat =
130oC.
By definition, any other properties could
be found;
In this region (L+V), P & T are no longer
independent.
P=2.7 bar

Critical pt
t
f-line

g-line
X=0.5

=93.5o

f-line

Critical pt
g-line

P=0.8
bar
Superheated
state
v=2.087m3/kg

34oC

vf = 0.00107 m3/kg (pg. 10 of Table)., vg

=0.6686 m3/kg (pg.4),

L+V

100oC
Critical pt

At P =2.7 bar, x=0.5,

v
Note: at low P, vf << vg,,
thus vi ~ x(vg) +(1-x)vf

=0

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ME2121/ TM1121- Thermodynamics

Chapter 3 6/ 12

Interpolation technique
- data in tables are sparsely tabulated.
-To interpolate for v at pressure (P) when values of v1 and v2
are available from tables at P1 and P2.

P P1
v 2 v1
v( P) v1

P
1
2

P2

Critical pt

g-line

P1

f-line

v (m3/kg)

P1 =20 bar

t = 250o C

0.1115 m3/kg

t =275o C

=(0.1115+0.1
255)/2
=0.1185

t =300o C

0.1255

L+V
v2

v1
v

P=25 bar

P2 =30 bar
0.0706 m3/kg

=(0.1185+0.0759)
/2
=0.0972

=(0.0706+0.0
812)/2
=0.0759
0.0812

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ME2121/ TM1121- Thermodynamics

Chapter 3 7/ 12

Gaseous Phase
The equation of state (EOS),
Two forms: (i) gravimetric , (ii) molar form

PV

R (a gas cons tan t )

Tm lim

Compressibility

or
PV

Ro (universal gas cons tan t

Tn

lim
8.314 J / mol.K )
factor
Tr = 10

Pv
1.0
RT
for ideal gas

Z=Pv/RT
1.0
Tr= 1.5
Tr = 1.0

Tr = T/Tcr

10

Pr = P/ Pcr

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ME2121/ TM1121- Thermodynamics

Chapter 3 8/ 12

Empirical equations for real gases

Losses incurred when gas molecules can be described by Virial Equations
of the form
B 2 ,v (T )
B 3 ,v (T )
PV
Z 1

R oT
V
V 2

or in terms

of

molar

volume

(V / n ) v ,

B 2 ,v (T )
B 3 ,v (T )

Ro
P

T
v
v
v2

It can represent many other forms of EOS. If written in

terms of pressure,

PV
Z 1 B2, p P B3, p P 2
RoT
where B2,p = B2,v /RoT, and B2,P =(B3,v B2,v2)/(RoT)2.

Example

van del Waals (1837), accounted for the intermolecular

attractions or pressure (
) and the presence or effect
of gas molecules (b) on the free volume
Critical pt,

P 2 v b RoT
v

2P
P
0

2
V TC V TC

TC

Comparing with the Virial Eq.,

P Ro B2,v (T ) B3,v (T )

2
T
v
v
v

T
L+V

And expanding the van der Waals as

B2 ,v (T )
,v (T )

B3

a
2
P R 1 a b

then we see that B2,v(T) = b
1 b

RT
2
T v v RT v 2
and B3,v (T) = b

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ME2121/ TM1121- Thermodynamics

Chapter 3 9/ 12

Example 3.1
Derive, from first principles, the ideal gas law, PV/T = constant?
From experiments, the expansion and compressibility factors
are
1 V
1
1 V
1

and

V
P

T P
V T P T
The volume of ideal gas in a system is V=V(P,T) and the
change
V
V
dV VdT VdP
dV
dT

dP

P T
T P
dT
dP
Substitute for
V
V
T
P
or
Ln V - ln T+ln P = ln (constant),
dV dT dP
or

0
V
T
P
PV/T = constant. (QED)

Example 3.3 (notes)

Calculate the van der Waals parameters (a
and b) for the following gases with the
experimental values at the critical point:
Gases
Benzene

Pc (bar)

Tc (K)

49.1

562

Comparing equations for the roots

(solution) of v,
3
ab
vc
o
The root of v :
Pc

a
3 vc
Pc

The root of v1:

The root of v2:

Water

221.2

647.3

Write the van der Waals equation in

another form as

Thus,

R T
2 a
ab
v o c bv v 0
Pc

Pc
Pc

vv 0

have

o c
c

Gas molecule effect on

the free volume

Effect of intermolecular forces

Gases

Pc (bar)
or 105 Pa

2
27 Ro Tc
a
64
Pc

Tc (K)

[Jm3 / mol2].
Benzene

v 3v vc 3v vc vc
2

49.1

562

After expanding, we have

2

v 83 RPT

Thus, substitute for a and b, we

At the critical point, the three roots (solutions)

of v, as given mathematically by a cubic
equation, must converge i.e.,
3

v P v
b
3
3v P

And at the critical point, T=Tc, P=Pc,

3

RTc
b 3 vc
Pc

a 3 vc Pc

2 a
R T
ab
0
v 3 o b v v
P
P
P

Water

221.2

647.3

27 8.3143x(562)2
64
49.1x105

RoTc
8 Pc

[m3/mol]

8.3143 x562
8 x 49.1x10 5

=1.88

1.19 E-4

0.552

3.04 E-5.

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ME2121/ TM1121- Thermodynamics

Steam Tables by Rogers & Mayhew

Chapter 2 10/ 12

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Saturated liquid properties

ME2121/ TM1121- Thermodynamics

Chapter 3 11/ 12

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Superheated properties

ME2121/ TM1121- Thermodynamics

Chapter 3 12/ 12