CHAPTER 2

PROPERTIES OF PURE
SUBSTANCE
 Outline
• Thermodynamic Properties Of Pure
Substances
• PVT Diagram
• Property Table
• Ideal Gas Law
• Compressibility Factor
• Others Equation of States
• Specific heat
 Learning Outcomes
At the end of the lesson, students should be able to:

• Understand the concept of a pure substance.

• Describe the physics of phase-change processes and
illustrate on property figures such as P-v and T-v
diagrams.
• Determine thermodynamic properties of pure substances
from tables of property data.
• Solve problems related to properties and processes of
pure substance.
• Understand the concept of ideal gas and real gas.
• Understand the concepts of other equation of state.
• Understand the concepts of specific heat.
Thermodynamics Properties
of Pure Substance
Pure Substance
• Pure substance - A substance that has a fixed
chemical composition. Eg: H2O, N2, CO2
• A pure substance does not have to be of a single
chemical element or compound
• A mixture of chemical elements/compounds also
qualifies as a pure substance as long as the
mixture is homogeneous, e.g. Air
• However, a mixture of oil and
oil
water is not a pure substance -
oil is not homogeneous/soluble
in water, forming two chemically water
dissimilar regions
• A mixture of two or more
phases of a pure substance is
still a pure substance as long
as the chemical composition of
all phases is the same

• Example: A mixture of ice and

liquid water is a pure substance
because both phases have the
same chemical composition
Phases Of Pure Substances

• A phase is identified as having a distinct

molecular arrangement that is homogeneous
throughout and separated from the others by
easily identifiable boundary surfaces. Eg: Two
phases of water in iced water

• Three principal phases: solid, liquid and gas

Phase Change Processes of Pure Substance (Water)
• Consider a piston–cylinder device containing liquid water at
20 °C and 1 atm pressure (state 1) that undergoes a heating
process at constant pressure.
PROCESS 1-2

State 2
Water exists as
State 1 saturated liquid
Water exists in
the liquid phase
 compressed
liquid or
subcooled liquid

Along process 1-
2, T as v
 PROCESS 2-3
During vaporization:
• Phase changes from liquid
to vapour.
Saturated • Both T and P remain
constant (water boils at
temperature 100oC when pressure is 1
(Tsat) = atm).
Temperature • Both liquid and vapour are
at which in equilibrium - have the
same T and P.
phase change
occurs at
given P.

State 2
State 3
Water exists as
Water exists as a
saturated liquid
mixture of saturated
liquid and saturated
vapour
v2=vf
 PROCESS 3-4

Saturated State 4
pressure Water exists as
(Psat) = saturated vapour -
Pressure at about to condense
which phase and the vaporization
change ends here
occurs at
given T

Tsat

State 3 Thermodynamic properties of

Water exists as saturated liquid and
a mixture of saturated vapour are listed in
saturated liquid Saturated Tables
and saturated
vapour v4=vg
 State 5
PROCESS 4-5 Water exists as
superheated vapour
when T5 > Tsat at
State 4 given P
Water exists as
saturated vapour -
about to condense
and the vaporization
ends here

Tsat
Properties of water in
the superheated
region listed in
Superheated Tables

v2=vf v4=vg
 SUMMARY OF PROCESS 1-2-3-4-5

State 4
Saturated
State 2 vapour
Saturated
liquid
State 5
Superheated
Tsat
vapour

State 1
Compressed
liquid State 2-4
Saturated
mixture

v2=vf v4=vg
PVT Diagram
• If the heating process at constant P is
repeated at other constant P, the
phase change lines look like as in
Figure 1.
• If all the saturated liquid points are
joined together  saturated liquid line
formed. Similarly for saturated vapour
points  saturated vapour line
formed.
• Both lines meet at critical point and Figure 1
form “steam dome” (Figure 2).
• At critical point – saturated liquid
conditions are similar to those of
saturated vapour.
• The region between saturated liquid
and saturated vapour line  saturated
mixture region.
• The region to the left of saturated
liquid line  compressed liquid region.
• The region to the right of saturated
vapour line and above the critical point Figure 2
 superheated vapour region.
 T v  P v

T-v diagram of a pure substance P-v diagram for a pure substance

• The general shape of the P-v diagram of a pure substance is

very much like the T-v diagram, but the constant T lines on P-v
diagram have a downward trend.
• The temperature trend of constant P lines on T-v diagram
increases as the volume increases.
• The pressure trend of constant T lines on P-v diagram
decreases as the volume increases.
P-v Diagram that combines all the three
phases of solid, liquid and vapour
 P-T Diagram
•P-T diagram of a pure substance
also known as phase diagram –
all the three phases are
separated by three lines.
•Sublimation line separates solid
and vapour; vaporization line
separates liquid and vapour;
melting or fusion line separates
solid and liquid.
•The three lines meet at a triple
point – all the three phases are in
equilibrium. The triple point of
water is at 0.01oC and 0.6113
kPa.
Property Table
• Relationship between thermodynamic properties of
most substances are complex – most data simplified
in tables  Property Tables.

• Besides temperature, pressure and specific volume

data, it also contain data of internal energy u,
specific enthalpy h and specific entropy s.

• Enthalpy (H) = Combination of internal energy (U),

pressure (P) and volume (V), correlated as:
H = U + PV (kJ) or h = u + Pv (kJ/kg)

• Entropy – A thermodynamic property that relates to

Second Law of Thermodynamics and is equal to
heat transfer to a system divided by the temperature
(kJ/K).
 Types Of Property Tables for Water

PROPERTY TABLES FOR WATER

COMPRESSED SUPERHEATED
LIQUID TABLE TABLE
(Table A-7) (Table A-6)
SATURATED
TABLE

Temperature- Pressure-
based based
(Table A-4) ( Table A-5)
 Saturated Tables
• Properties of saturated liquid and saturated vapour for water are
listed in Table A-4 and A-5:
–Both give similar data but arranged differently.
–Table A-4 arranged based on temperature (referred when
temperature given) and Table A-5 arranged based on pressure
(referred when pressure given).
• Subscripts used in saturated tables:
– f = Property for sat. liquid,
– g = Property for sat. vapour
– fg= The difference of similar property between sat. liquid and
sat. vapour.
 Quality and Saturated Region
• During vaporization, a substance exists in two
phases (a mixture of saturated liquid and saturated
vapour)
• Quality,x - The ratio of vapor to the total mass of
mixture.
x  
mvapour mvapour mg
mtotal mliquid mvapour m f  mg

• For saturated liquid, x=0 (or 0%)

• For saturated vapour, x=1 (or 100%),
• The range for quality is 0  x  1.
• Quality has significance for saturated phases only. It
has no meaning in the compressed liquid or
superheated vapor regions.
When a system consists a mixture of saturated liquid
and saturated vapor, the relation for any intensive
property is:
y  y f  x( yg  y f )
 y f  x y fg

where y can be represented by v, u, h or s

The values of the

average properties of
the mixtures are always
between the values of
the saturated liquid and
the saturated vapor
properties:
yf y  yg
 Superheated Vapour Table
• Table A-6 lists down the properties for superheated vapour
for water. In this tables T and P are independent.
Compressed Liquid Table
• Compressed liquid tables are not as commonly available, and
Table A–7 is the only compressed liquid table for water.
• Data in Table A-7 starts at 5 MPa. For water, data at
pressure below 5 MPa are similar to the saturated liquid data
at a given temperature:
– Data for v, u and s data can be estimated as:
y  y f @T
– Enthalpy of compressed liquid is highly dependent on the
pressure change. Hence, at high pressure, enthalpy can
be estimated as:
h  h f @T  v f @T P  Psat@T 
 Types Of Property Tables for
Refrigerant-134a

PROPERTY TABLES FOR REFRIGERANT-134a

COMPRESSED SUPERHEATED
LIQUID TABLE TABLE
(no available) (Table A-13)
**Please refer to saturated SATURATED
table temperature TABLE
based(refer to saturated
liquid column)

Temperature- Pressure-
based based
(Table A-11) ( Table A-12)
 Phase Conditions

PROPERTY
TABLES

COMPRESSED SATURATED SUPERHEATED

LIQUID TABLE TABLE TABLE

IF, IF,
IF,
a) TTsat, or a) TTsat, or
a) T=Tsat, or
b) PPsat, or b) PPsat, oru
b) P=Psat, or
c) yyf c) yyg
c) y=yf, (sat liq)or
d) y=yg (sat vap), or
e) yfyyg (sat mix)
Guideline for data acquisition
from property table
 Data interpolation
(a) Single interpolation – performed when the required data is within the
two-listed data.
c

P or T a b c b

y d e f a

d e f

Values of a, c, d, e and f are found from Property Tables and value of b can
be determined from:
 e  d  
ba  c  a 
  f  d 
Values of a, b, c, d and f are found from Property Tables and value of e can
be determind from:
 b  a 
ed   f d
 c  a  
 Data interpolation
(b) Triple interpolation – performed when the required data are between the four-
listed data.
T P P1 P P2
T1 a e b
T f y=?? g
T2 c h d
If y at given T and P to be determined and values of a, b, c and d that represent
properties of y’s are found in Property Tables:
(i) Horizontal interpolation: f and g are firstly determined before calculating y.

 T  T1    T  T1    P  P1  
f a c  a ; g b d  b; y  f  g  f 
 T2  T1   T2  T1   P2  P1 

(ii) Vertical interpolation: e and h are firstly determined before calculating y.

 P  P1    P  P1    T  T1  
ea b  a ; h c d  c ; y  e h  e
 P2  P1   P2  P1   T2  T1 
Both ways should end up with the same value for y.
 Data extrapolation
(c) Data extrapolation – performed when the required data is
beyond the listed data.
P or T a b c
y d e f c

b
If c to be determined: a

c  b   b  a 
d e f
 f  e e  d 
 b  a  
c  b     f  e
 e  d 
 Example 2.1
Using Property Tables, complete this table for H2O

P (MPa) v (m3/kg) T (oC) Phase and Quality

(a) 1.725 100
(b) 0.85 0.227
(c) 15 400
(d) 0.001124 180
(e) 0.75 0.221
(f) 0.3879 150
(g) 0.25 0.095
 Example 2.2
A rigid tank with a volume of 1.8 m3 contains
15 kg of saturated liquid-vapor mixture of
water at 90 oC. Now the water is slowly
heated. Determine the temperature at which
the liquid in the tank is completely
vaporized. Also show the process on a T-v
diagram with respect to saturation lines.
Ideal Gas
• Any equation that relates the properties of pressure
( p ),temperature ( t ) and specific volume ( v ) of a
substance is called an equation of state.

• The simplest and the best known equation of state

for substance in gas phase is the ideal gas
equation of state.

• The equation of state predicts p, t and  behaviour

of a gas quite accurately but within some properly
selected region, i.e. it has limitation.
Equation of State for ideal gas
PV  mRT
or
Pv  RT
where:
R = Gas constant
(Different value for different gas)
P = Absolute pressure, kPa
v = Specific volume, m3/kg
T = Absolute temperature, K
• The relationship between gas constant, R and universal
gas constant Ru is
Ru
R
M
where:
M= Molecular weight of the gas
Ru : 8.314 kJ/(kmol K)
• Examples of Gas Constant, R value.
Substance R, kJ/kg.K
Air 0.2870
Helium 2.0769
Argon 0.2081
Nitrogen 0.2968
Compressibility Factor, Z
Limitations of Ideal-Gas Equation of State
• It has been experimentally observed that ideal-gas
relation closely approximates the p-v-t behaviour of
ideal-gas at low densities.
• At low pressures and high temperatures, the density
of a gas decreases and therefore the gas behave
like an ideal-gas at low densities.
• Many familiar gases such as air, nitrogen, oxygen,
hydrogen, helium, argon, neon, krypton and even
heavier gases such as carbon dioxide can be treated
as ideal-gas with negligible error (often less than
1%).
 Dense gases such as Water Vapour in Steam
Power Plants and Refrigerant Vapour in
Refrigerators should not be treated as Ideal-Gas.
Instead, the Property Tables should be used.
Percentage of error involved in assuming steam to be an ideal gas, and the
region where steam can be treated as an ideal gas with less than 1%error
• This deviation from Ideal-Gas behaviour at a
given Temperature and Pressure can accurately
be accounted for by the introduction of a
Correction Factor called the Compressibility
Factor, Z.
Pv
Z
RT
• For ideal gas, Z = 1, thus Pv = RT.
• Z > 1 - Real gas
• The farther away Z is from unity, the more the
gas deviates from Ideal Gas behaviour.
• The Z factor is approximately the same for all
gases at the same reduced temperature(Tr) and
reduced pressure(Pr) , which are defined as

T P
TR  and PR 
Tcr Pcr
• When either P or T is unknown, Z can be
determined from the compressibility chart with
the help of the pseudo-reduced specific volume,
defined as
vactual
vR 
R Tcr
Pcr
From the Generalized Compressibility Chart, the
following observation can be made :
• At very low Pressures (PR << 1), gases behave
as an Ideal Gas regardless of Temperature.
• At high Temperatures (TR > 2), Ideal Gas
behaviour can be assumed with good accuracy
regardless of Pressure except when PR>>1.
• The deviation of a gas from Ideal Gas behaviour
is greatest in the vicinity of the Critical Point.
 Example 2.3
Determine the specific volume of refrigerant-134a
at 1 MPa and 50 °C, by using:
a) The ideal gas equation of state
b) The generalized compressibility chart
Compare the value obtained to the actual
value of 0.02171 m3/kg and determine the
error involved in each case.
Other Equation of State
• The ideal-gas equation of state is very simple  limits its range of
applicability.
• Other EOSs that represent the P-v-T behavior of substances
accurately over a larger region with no limitations:
1) Van der Waals equation (2 constants) – considering the
intermolecular attraction forces (a/v2) and the volume occupied
(b) by the molecules:
 a 27 R 2Tcr2
 P  2 v  b   RT
RTcr
with a and b
 v  64 Pcr 8Pcr

2) Beattie-Bridgeman Equation (5 constants) – for densities up to

0.8cr
RuT  c   a  b
P  1   v  B  
A
with A  Ao 1   and B  Bo 1  
v2  vT 3  v2  v  v

3) Benedict-Webb-Rubin Equation (8 constants) – for < 2.5 cr

RT  C  1 bR T  a a c   
P  u   Bo RuT  Ao  o2  2  u 3  6  3 2 1  2  e   v2

v  T v v v vT  v 
Specific Heat
• Specific heat - The energy required to raise the
temperature of a unit mass of a substance by one
degree.

• Two types of specific heats:

(a) Specific heat at constant volume (Cv)
Energy required to raise the temperature of the unit
mass of a substance by one degree as the
volume is maintained constant.

(b) Specific heat at constant pressure (Cp)

Energy required to raise the temperature of the unit
mass of a substance by one degree as the
pressure is maintained constant.
• Other definition of specific heats:
a) CV = The change in the internal energy
of a substance per unit change in
temperature at constant volume.
 u 
Cv   
 T v
b) CP = The change in the enthalpy of
a substance per unit change in
temperature at constant pressure.
 h 
CP   
 T  P
• Units for specific heats :
Mass basis - kJ/(kg.K) = kJ/(kg.oC)
Molar basis(ĈV and ĈP) - kJ/(kmol.oC) = kJ/(kmol.K).
• Relationship between Cv and Cp:
C P  CV  R or C P  CV  Ru
 • Thus, the differential changes in the internal energy and
enthalpy of an ideal gas can be expressed as:

du  CV (T ) dT   u  u 2  u1   CV (T ) dT  CV ,ave T2  T1  kJ kg 

2
integration
1

dh  C P (T ) dT   h  h2  h1   C P (T ) dT  C P ,ave T2  T1  kJ kg 

2
integration
1
• There are 3 ways to determine average values of specific heats of an
ideal gas:

1) Acceptable average by taking specific heat values at 300 K:

Cv ,ave  CV (300K ) and CP ,ave  CP (300K )

Table A-2(a)  Cp and Cv (kJ/kg.K) for common gases at 300 K.

2) Good average :
C (T )  CV (T1 ) CP (T2 )  CP (T1 )
Cv ,ave  V 2 and CP ,ave 
2 2
Table A–2(b)  Cp and Cv (kJ/kg.K) for some common gases as
function of T (K)

3) Best average :
2 2

CV ,ave 

1
CV (T )dT
and C P ,ave 

1
C P (T )dT
(T2  T1 ) (T2  T1 )
Table A-2(c)  CP (kJ/kmol.K) as function of T (K) in the form of:
CP = a + bT + cT2 + dT3 .