The fascinating world

of
Thermodynamics
Instructor
Dr. Madhusree Kundu
Thermodynamics
Lecture # 3
Pure Substance
The pure substance is one that has a
homogeneous and invariable chemical
composition.
A pure substance may exist in many
phases, but the chemical composition is
same in all the phases.
In our analysis, we will deal only with
simple compressible substances and
substances whose surface effects,
magnetic effects, and electric effects are
negligible.
Example: liquid water, water vapor, ice, a
mixture of liquid water and water vapor
are all pure substances.
Depending on the nature of substance,
applied pressure and temperature, the
change in molar volume of the
substances may be large, the
substances are compressible and where
the change in molar volume is less
then those are incompressible.
Liquids and solids are generally
incompressible, gases are compressible
Properties of a pure
substance
What we need to study about a pure substance?
The phases in which a pure substance
may exist.
The number of independent
properties of pure substance.
Methods of presenting thermodynamic
properties.
Properties of a pure
substance
Example: We need to know properties of
water to determine pipe diameter through
which it has to flow.
Example: We need to know properties of
steam in order to design a boiler.
Understanding the properties and
behavior of substances is essential for
designing and sizing various equipment.
In the thermodynamic analysis of the
processes we are concerned with the
estimation of energy change of a system
while it exchanges energy, in the form of
work and heat, with its surroundings. To
estimate work and heat interactions, it is
essential to have knowledge of the
properties of the system and the
relationship that exist among various
properties.
The state of a thermodynamic system can be
specified by measurable intensive properties
like P, v, T, u etc.
Since f (P, v, T)=0, implies the state of a
pure homogeneous fluid is fixed Whenever
two intensive thermodynamic properties are
set at definite values. Only two of the
properties of P, v, T, can be varied
independently, the value of the third
property can be fixed in terms of the other
two.
Phase Rule
The number of intensive parameters
that can be varied independently to
establish the intensive state of a system,
is called the degree of freedom, F of
the system and is given by the
celebrated phase rule of J. Willard
Gibbs (1875).
F=N- +2, where N is the number of
components, is the number of
coexisting phases.
The intensive state of a system containing
N chemical species, and phases in
equilibrium is characterized by the
intensive variables pressure(P),
temperature T and (N-1) mole fractions
for each phase. These are called phase
rule variables
The number of phase rule variables are
2+(N-1) .
The masses of the phases are not phase
rule variables. The masses of the phases
have nothing to do with the intensive state
of the system.
Example:Liquid water is in equilibrium
with its vapour, Find the degree of
freedom of the system?
This result is in agreement with the well
known fact that at a given pressure water is
having only one boiling point. Either
temperature or pressure can be varied
independently when water is in equilibrium
with its vapour
Applying phase rule F=N- +2. Here
N=1, =2, Hence F=1.
Example:Liquid water is in equilibrium
with a mixture of water vapour and
nitrogen. Determine F
Applying phase rule F=N- +2. Here
N=2, =2, Hence F=2.
T and P may be independently varied, but
once they are fixed, The system described
can exist in equilibrium only at a
particular composition of of the vapour
phase.
Vapor-Liquid-Solid Phase
Equilibrium in a Pure
Substance
Constant pressure change from liquid to
vapor phase for pure substance
Initial
Conditions:
T = 20
O
C
P = 100 kP
T increases
considerably
n increases
slightly
P remains const.
(100 kP)
T remains const.
(99.6
O
C)
n increases very
much
P remains const.
(100 kP)
T increases
n increases
P remains
const.
Phase Equilibrium in a Pure
Substance
Saturation temperature means the
temperature at which vaporization takes
place at a given pressure. This pressure
is called the saturation pressure for the
given temperature.
Example: For water at 99.6
O
C the
saturation pressure is 100 kP, and for
water at 100 kP the saturation
temperature is 99.6
O
C.
Vapor-pressure curve of a pure
substance
A point on this
diagram represents
a state of the
substance. Any point
lying on the curve is
a saturated state.
0
200
400
600
5 50 100 150 200
T
sat,
o
C
P
sat,
kPa
475.8kPa
101.35kPa
Temp,
T
sat
,
o
C
Saturation
pressure,
P
sat
, kPa
0.01 0.6113
5 0.4
10 0.87
30 4.25
50 12.35
100 101.3
150 475.8
200 1554
250 2973
Generating vapor-pressure curve of water
Phase Equilibrium in a Pure
Substance
At saturation temperature and pressure, If a
substance exists as vapor, it is called
saturated vapor.
At saturation temperature and pressure,
If a substance exists as liquid, it is called
saturated liquid.
If for given pressure, the temperature of
liquid is lower than saturation temperature,
it is called a subcooled liquid (T < T
S
) or a
compressed liquid (P > P
S
).
If for given pressure, the temperature of
vapor is greater than saturation
temperature, it is called a superheated
vapor.
The substances called gases are actually
highly superheated vapors.
Quality has meaning only for
substance at saturated state.
A substance exists as part liquid and
part vapor at saturation temperature.
Quality, x = mass of vapor/ total mass
Quality is an intensive property.
Example: For saturated vapor,
quality, x = 100%
Quality, x
Only defined when the system contains
two-phase mixture of a single substance.



x =
m
m
g
Liquid, m
f

Vapor, m
g

g f
m m m
Saturated
Saturated
P, T
sat

A piston cylinder contains 5 kg of water
liquid-vapor mixture, in which 3 kg is in
liquid phase. Find the quality. (How much
percent of the mixture is in vapor phase?)






x =
Example
m
m
g
Liquid,
m
f
=3kg
Vapor, m
g

g f
m m m
kg 3
f
m 5kg, m
2kg 3kg 5kg
m m m
f g


40% or 4 . 0
5
2

kg
kg
m=5kg
A piston cylinder contains 5kg of water-water
vapor mixture, in which 80% is in vapor phase.
How much liquid is in the mixture?






Example
m m x
g
/
Liquid,
m
f
=1kg
Vapor, m
g

g f
m m m
5kg, m
xm - m
m m m
g f

m=5kg
0.2 x - 1
1kg 0.8) - (1 5kg
x) - m(1

Generating the T-v diagram

P=1 atm
T=20
o
C
State 1
heat
W1
W2
W3
Generating the T-v diagram
P=1MPa
T=20
o
C
State 1
heat
W1
W2
W3
Temperature-Volume Diagram for
water (showing liquid & vapor phases)
T-v diagram of a pure substance
T
c
v
c
Subcritical
isobars
Supercritical
isobar
Liquid+vapor region
Compressed liquid region
Superheated vapor region
Supercritical fluid region
Supercritical fluid region
Important Points
The boiling temperature of a pure substance
increases with pressure. The specific volumes v
f
and
v
g
of the saturated liquid and vapor also change with
pressure.
The normal boiling temperature of a pure substance
is the temperature at which it boils under a pressure
of exactly 1 atm.
A series of isobars can plotted on a T-v diagram. If
the locus of all saturated liquid and vapor states are
connected, a dome enclosing the region of two phases
(liquid+vapor) results.
Each pure substance has one isobar that becomes
horizontal (flat) at only one point: critical point. This
point coincides with the top of the two-phase dome.

Important Points
The T-v diagram contains three single phase regions
(liquid, vapor, supercritical fluid), a two-phase
(liquid+vapor) region, and two important curves - the
saturated liquid and saturated vapor curves. The number
of regions and curves will increase when we consider
solids.
The saturated liquid and vapor curves meet at the critical
point, which represents the highest temperature and
pressure in which vapor and liquid phases can coexist.
The single phase liquid region is also called subcooled
liquid because, at a given pressure, temperature will be
below the boiling temperature.
The single phase vapor region is also called superheated
vapor because, at a given pressure, temperature will
always be above the boiling temperature.