PURE SUBSTANCE

A pure substance is identified as a substance which has a

fixed chemical composition throughout its mass ie
Homogenous.
It can be a mixture of two or more substances as long as
the mixture is homogenous. For example Air
It can be of different physical appearance as long as the
chemical composition is same. For example
Water and Steam is a pure substance (H
2
O)
Oil and Steam is not a pure substance as they have
different chemical composition and do not mix to become
homogenous. On the other hand Salt and water could be
considered a pure substance if salt dissolves
homogenously in water.
Further the composition must not change with time eg
Mixture of Air and Fuel Vapor is Homogenous as long as
they do not react. Once reaction starts then the
composition changes and it is not a pure Substance
Now it may be possible that once Reaction is completed
then the products could form a homogenous mixture and
could be considered a pure substance.
It is important for us to identify the pure substance and
then analyse it.
PHASES OF A PURE SUBSTANCE
We have seen in daily life that material as well as pure
substances can exist as Solids, Liquids and Gas. One
lid)example is H
2
O which can be found as
Ice( Solid) , Water(Liquid) and Gas ( Steam)
Furthermore a Pure Substance can have different
appearance in its Principal Phase:-
Carbon in its solid phase can exist as Graphite as well as
Diamond. They are made of the same molecules but their
molecular structure is different.
Iron has three solid phases
Ice has seven solid phases at High Pressures
Why do we have different phases?
The answer lies in their molecular structure and the
bonding between the molecules.
Molecular Bonds are the strongest in Solids and are the
weakest in gases. When we heat a solid , it melts because
the molecular bonds are weakened by heat and the
substance becomes a liquid and on further heating
becomes a Gas.
Heat has a profound effect on change of phase, alongwith
pressure.
Lets look at the three phases in details.
SOLIDS
The molecules in a solid are arranged in a fixed pattern,
and remain in these fixed positions by the strong inter-
molecular bonds.
So in solid phase Molecules oscillate about their fixed
positions.
These oscillations become faster as the temperature of
the substance rises. The effect of high temperature is to
weaken the molecular bonds , and the molecules break
away.
THIS IS WHAT IS KNOWN AS MELTING PROCESS
LIQUIDS
In liquids , the molecules are no longer in fixed positions
relative to each other. Group of molecules float about
each other , but the group of molecules maintain an
orderly structure among themselves, and remain fixed in
their groups.
Inter molecular distances are larger than those in solids
and bonds are also weaker compared to solids.
GASES
Here the molecular distances are large , and there is no
fixed molecular pattern. Molecules are moving randomly,
and continuously collide with each other. Bonds are very
weak and molecules in the gaseous phase have high
energy levels.Thus we a Gas condenses or freezes, it
releases a large amount of Energy, mostly in the form of
heat.
PHASE CHANGE
Now we are aware that pure substances have different
phases , and also two or three phases of a pure
substance can co-exist in equilibrium.
Water and ice can exist as two phases at a particular
Temperature and pressure
Water and Steam can also exist as two phases.
Now we also know that phase change can take place but
not all the time. It requires a specific condition.
Lets look into this in more detail by investigating the phase
change of water.
Lets take water at 1 atm and 20
o
C, in a piston cylinder
arrangement. We heat the water at CONSTANT PRESSURE.
If we keep heating until the temperature is 100
o
C , and if
we keep heating we find that the temperature reaches
100
o
C , and further heat will cause vaporization.
A liquid about to vaporize is known as
SATURATED LIQUID.
1 Atm
20
o
C
As we heat the water we see that its
temperature rises, but it remains a
liquid.
This state is known as
COMPRESSED LIQUID or
SUB COOLED LIQUID
Now if we keep on heating the water starts boiling and
steam starts to form, but
THE TEMPERATURE DOES NOT RISE
Here both Liquid and Gas phase co-exist and their mixture
is known as SATURATED MIXTURE
Because of heat addition , all the water will vaporize into
steam.
HERE THE VAPOR IS SATURATED VAPOR
This is because if we remove heat , at point the vapor will
condense. Lets see this on a Temperature and specific
volume diagram:-
State 1-2 is compressed liquid
State 2-4 is saturated state, a mixture of Saturated Liquid
and Saturated Vapor
Once the liquid is completely vapor, ADDITION OF HEAT
WILL CAUSE TEMPERATURE OF VAPOR TO RISE
This is known as SUPERHEATED VAPOR
T
v
20
o
100
o
Compressed Liquid
Saturated Mixture
1
2 3
4
5
Super
Heated
Vapor
180
o
So if we have steam at 1 atm and 180
o
C, and if we
remove heat , the process will move in reverse direction,
but condensation will take place at 100
o
C.
So we see that at a pressure of 1 atm between
20 100
o
C Temp of water changes but it remains as
water. Phase does not change.
At 100
o
C Temp. does not change. Phase Changes
100 180
o
C Temp of vapor changes but it remains as
vapor. Phase does not change
SATURATION TEMPERATURE AND PRESSURE
We have seen that at 1 atm , the change of phase takes
place at 100
o
C.
If the pressure was not allowed to remain constant , then
the phase would be at a different temperature.
THUS CHANGE OF PHASE OCCURS AT A FIXED
TEMPERATURE FOR A FIXED PRESSURE.
This combination of Pressure and Temperature is known
as Saturation Pressure and Saturation Temperature
For water we have
T
Sat
in
o
C P
Sat
in kPa T
Sat
in
o
C P
Sat
in kPa
-10 0.26 100 101.3
0 0.61 150 475.8
10 1.23 200 1554
30 4.25 300 8581
LATENT HEATS
To change phase we need to either add Heat or remove
Heat. This energy is known as LATENT HEAT.
When we change from solid to liquid ( MELTING)
or change from liquid to solid ( FREEZING)
Then the heat required for melting of heat removed for
freezing is called as LATENT HEAT OF FUSION
When we change from liquid to gas ( VAPORIZATION)
or change from gas to liquid ( CONDENSATION)
Then the heat required for VAPORIZATION of heat
removed for condensation is called as LATENT HEAT OF
VAPORIZATION.
The Latent Heats have specific value for each
combination of Saturation Temperature and Pressure. We
will see how to evaluate these values at a later stage.
LIQUID VAPOR SATURATION CURVES
We have seen that T
Sat
and P
Sat
have a fixed relationship
for each pure substance. ( )
SAT SAT
T f P
. So if we plot it
for a pure substance we get
Thus if Saturation pressure drops Saturation temperature
also reduces.
Thus at high altitudes Water boils at less than 100
o
C,
because of low pressures at high altitude
Sometimes one wants to cook at high temperature , so we
use pressure cookers. This allows Boiling temperature to
increase.
P
Sat
T
Sat
LIQUID-VAPOR SATURATION CURVE
Property Diagrams
We can draw P-v-T diagrams of phase change by keeping
one property constant. If we want to make a T-v diagram
we keep Pressure Constant , and then make it for water.
We will observe the following trend
We see that at each pressure there is a temperature
where the liquid changes to gas and then again the
temperature increases. Now as the pressure increases
the phase change line becomes shorter and shorter. At a
pressure of 22.09 MPa the phase change becomes a
T
v
0.1 MPa
1.0 MPa
8 MPa
15 MPa
22.09 MPa
25 MPa
Critical Point
374.14
point. At this point the temperature is 374.14
o
C. This point
is known as CRITICAL POINT. Here Saturated Liquid and
Saturated vapor States are identical.
At this point the we have Critical Pressure, Critical
temperature and critical specific volume. For water
Critical Pressure is 22.09 Mpa
Critical temperature is 374.14
o
C
Critical specific volume is 0.003155 m
3
/kg
For helium it is
Critical Pressure is 0.23 Mpa
Critical temperature is -267.85
o
C
Critical specific volume is 0.01444 m
3
/kg
At pressures above P
Critical
the phase change will not be
distinct. A sudden change will take place and it cannot be
predicted.
Generally we refer to any substance as SUPERHEATED
VAPOR above its Critical Temperature. and as
COMPRESSED LIQUID below Critical Temperature.
Now in the above diagram we connect the saturated
states points we get the following:-
Similarily we can get a P-v diagram keeping the
temperature constant.
In P-v diagrams the constant temperature line are nearly
straight.We will learn about how to use these diagrams at
a later stage in the course

Saturated Liquid Line
Saturated
Vapor Line
T
v
Critical Point
Saturated Liquid and
Saturated Vapor Region
Saturated Liquid Line
Saturated
Vapor Line
P
v
Critical Point
Saturated Liquid and
Saturated Vapor Region
SOLID PHASE. We have uptill looked at equilibrium
states of liquid , vapor and liquid- vapor states. We will
now look at the Solid Phase. So if we reduce pressure
and temp. we get into solid phase. Lets make a P-v
diagram
S
O
L
I
D
S
O
L
I
D
+
L
I
Q
U
I
D
L
I
Q
U
I
D
TRIPLE LINE
LIQUID + VAPOR
SOLID + VAPOR
CHANGE FROM
SOLID TO VAPOR
CHANGE FROM
VAPOR TO SOLID
This is a P-v diagram of a substance which contracts on
freezing. There are substances which expand on freezing
like water. This entails a slightly P-v diagram .
The Triple Line is the point where Vapor + Liquid + Solid
can exist together. At Triple Line the Pressure and
Temperature is fixed. The specific volume can change.
The change from Solid to Vapor is known as
SUBLIMATION
The triple point data of a few substances is as follows
Substance Pressure
T.Point
Temperature
T.Point
WATER 0.6113 kPa 0.01
o
C
OXYGEN 0.1502 kPa -218.81
o
C
TITANIUM 0.0053kPa 1668.0
o
C
We can also make a P-T diagram and it will look like this
At triple point all three phases co exist.
P-v-T SURFACES.
We had earlier stated the two property rule. So we can fix
the state of a substance by two Independent Intensive
Properties. Then other properties will become dependent
on these two properties. We can thus relate P-v-T and
present it on a 3-Dimensional graph. These are shown in
Fig 2-26 and 2-27.
VAPOR
Liquid
Solid
Expands on
Freezing
Sublimation
Melting
Vaporization
TRIPLE POINT
Contracts on
Freezing
Vapor Pressure and Phase Equilibrium
A gas exerts pressure . This pressure is due to the force
exerted by the moving molecules in the gas. In fact
( )
( )
( )
F Avg Velocity of molecules No of molecules per unit volume
so P f T and density

If a gas has five individual pure substances then

( )
Total a b c d e a
P p p p p p where p are the partial pressures
so p No of molecules Moles
+ + + +

Now atmospheric air consists of Dry air and water vapor
so
atm dry air water vapor w v
P p p p is known as vapor pressure +
P
w v
is generally about 3 % of P
atm
The vapor pressure is due to the molecules of water vapor
in atmospheric air. However air can only absorb a certain
amount of water vapor. We thus define a term called
Relative Humidity which is defined as
.
. .
Actual amount of water vapor in air at temp T
Max amount of which can be held in air at temp T

varies from 0 to 100 %
0 % is called dry air
100 % is moist air or Rain
Now the vapor pressure of water vapor is a max when the
water vapor present exerts a pressure equal to its
saturation pressure at the existing temperature. It has
been found that
@ v Sat T
P P
so
if =60 % and T=25
o
C then at 25
o
C the value of
P
sat
=3.17 kPa so P
v
=0.6(3.17)=1.9 kPa
Since P
sat
increases with increase of Temperature so at
high Temperatures air can hold more moisture. So
wherever we have high humidity area ie moist climates we
have FOG(suspended droplets) when temperature drops
or DEW(Liquid Water) on cold surfaces.
PHASE EQUILIBRIUM
Now if we take liquid water in open air , we find that it will
start evaporating.
In DRY AIR evaporation is faster , because air has more
capacity to hold water vapor.
Now as the vapor goes into atmosphere it increases the
quantity of vapor in the air. A time will come when the air
will not accept any more water vapor. This is because the
air has become saturated with water vapor.
This is the point of phase equilibrium. This is governed by
the fact that :
THE VAPOR PRESSURE IN THE AIR IS EQUAL TO
THE SATURATION PRESSURE OF WATER AT THE
TEMPERATURE OF THE AIR.
w vapor Sat of water Water
p P at T
This is valid for water exposed to air.
If p
vapor
in air is less than P
sat of water
at water temperature ,
then water will evaporate in open air. The larger the
difference between P
Sat of water
and p
vapor
, the greater the
evaporation.
Evaporation will cool the water and water temperature will
reduce. As a reduction in water temperature will reduce
P
Sat of water ,
so evaporation will reduce until a balance is
achieved. This is phase equilibrium between the vapor
and liquid water.
We can however increase the evaporation , by increasing
the water temperature. Hence hot water will evaporate
faster than cold water in the same environment. We will
study about this when we study air conditioning in the next
semester.
PROPERTY TABLES AND CHARTS
Since systems require values of properties for their state
identification , so we need to know how to evaluate the
properties. This is done by
A. Generating mathematical functions to relate
properties
B. Do experiments and develop experimental data
C. Both
Also sometimes we combine certain properties to get a
new property . We will see a lot of these but at present we
look at one very important combination called ENTHALPY
ENTHALPY is a property made up by combining Internal
energy , Pressure and Volume and given symbol H
.
/
, int
H U PV with units of Joules called Enthalpy
If we divide by mass
H U PV
then we have h u Pv J kg
m m m
h specific enthalpy u specific ernal energy
and v specific volume
+
+ +

( )
3
2
We check the units U is in Joules
N
PV m N X m Joules
m

s
So Enthalpy is a property which is representative of
energy.
SATURATED LIQUID AND SATURATED VAPOR STATE
Lets us look at these phases
Saturated Liquid Line
Saturated
Vapor Line
T
v
Critical Point
Saturated Liquid and
Saturated Vapor Region
f g
On the saturation line points left of Critical point are
Saturated Liquid points.(f)
Points right of Critical point are Saturated vapor points.(g)
So volume at Sat. Liquid line is denoted by v
f
and volume
of saturated by v
g
Similarily all properties related to saturated liquid will be
indicated by subscript f . Thus u
f
, h
f
,
And Similarily all properties related to saturated vapor will
be indicated by subscript g . Thus u
g
, h
g
,
v
f-g
= v
g
v
f
= Difference of Sat vapor and Sat Liquid
Specific volumes at the same saturation conditions.
h
f-g
= h
g
h
f
= Difference of Sat vapor and Sat Liquid
Specific enthalpies at the same saturation conditions.
u
f-g
= u
g
u
f
= Difference of Sat vapor and Sat Liquid
Specific internal energies at the same saturation
conditions.
h
f-g
is called Enthalpy of Vaporization or
LATENT HEAT OF VAPORIZATION
h
f-g
decreases at P
sat
and T
Sat
increases
h
f-g
=0 at Critical Point
For water these properties are given in what is known as
Steam tables and these are given in your book as table
4,5,and 6. Lets look at few examples like 2-2,2-3 and 2-4.
SATURATED LIQUID-VAPOR MIXTURE REGION
Saturated Liquid Line
Saturated
Vapor Line
T
v
Critical Point
Saturated Liquid and
Saturated Vapor Region
f g
In the saturated liquid-vapor region both exist in
equilibrium. So here mass of mixture is equal to the
mass of liquid + mass of vapor.
At this point we define the quality of the mixture as
Vapor g
Total f g
m m
x
m m m

+
If all the mass is liquid then
0
0
0
f
x
m

+
If all the mass is vapor then
1
0
g
g
m
x
m

+
So quality varies from 0 to 1.00 for Saturated mixture with
Saturated Liquid has x = 0 and
Saturated Vapor has x = 1.00
What happens if we are not at saturated conditions.
So we are at point 1 then here V
1
= m
total
(v
1
)
Saturated Liquid Line
Saturated
Vapor Line
T
v
Critical Point
Saturated Liquid and
Saturated Vapor Region
f g
1
2
( ) ( )
( ) ( ) ( )
( ) ( ) ( )
( ) ( ) ( )
1 1
1
1
( )
( )
(1 )
(1 )
(1 )
f g Total f f g g
g g
Total g f
Total Total
f g f g f
f g f g f
f g f g f
V V V or m v mv m v
m v
m m v
v
m m
v x v x v v x v v
This is also valid for other properties
u x u x u u x u u
h x h x h h x h h
+ +

+
+ +
+ +
+ +
SUPERHEATED VAPOR
All vapor having Temperature greater than T
Sat
for its
existing pressure is called SUPERHEATED VAPOR
Point 2 is in superheated region . For their properties we
have separate table namely Table A-6
COMPRESSSED LIQUID.
Saturated Liquid Line
Saturated
Vapor Line
T
v
Critical Point
Saturated Liquid and
Saturated Vapor Region
f g
1
2
3
All liquid have temp less than T
sat
for its pressure.
Generally very less data is kept for compressed liquid as it
is Independent of Pressure. Generally v
Comp. Liquid
= v
f
at its
temp ,
u
Comp. Liquid
= u
f
at its temp and h
Comp. Liquid
=h
f
at its temp
This is valid for low pressures like point 3
For high pressure h=h
f
+ v
f
(P P
sat
) only as enthalpy is
sensitive to pressure.
REFERENCE STATE
Generally the value of u and h are calculated with
respect to a reference state where h and u of the
substance is considered zero.
For water this is 0.01
o
c as T
sat
For refrigerant 134-A it is -40
o
C
The calculation of these properties will be learnt in
semester III
IDEAL GAS EQUATION OF STATE
We have seen that properties of water is found
experimentally, and presented in tables. We will now look
at Ideal Gases.
Any Equation that relates Pressure,Volume and
Temperature is called as EQUATION OF STATE.
The other properties can then be defined by further
equations like H = U+PV. This can also be called an
Equation of State. However for our studies we will refer to
only that equation which links P,V and T.
Before we look at the IDEAL GAS EQN. OF STATE we
need to be clear about what is a Gas and what is a vapor.
A SUBSTANCE IS A GAS WHEN IT IS ABOVE ITS
CRITICAL TEMPERATURE.
It is a vapor when it is below its critical temperature . A
vapor is easily condensable , while a gas is not easily
condensable.
The EQUATION OF STATE OF AN IDEAL GAS is given
by PV=mRT where P= Pressure in Pa
T=Absolute Temperature in
o
K , V=Volume in m
3
R=Gas Constant in Joules per kg per
o
K
m= mass in kg
R= Gas Constant and is different for each gas.
Now PV=mRT can be written as Pv=RT by dividing both
sides by the mass and designating v= specific volume.
tan 8314
u
U o
R Joules
R where R Universal Gas Cons t
M k mol K

The value of R
U
is the same for all Gases.
M=Molar Mass and it is equal to mass of one Mole of gas.
Mole of a gas is the Molecular weight( Mass of Molecules)
of the gas expressed in grams or kilograms. generally
K.Mol is used.
So if we have Oxygen then its molecular weight is 32 so
1 K.mol of Oxygen has a mass of 32 kg/K.mol
Hydrogen has molecular weight of 2 so 1 K.mol of
hydrogen has mass of 2kg/k.mol
The number of molecules in a mole is given by the value
of N. Generally if m=mass then m=MN
so if we have 93 kg of oxygen then since for oxygen
M=32 kg/K.mol so
93 kg= 32 kg/K.mol(N) so N=2.906 K.mol
If we now have to find R of other gases we can do the
following
2
2
2
2
.
8314
.
4157
2
.
o
o
U
H o
H
o
kg
H has M
K mol K
Joules
R Joules K mol K
so R
kg
M kg K
K mol K

2
2
2
32
.
8314
.
259.8
32
.
o
o
U
H o
H
o
kg
O has M
K mol K
Joules
R Joules K mol K
so R
kg
M kg K
K mol K

Now Pv=RT then the units will be as follows
( )
3
2
3
2
,
o
o o o
N m
P v and T is in K
m kg
N m
N m
Pv Joules m kg
so
T K kg K kg K
1

1
]
1
1
]

2
8314
188.95
44
8314
286.7
29
CO o
Air o
Joules
Now R
kg K
Joules
R
kg K


Values of R and M of several gases are given in Table A-1
3
.
U
U
U U
R
V mv and m MN so PV MNRT MN T NR T
M
V
or P R T we write this as Pv R T
N
m
v is defined as Molar Specific Volume with units of
K mol


Now if an ideal gas goes from one state to another state
IDEAL GASES ARE NOT FOUND IN NATURE.
However most gases found in our world ( known as Real
Gases) behave like ideal gases with great degree of
accuracy.
Most gases behave in an Ideal Manner at
LOW PRESSURES AND HIGH TEMPERATURES.
Water Vapor behaves like an ideal gas below 10 kPa even
if temperature is Low. ( Area of low density)
At High Pressures Water vapor does not behave like an
ideal gas.( Area of high density)
Since most gases may not behave as an ideal gas for
accuracy , so we must have some way of dealing with
non-ideal gases with accuracy. This is done by looking at
the concept of Compressibility Factor.
COMPRESSIBILITY FACTOR
1
2
Then at state 1 P
1
v
1
=RT
1
and
at state 2 P
2
v
2
= R T
2
and since
R remains constant so we say
Most gases deviate from Ideal gas behaviour near the
Saturation Region and near the Critical point. To account
for this deviation we use the concept of COMPRSIBILITY
FACTOR (Z) where

actual
ideal
v Pv
Z or Pv ZRT so Z
RT v

For Ideal Gas Z=1.00
Now we had earlier said that most gases behave ideally at
Low Pressures and High Temperatures.
But what is Low Pressures and High Temperatures?
at -100
o
C N
2
and Air behave as ideal gases. Now
we see that for N
2
CP Temp is -147
o
C and
for Air is -140
o
C
Most gases will liquefy at these temperatures. So to
determine the region of Ideal gas behavior we define two
quantities
Re Pr
Re
R
CR
R
CR
P
duced essure P
P
T
duced Temperature T
T


THIS IS CALLED AS
PRINCIPLE OF CORRESPONDING STATES
In Fig 2-57 Z is plotted against P
R
for various T
R

Most gases have same Z at the same P
R
and T
R
Real gases obey the Principle of Corresponding states.
The charts are known as generalized charts and are given
in Figures A-29 a,b,c. If we look at these charts we see
a. At very low pressures P
R
<<1. Most gases behave
as Ideal gas regardless of temperature as Z is
nearly equal to 1
b. At high temperatures T
R
>>>2, Ideal gas behaviour is
experienced regardless of Pressure except when
P
R
>>1
c. Z has very low values at P
R
=1 and T
R
=1. Very poor
ideal gas behaviour.
If P and v are given or T and v are given then we can still
use the compressibility chart . For this we define
actual
R
CR
CR
v
v
RT
P

. Lines of constant v
R
are also plotted on
compressibility charts.
Other Scientists have also worked on generating
Equations of state for real gases. These are as follows:-
VAN DER WALLS
( )
2
a
P v b RT
v
_
+

,
this equation accounts for
a. Intermolecular forces accounted by a/v
2
b. Volume occupied by molecules themselves accounted
by b
The value of a and b is found experimentally and they are
( )
2
2
27
64 8
CR
CR
CR CR
R T
RT
a b
P P
where a and b can be evaluated from CP data

BETTIE-BRIDGEMAN EQUATION
has five constants and is accurate upto 0.8
CR
( )
2
3
1
U
R T c A
P v B
vT v
v
_
+

,
BENEDICT-WEBB-RUBIN
has eight constants and is accurate upto 2.5
CR
Eqn given in book (2-27)
VIRIAL EQN. OF STATE
Expressed in series.
Eqn given in book( 2-28)