Properties of Pure Substances

What is a Pure Substance?

Pure substance has homogeneous and invariable chemical composition.

It can exist in different phase, but should have uniform chemical composition
throughout the extend of mass.
 Solid-Liquid-Vapour Phase Equilibrium of Pure Substances

The present study is based on an experiment, in which a substance is heated at

constant pressure.
The substance is allowed to pass through three different phases, temperature and
specific volume are recorded.
The change of state occurring in this process are carefully studied and plotted in
p-v, p-t and t-v diagrams. 100 kPa

100 kPa
100 kPa
100 kPa

ice at -15°C Water at 0°C Water at 100°C Steam at 120°C

The heat required for change of solid to liquid phase is called latent heat of fusion.

A saturation state is a state from which a change of phase may occur without a
change in pressure or temperature.
Ice at 0°C is at saturated solid state and water at 100°C is at saturated vapour
state for a pressure of 100kPa

T
T-v diagram for heating of a pure substance at constant pressure
T 1200C
p=100kPa

1000C

40C
00C

-150C

v
The variation of saturation temperature with pressure for water
T 0C

p = 0.8455 bar
95

0.00103 1.982
v m3/kg

p bar

T = 127.40C
2.5

0.00106 0.7187
v m3/kg
A pure substance can exist as part liquid and part vapour during a vaporisation
process and the part of saturated liquid decreases as it progresses. For
thermodynamic analysis of such mixtures, the proportions the liquid and vapour
phase is to be determined. It is done with the help of a new property called quality
(x) which is defined as the ratio of the mass of vapour to total mass of the mixture.

mg
x=
mf + mg

The specific volume, internal energy, and enthalpy of a pure substance which is a
mixture of saturated liquid and saturated vapour can be evaluated by knowing its
quality as follows

v = v f + xv fg
u = uf + xufg
h = hf + xhfg
Thermodynamic properties in superheated vapour region
Properties of Saturated Water (Liquid–Vapor): Temperature Table

Properties of Superheated Water Vapor p = 10 bar

T 0C u =u f+ x u( −
g uf ) =h +h f xh fg
400 Superheated state
x = 0.7 mixture of saturated liquid
and saturated vapour

180
p = 10bar

v m3/kg
vf = 0.0011274 vg = 0.1941 0.3066

u=
u+ g(
f − u
xu f )
h=
h+x
fh fg
 The Ideal Gas Equation of State
Equation of state relates pressure, temperature, and specific volume. An ideal-
gas equation of state which predicts p –v –T behaviour of a gas is given by

pv = RT
R is gas constant of the gas under consideration R
R=
M
The deviation from ideal behaviour can be easily accounted by introducing a
correction factor called compressibility factor pv = ZRT

Different gases behave differently from ideal behaviour as pressure and

temperature are varied.
But they behave alike if pressures and temperatures are normalised with respect
to critical pressures and temperatures.
Thus reduced pressure (pr) and reduced temperature (Tr) obtained by
normalisation is
p T
pr = and T r =
pcr Tcr
Comparison of compressibility factors for some gases
  a 
2 (
The Van der waals equation of state  p + v − b ) = RT
 V 
27R 2Tcr2 RT
a= and b = cr
64pcr 8pcr

RT a( T ) b (T ) c (T ) d (T )
The Virial equation of state p= + 2 + 3 + 4 + 5
+ ...
v v v v v

The Beattie-Bridgemann equation of state

RT  c  A
pv = 1 −
 vT 3  ( v + B ) −
v2   v2

 a  b
A = A0  1−  and B = B0  1− 
 v  v