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Chapter 2
Properties of Pure Substance
2.1 Pure substance
A substance that has a fixed chemical composition throughout is called a pure substance.
Example: - Water, nitrogen, air, helium, carbon dioxide etc
Pure substance may exist in different phases, but the chemical compositions is the same. For
example water made up of two atoms of hydrogen and one atom oxygen. It will have the same
composition when in ice, liquid and vapor forms.
2.2 Fixing the state of a simple pure substance
The number of properties required to fix the state of a system is given by the state postulates.
The state postulate for a simple pure substance state that, equilibrium state can be determined by
specifying any two independent intensive properties.
Phase of pure substances
A phase is identified as having a distinct molecular arrangement that is homogenous throughout
and separated from the others by easily identifiable boundary surface.
Under different conditions a substance may appear in different phases. The three principal phases
are solid, liquid and gas.
Considering water, it can be exist as
- Pure solid phase (ice)
- Pure liquid phase
- Pure vapor phase (steam)
It can also exist as an equilibrium mixture of different phase.




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Phase-change processes of pure substances

Consider the piston-cylinder device containing liquid water at 2u
0
C and 1atm.

Under these conditions, water exists in the liquid phase, and it is called a
compressed liquid, or a sub cooled liquid.
As the temperature rises, the liquid water expands slightly, and so its
specific volume increases.


Figure 2.1 At 1 atm and 20C, water exists in the liquid phase (compressed liquid).

At this point water still a liquid, but any heat addition will cause some of
the liquid to vaporize.
That is, a phase change process from liquid to vapor is about to take place.
A liquid about to vaporize is called saturated liquid.


Figure 2.2 At 1 atm pressure and 100C, water exists as a liquid that is ready to vaporize
(saturated liquid).
Once boiling starts, the temperature stops rising until the liquid is
completely vaporized (it is a constant phase - change process at p-
constant).
During this process the only thing is change in volume.
At this stage liquid and vapor phase coexist in equilibrium and it is
called saturated liquid-vapor mixture.
Figure 2.3 As more heat is transferred, part of the saturated liquid vaporizes (saturated liquid
vapor mixture).
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At this point, the entire cylinder is filled with vapor that is on the borderline
of the liquid phase.
Any heat loss from this vapor will cause some of the vapor to condense
(phase change from vapor to liquid).
The vapor that is about to condense is called a saturated vapor.

Figure 2.4 At 1 atm pressure, the temperature remains constant at 100C until the last drop of
liquid is vaporized (saturated vapor).
At this stage the phase-change process is completed is completed, we back
to a single-phase region (vapor).
Further transfer of heat will result in an increase in both the temperature and
the specific volume.
A vapor that is not about to condense (i.e. not a saturated vapor) is called a
superheated vapor.
Figure 2.5 As more heat is transferred, the temperature of the vapor starts to rise (superheated
vapor).
The above process is shown on a T-V diagram at constant pressure.

Figure 2.6 T-: diagram for the heating process of water at constant pressure
Thermodyn
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At a giv
saturatio
substance
is 99.97
The amo
heat. Th
vaporizat
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_____________
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, pressure a
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____________
____________

hich a pure
a given tem
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99.97C, P
sat
pressure of w
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during vapo
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he latent he
and temperat

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_____________
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sat
. At a
t
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water at vario

phase-change
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curve of a pu
____________
____________

changes ph
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pressure of
kPa.
ous temperat
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called the
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n and it is e
viously depe
ure substanc
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Page4
ase is called
at which a
101.325 kPa
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latent hea
. The amou
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2.3 P
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b) Phase diag
____________
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can be three
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for a substa
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are best stu

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T-P, P-V a
nce that exp
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____________
____________

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and T-V dia
pands on fre
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Page5
derstood wit
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it will beco
____________
____________

for a substan
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is increased
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_____________
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further, the
This point i
____________
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is called the
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the substance and it may be defined as the point at which the saturated liquid saturated vapor
states are identical.

Figure 2.10 T-v diagram of constant-pressure phase-change processes of a pure substance at
various pressures (numerical values are for water).

At pressures above the critical pressure, there is not a distinct phase-change process. Instead, the
specific volume of the substance continually increases, and at all times there is only one phase
present. Eventually, it resembles a vapor, but we can never tell when the change has occurred.
Above the critical state, there is no line that separates the compressed liquid region and the
superheated vapor region. However, it is customary to refer to the substance as superheated
vapor at temperatures above the critical temperature and as compressed liquid at temperatures
below the critical temperature.
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Figure 2.11 T-V diagram of a pure substance.
The P-V diagram
It is the same as T-V diagram but the T-constant line on this diagram have a down ward trend

Figure 2.12 P-V diagram of a pure substance.
The P-T diagram
This diagram is often called the phase diagram since all three phases are separated from each
other by three lines.
Thermodyn
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this book
(melting)
consistin
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ublimatio
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it is also in
solid to vap
mass of ice a
Fig
_____________
___________

e 2.13 P-T di
n
m liquid to va
nstructive to
por (sublima
at a temperatu
gure 2.14 Ph
____________
____________

iagram of pu
apor (vapori
o consider t
ation). To stu
ure below th
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_____________
___________

ure substanc
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the phase ch
udy these tr
he triple poin
m for water
____________
____________


ces.
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Page9
incipal intere
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Let us b
greater th
pressure
on Fig. 2
pressure
heated fu
contains
constant.
specific v
pressure
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less than
passes th
shown on
line a''
2.4 Th
Thermod
calculatio
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egin with th
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____________
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ase where th
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The case of
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them satur
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_____________
___________

ere the syste
sure. Suppos
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state the ice
n of liquid w
es to melt u
During the m
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ess than the
n temperatu
he system is i
ure. In this c
olidvapor re
f vaporizatio
les
substance
rated, superh
____________
____________

em is at stat
se the system
The tempera
is a saturate
without any
until eventu
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volume incr
specific volu
ure as the sy
initially at st
case, if the
egion into th
on discussed
are usually
heated steam
_____________
___________

te a of Fig.
m is slowly h
ature increas
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change in te
ually the las
ess the temp
reases durin
ume of the s
ystem is brou
tate a' of Fig
system is h
he vapor reg
previously
y given in
m and comp
____________
____________

2.14, wher
heated while
ses with heat
ditional heat
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st bit melts,
perature and
ng melting, b
solid. Furthe
ught to poin
g. 2.14, whe
eated at con
gion along th
is shown on
tabular fo
pressed liqu
_____A
___________
Page10
re the pressu
e maintainin
ting until po
t transfer at
As the syste
and the sy
d pressure re
but for wate
er heating at
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ere the pressu
nstant pressu
he line a b '
n Fig. 2.14 b
orm to faci
uid are the

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During a
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Quality h
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are the
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can be sa

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e properties
same whet
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____________
____________
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the quality
x
total li
m m =
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r regions. Its
s 0 (or 0 per
t). In satura
needed to d
ther it exist
s, only the a
aturated vap
_____________
___________

mixture
a substance
saturated va
uid and vapo
y (x) as the
vapor
total
m
x
m
=
iquid vapor
m + =
urated mixtu
s value is be
rcent), and t
ated mixture
describe a sta
ts alone or
mount of sa
por.
____________
____________

exists as pa
apor. To an
or phases in
ratio of the

f g
m m = +
ures only. It h
etween 0 and
the quality o
s, quality ca
ate. Note tha
r in a mixt
aturated liqu
_____________
___________

art liquid an
alyze this m
n the mixture
mass of va
(2.1)
(2.2)
has no mean
d 1. The qua
of a system c
an serve as
at the prope
ture with sa
uid changes,
____________
____________

nd part vapo
mixture prop
e. This is do
apor to the t
ning in the c
ality of a sys
consisting of
one of the
erties of the
aturated vap
not its prop
_____A
___________
Page11

or. That is, i
perly, we ne
one by defin
total mass o
ompressed l
stem that con
f saturated v
two indepen
saturated l
apor. During
perties. The
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vapor
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same
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Consider
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the sum o
to denote
Since x =
also be ex
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Fi
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f
of the two. (
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t
and
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for quality, w
____________
____________
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igure 2.15 L
at contains
V
f
, and the vo
(The subscri
vapor).
V
V mv =
m
f tot
m m =
tot avr
m v
ing by
tot
m
(
avr
v =
v
fg
is the dif

avg
v =
we obtain
v
x =
_____________
___________

iquid and va
a saturated
olume occup
ipt f is used t
f g
V V V = +
tot avr f
m v m v =
g
m
(
r tot g
m m =
(1 )
f
x v xv +
fference betw
f fg
v xv = + (m
avg f
fg
v v
v

____________
____________

apor phases
d liquidvap
pied by satur
to denote sa

f g g
v m v +
)
g f g g
v m v +
g
v
ween v
g
and
m
3
/kg)
_____________
___________

in a saturate
por mixture
rated vapor
aturated liqui
(2.3)
(2.4)
(2.5)
(2.6)
v
f
(that is, v
f
(2.7
(2.8
____________
____________

ed mixture
. The volum
is V
g
. The t
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)
)
fg
=v
g
- v
f
).
7)
8)
_____A
___________
Page12
me occupie
total volume
ubscript g is

This relation
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The abov
In
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E
Satura
The prop
tables
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In the reg
temperatu
phase reg
and they
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____________
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also holds tru
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s =
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aturated liqui
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ance exists
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_____________
___________

ue for other
f fg
u xu = +
f fg
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f fg
s xs = +
aturated
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16 A partial
e
saturated va
as superheat
), temperatu
ed as the two
____________
____________

properties



Vapor St
rated vapor
l list of Ther
apor line and
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ure and pres
o independen
_____________
___________

(

(

(
tates
for water ar
rmodynamic
d at tempera
Since the sup
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nt properties
____________
____________

2.9)
2.10)
2.11)
re listed in T

Table
atures above
perheated re
longer depe
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Page13
Thermodyna
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ected read fr
Figure 2.17
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er temperatur
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tables. Com
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at the given t
_____________
___________

able, where
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perheated va
(P < P
sat
at a
res (T > T
sat
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nergies (u >
(h >h
g
at a
e
given witho
mpressed li
properties de
quid data, a g
temperature
____________
____________

T and P are

d region in g
apor is chara
a given T)
at a given P
v
g
at a given
u
g
at a given
given P or T
ut subscript
quid tables
epend on tem
general appro
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_____________
___________

e given and
graph and ta
acterized by
P)
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T)
ts. Pressure
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____________
____________

d the other p
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and temper
commonly
much more st
s to treat com
_____A
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Page14
properties ca
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available th
trongly than
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In genera
How to
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Given th
following
questions

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al, a compres
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Lower
Lower
Lower
o Choose
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ned by comp
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s are asked:

wer to one o
n the compr
____________
____________
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er pressures (
r temperatur
r specific vo
r internal en
r enthalpies
Fig
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For the give
Is ?
f
v v <
Is
f
v v < <
Is ?
g
v v <
of these ques
ressed liquid
_____________
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sat
at a
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sat
a
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the thermody
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?
g
v <
?
stions must b
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____________
____________

zed by
a given T)
at a given P)
v
f
at a given
u
f
at a given
given P or T
ompressed li
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properties to
e other prop
the pressure
be yes. If th
nd the comp
_____________
___________

)
P or T)
P or T)
T)
iquid region
perties of a r
o the proper
perty from th
e and specifi
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pressed liqui
____________
____________


real substanc
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he group v,
ic volume ar
the first qu
d tables are
_____A
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Page15
ce can alway
saturation re
u, h, and s
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used to fin
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properties of the state. If the answer to the second question is yes, the state is in the saturation
region, and either the saturation temperature table or the saturation pressure table is used to find
the properties. Then the quality is calculated and is used to calculate the other properties, u, h,
and s. If the answer to the third question is yes, the state is in the superheated region and the
superheated tables are used to find the other properties.
2.5 Equation of State
The relationship among the state variables, temperature, pressure, and specific volume is called
the equation of state.
Property relations that involve other properties of a substance at equilibrium states are also
referred to as equations of state. There are several equations of state, some simple and others
very complex. The simplest and best-known equation of state for substances in the gas phase is
the ideal-gas equation of state. This equation predicts the P-v-T behavior of a gas quite
accurately within some properly selected region.
Based on our experience in chemistry and physics we recall that the combination of Boyles and
Charles laws for gases at low pressure result in the equation of state for the ideal gas as
T
P R
v
| |
=
|
\ .
(2.12)
It is given by:
Pv RT = , PV mRT nMRT = = (2.13)
Where:
P =Absolute Pressure, KPa
V =Volume, m
3

T =Absolute Temperature, K
R =Gas Constant. KJ /KgK
M =Molecular Weight, Kg/Kmol
n =Number of Mole
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The constant of proportionality R is called the gas constant. Equation (2.12) is called the ideal-
gas equation of state, or simply the ideal-gas relation, and a gas that obeys this relation is called
an ideal gas.
The gas constant R is different for each gas and is determined from
( / . )
u
R
R kJ kg K
M
= (2.14)
Where R
u
is the universal gas constant and M is the molar mass (also called molecular weight)
of the gas. The constant R
u
is the same for all substances, and its value is8.314KJ /KmolK
m nM = (2.15)
The ideal-gas equation of state can be written in several different forms
V mv PV mRT = = (2.16)
( )
u u
mR MN R NR PV NR T = = = (2.17)
u
V Nv Pv R T = = (2.18)
By writing Eq. 2.16 twice for a fixed mass and simplifying, the properties of an ideal gas at two
different states are related to each other by
1 1 2 2
1 2
PV PV
T T
= (2.19)
Air, nitrogen, oxygen, hydrogen, helium, argon etc can be treated as ideal gases.
Compressibility factor (measure of deviation from ideal gas)
The ideal-gas equation is very simple and thus very convenient to use. However, gases deviate
from ideal-gas behavior significantly at states near the saturation region and the critical point.
This deviation from ideal-gas behavior at a given temperature and pressure can accurately be
accounted for by the introduction of a correction factor called the compressibility factor Z
defined as
PV ZRT = (2.20)
Z =1 for ideal gases. For real gases Z can be greater than or less than unity. The Z factor is
approximately the same for all gases at the same reduced temperature and reduced pressure. This
is known as the principle of corresponding states.

Thermodyn
________
Compiledb

W



namicsI______
___________
byYidnekache
Where:
P
R
=re
P
cr
=cr
T=act
____________
____________
wM.
R
P
P
=
educed pressu
ritical pressu
tual pressure
Figure 2 19
_____________
___________

cr
P
P
and
R
T =
ure
ure
e
9 Compariso
____________
____________

cr
T
T
=
on of Z facto
_____________
___________

(2.2
or for variou
____________
____________

1)
us gases
_____A
___________
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