CMT 458

PROPERTIES OF
PURE CHAPTER

2
SUBSTANCES
 PURE SUBSTANCES

A substance that has a fixed chemical composition and

properties.

A pure substance can be:

a)A mixture of various elements or compounds as long as

the mixture is homogeneous.
Eg: water, carbon dioxide

b) A mixture of two or more phases as long as the

chemical composition for each phase is the same.
Eg: ice-water mixture, water-vapor mixture
EXAMPLE

Identify which of the following are pure substance.

i)Diamond
ii)Mixture of oil and water
iii)Mixture of liquid air and gaseous air
iv)Pure sugar (sucrose)
v)Sulfur
vi)Sodium chloride
vii)Carbon monoxide
viii)Air
PHASES OF A PURE SUBSTANCE

A phase is a quantity of matter characterized by both

uniform physical structure and uniform chemical
composition.

A phase can be solid, liquid, vapor or gas.

The atoms in a solid phase are fixed
relative to other atoms in the solid.
They are however can vibrate about
this fixed position.

Solids can coexist in different

phases.

For example, solid carbon can exist SOLID

in the diamond phase or the graphite
phase.
Like a solid, molecules within the
liquid phase are in close proximity to
one another due to intermolecular
forces.

However, the molecules in a liquid are

not fixed relative to other molecules
in the liquid.

They are constantly in motion, free to

move relative to one another.

LIQUID
More than one liquid phase can coexist
such as oil and water. They are
considered separate liquid phases
since they are not miscible.
Gas molecules move randomly to
fill the entire volume of the
container in which they are
housed.

The molecules continuously

change direction as they collide
with each other and bounce off
the container surface creating
the measurable pressure p. GAS
PHASE CHANGES OF
PURE SUBSTANCES
 State 1
Consider water at room
temperature (20C) and
normal atmospheric pressure
(1 atm) in a piston-cylinder
device.

The water is in liquid phase,

and it is called compressed
liquid or subcooled liquid (not
Compressed liquid about to vaporize).
 If we add heat to water, its
temperature will increase; let
us say until 50C.

Due to the increase in

temperature, the specific
volume, v will increase.

As a consequence, the piston

will move slightly upward
therefore maintaining constant
Compressed liquid pressure (1 atm).
 State 2
Now, if we continue to add
heat to the water, the
temperature will increase
further until 100C.

At this point, any additional

addition of heat will vaporize
some water.

This specific point where

water starts to vaporize is
Saturated liquid called saturated liquid.
 State 2 - 3

The state between saturated

liquid (only liquid) and
saturated vapor (only vapor)
where two phases exist is called
saturated mixture.

Saturated mixture
 State 4 If we continue to add heat to
water, more and more vapor will
be created, while the
temperature and the pressure
remain constant (T = 100C and
P = 1 atm).

The only property that changes is

the specific volume. These
conditions will remain the same
until the last drop of liquid is
vaporized.

At this point, the entire cylinder

Saturated vapor is filled with vapor at 100C. This
state is called saturated vapor.
 State 5

After the saturated vapor

phase, any addition of heat will
increase the temperature of the
vapor.

This state is called superheated

vapor.

Superheated vapor
 Condensation is where a vapor (gas) is cooled, and
droplets of liquid form.

The reverse process of condensation is known as

vaporization.

Vaporization is where a liquid is heated, and the

liquid turns into vapor (gas).
 Saturated
liquid

Saturated
vapor

T-v diagram for the heating process of water at constant

pressure
 SATURATION TEMPERATURE
,Tsat

The temperature at which a pure

substance changes phase at a given
pressure.
EXERCISE

Find the saturation temperature, Tsat at:

i)P = 101.325 kPa

ii)P = 1 kPa
iii)P = 225 kPa
iv)P = 1.2 MPa
v)P = 22 MPa
 SATURATION PRESSURE, Psat

The pressure at which a pure substance

change at given temperature.
EXERCISE

Find the saturation pressure, Psat at:

i)T = 50 C
ii)T = 165 C
iii)T = 335 C
iv)T = 95 C
v)T = 373.95 C
T-v DIAGRAM
 As heat is transferred to the water at new pressure, the
process follows a path at 1atm pressure as shown in figure 1.1
i) water starts boiling at a much higher temperature at this
pressure.
ii) The specific volume of the saturated liquid is larger and the
specific volume of saturated vapor is smaller than the
corresponding values at 1 atm pressure.

That is the horizontal line that connects the saturated liquid

and saturated vapor states is much shorter.

As the pressure is increased further, this saturation line

continues to shrink, and it becomes a point when the pressure
reaches 22.06 MPa for the case of water.

This point is called the critical point.

T-v diagram of constant-pressure phase-change
processes of a pure substance at various pressures
(numerical values are for water).
P-v DIAGRAM
P-T DIAGRAM
 P-v-T DIAGRAM
The P-v-T surfaces present a great deal of information at once, but in a
thermodynamic analysis.
It is more convenient to work with two-dimensional diagrams, such as the
P-v and T-v diagrams.
 CRITICAL POINT

The point at which the saturated liquid and

saturated vapor states are identical.

At this point, the temperature, pressure and specific

volume of a substance are called respectively, the
critical temperature Tcr, critical pressure Pcr and
critical specific volume vcr.

The critical point properties of water are:

a)Pcr = 22.06 MPa
b)Tcr = 373.95 C.
c)vcr = 0.003106 m3/kg
P-T DIAGRAM
 TRIPLE POINT

The point at which three phases of liquid, vapor

and solid of a pure substances coexist in
equilibrium.

For water, the triple point temperature and

pressure are 0.01 C and 0.6117 kPa,
respectively.

The triple point appears in P-T diagrams.

P-T DIAGRAM
PROPERTY TABLE/
STEAM TABLE
SATURATED WATER TABLE

Since temperature and pressure are dependent properties

using the phase change, two tables are given for the
saturation region.

Table A-4 has temperature as the independent property

Table A-5 has pressure as the independent property.

These two tables contain the same information and often

only one table is given.

For the complete Table A-4, the last entry is the critical
point at 373.95 oC.
 A) SATURATED LIQUID AND SATURATED
VAPOR
Table A4: Saturation properties of water under temperature.
Table A5: Saturation properties of water under pressure.

A partial list of Table A4.

 b) Saturated Liquid-Vapor Mixture

Since state 3 (vaporization) is a mixture of saturated

liquid and saturated vapor, a new parameter called the
quality, x is established to locate it on the T-v diagram.
 Quality, x = mass vapor
mass total
Where:
mtotal = mliquid + mvapor
= m f + mg

Quality, x has significance for saturated mixtures

only.
It has no meaning in the compressed liquid or
superheated vapor regions.
The quality is 0 for the saturated liquid and 1 for the
saturated mixture.
VALUES FOR QUALITY

Phase Value of quality, x

Saturated mixture 0<x<1

Saturated liquid 0

Saturated vapor 1

Compressed liquid NA

Superheated vapor NA
Consider a tank that contains a saturated liquid-vapor
mixture:

Total volume = vol occupied by sat.liquid + vol occupied by sat.vapor

V = Vf + V g

V = mv

So, mv = mfvf + mgvg (1)

Total mass = mass occupied by sat.liquid + mass occupied by

sat.vapor
m = mf + mg
mf = m - mg (2)
Substitute equation (2) into (1):

mv = (m mg)vf + mgvg
v = (m mg)vf + mgvg
m m
= (1 mg)vf + mgvg
m m

Since x = mg
m

So, v = (1-x)vf + xvg

= vf xvf + xfg
= vf + x(vg vf)
Thus, the specific volume of the saturated
mixture becomes:
(3)
v = vf + xvfg

Equation (3) can be repeated for u, h

u = uf + xufg

h = hf + xhfg
SUPERHEATED VAPOR
TABLE
 CHARACTERISTICS OF
SUPERHEATED VAPOR

Lower pressures (P < Psat at a given T)

Higher temperatures (T > Tsat at a given P)
Higher specific volumes (v >vf at a given P or T)
Higher internal energies (u > uf at a given P or T)
Higher enthalpies (h > hf at a given P or T)
COMPRESSED LIQUID WATER
TABLE
 One reason for the lack of compressed liquid data
is, the relative independence of compressed liquid
properties from pressure.
In the absence of compressed liquid data, a general
approximation is to treat compressed liquid as
saturated liquid at given temperature.
Thus,

Where y is v, u, or h
CHARACTERISTICS OF
COMPRESSED LIQUID
EXAMPLE
Use the property table to determine the missing properties and
phase descriptions in the following table for water

T, c P, kPa u, kJ/kg x Phase

description

a) 200 0.7

b) 125 1000

c) 1000 2800

d) 75 500

e) 850 0.0
Answer

T, c P, kPa u, kJ/kg x Phase description

a) ? 200 ? 0.7 ?

x = 0.7 means 70% of mass is vapor phase, 30% of mass

is liquid phase.
So, we have saturated mixture phase at 200 kPa

T = Tsat@200 kPa = 120.21 C (Table A-5)

uf = 504.5 kJ/kg
ufg = 2024.6 kJ/kg (Table A-5)

u = uf +ufg
= 504.5 + (0.7)(2024.6)
= 1921.72 kJ/kg
 T, c P, kPa u, kJ/kg x Phase description
b) 125 ? 1000 ? ?

To determine phase, find uf and ug values.

At 125 C, uf = 524.83 kJ/kg
ug = 2534.3 kJ/kg
Since uf < u < ug, we have saturated mixture.

P = Psat@125 C = 232.32 kPa

Quality, x = u uf
ufg
= 1000 524.83 kJ/kg
2009.5
= 0.24
 T, c P, kPa u, kJ/kg x Phase description
c) ? 1000 2800 ? ?

At 1MPa, uf = 761.39 kJ/kg (Table A-5)

ug = 2582.8 kJ/kg
Since u > ug, we have superheated vapor

For superheated vapor, quality, x = NA

To find T,
T u
300 2793.7 (Table A-6)
T 2800
350 2875.7

T - 300 = 2800 2793.7

350 - 300 2875.7 2793.7
T = 303.84 C
 T, c P, kPa u, kJ/kg x Phase description
d) 75 500 ? ? ?

T and P are given.

To determine phase, refer Table A-5

At 500 kPa, Tsat = 151.83 C
Since T < Tsat, we have compressed liquid

In compressed liquid, quality, x = NA

u = uf@75 C = 313.99 kJ/kg

 T, c P, kPa u, kJ/kg x Phase description
e) ? 850 ? 0.0 ?

x = 0, therefore we have saturated liquid phase

T = Tsat@850 kPa = 172.94 C (Table A-5)

u = 731.00 kJ/kg
 EXERCISE
Use the property table to determine the missing properties and
phase descriptions in the following table for water

T, c P, kPa h, kJ/kg x Phase

description

i) 200 0.6

ii) 140 1800

iii) 1750 0.0

iv) 80 500

v) 800 3162.2
EXAMPLE

Determine the phase of water at these

conditions:

i)P = 10 MPa, v = 0.003 m3/kg

ii)P = 1 MPa, T = 190 C
iii)T = 200 C, v = 0.1 m3/kg
iv)P = 350 kPa, T = 110 c
v)T = 293 K, h = 2350.00 kJ/kg
 P , MPa V, m3/kg

i) 10 0.003

From Table A5

At P = 10 MPa = 10 000 kPa:

vf = 0.001452 m3/kg
vg = 1393.3 m3/kg

Since vf < vgiven < vg

So, the phase is saturated mixture
Answer:

i)Saturated mixture
ii)Superheated vapor
iii)Saturated mixture
iv)Compressed liquid
EXERCISE

Determine the phase of water at the following

conditions.

i)P = 10 bar, T = 170 oC

ii)T = 140 oC, u = 625.11 kJ/kg
iii)v = 4.16 m3/kg, T = 75 oC
iv)h = 2046.03 kJ/kg, T = 85 oC
v)P = 0.4 MPa, s = 7.2323 kJ/kg.K
EXAMPLE

A rigid tank contains 80 kg of saturated liquid

water at 40 C. Determine the pressure in the
tank and the volume of the tank.
Phase = saturated liquid water

At T= 40oC, (table A4):

P = Psat at 40oC

= 7.3851 kPa
The specific volume of the saturated liquid at 40oC:
v = vf @ 40oC = 0.001008 m3/kg

Then the total volume of the tank:

V = vm

= (0.001008 m3/kg)(80kg)

= 0.0806 m3
EXERCISE

A rigid tank contains 58 kg of saturated vapor

water at 125 C. Determine:

a)The pressure in the tank.

b)The volume of the tank.
Phase = saturated vapor

At T= 125 oC, (table A4):

P = Psat at 125 oC

= 232.23 kPa
b) The volume of the tank.

From Table A4, at 125 oC:

v = vg at 125 oC
= 0.77012 m3/kg

Volume, V = vgm

= (0.77012 m3/kg)(58kg)

= 44.67 m3
EXERCISE

A piston cylinder device contains 0.6 m3 of

saturated vapor water at 350 kPa. Determine
the temperature and the mass of the vapor
inside the cylinder.
Phase = saturated vapor water

At P = 350 kPa,
T = Tsat @ 350 kPa = 138.86 C (Table A5)

The specific volume of saturated vapor at 350 kPa:

v = vg @ 350 kPa = 0.52422 m3/kg (Table A5)

Mass of water vapor inside cylinder:

V = mv

m=V = 0.6 m3
v 0.52422 m3/kg

= 1.145 kg
EXERCISE

A piston cylinder device contains 2.5 m3 of

saturated vapor water at 800 kPa. Determine
the temperature and the mass of the vapor
inside the cylinder.
i)Temperature

Phase = saturated vapor water

At P = 800 kPa,
T = Tsat @ 800 kPa = 170.41 C (Table A5)
ii) Mass of water vapor inside cylinder

Phase = saturated vapor water

The specific volume of saturated vapor at 800 kPa:

v = vg @ 800 kPa = 0.24035 m3/kg (Table A5)

Mass of water vapor inside cylinder:

V = mv

m=V = 2.5 m3
v 0.24035 m3/kg

= 10.401 kg
EXAMPLE

A rigid tank contains 10 kg of water at 90 C. If

8 kg of water is in the liquid form and the rest
is in vapor form, determine:

a)The pressure in the tank.

b)The volume of the tank.
Phase = saturated mixture

a) The pressure in the tank.

P = Psat @ 90 C = 70.183 kPa

Phase = saturated mixture

b) At 90 C,
vf = 0.001036 m3/kg , vg = 2.3593
m3/kg

V = Vf + Vg

= mfvf + mgvg

= (8 kg)(0.001036 m3/kg) + (2 kg)(2.3593

m3/kg)

= 4.73 m3
EXERCISE

A rigid tank contains 15 kg of water at 105 C. If

10 kg of water is in the liquid form and the rest
is in vapor form, determine:

a)The pressure in the tank.

b)The volume of the tank.
a) Determine pressure in the tank.

Phase = saturated mixture

P = Psat @ 105 C = 120.90 kPa

b) Deterime volume of the tank.

Phase = saturated mixture

At 105 C:
vf = 0.001047 m3/kg , vg = 1.4186
m3/kg

V = Vf + Vg

= mfvf + mgvg

= (10 kg)(0.001047 m3/kg) + (5 kg)

(1.4186 m3/kg)
EXERCISE

Three kilogram of water is placed in an

enclosed volume of 0.5 m3. Heat is added until
the temperature is 428 K.

a)Find the pressure.

b)Calculate the specific volume of vapor.
a) Find the pressure.

T = 428 K = 155 C

From Table A4:

At 155 C, P = 543.49 kPa

b) Calculate the specific volume of
vapor.

V = mv

v = 0.5 m3
3 kg

= 0.17 m3 /kg
EXERCISE

A piston cylinder device contains 0.1 m3 of liquid water

and 0.9 m3 of water vapor in equilibrium at 800 kPa.
Heat is transferred at constant pressure until the
temperature reaches 350 C.

a)Identify the initial temperature of the water.

b)Determine the initial total mass of the water.
c)Calculate the quality of the water system.
d)Determine the phase of the system at final phase.
e)Calculate the final volume.
f)Generate the process on a P-v diagram with respects
to saturation lines.
(Dec 2014)
a) Identify the initial temperature of the water.

From table A5, at 800 kPa:

T1 = Tsat@800 kPa

= 170.41 C
b) Determine the initial total mass of the water.

Mass of liquid, mf = Vf
vf

= 0.1 m3
0.001115 m3/kg

= 89.69 kg

Mass of vapor, mg = Vg
vg

= 0.9 m3
0.24035 m3/kg

= 3.74 kg
Mass total = mf + mg

= 89.69 kg + 3.74 kg

= 93.43 kg
c) Calculate the quality of the water system.

x = mass vapor
mass total

= 3.74 kg
93.43 kg

= 0.04
d) Determine the phase of the system at final phase.

Given P2 = 800 kPa, T2 = 350 C

From Table A5, at 800 kPa:

Tsat = 170.41 C
T>Tsat, so the system in superheated vapor phase.

Final phase is superheated vapor

e) Calculate the final volume.

From Table A6, at 0.8 MPa and 350 C:

V2 = mv2

= (94.43 kg)(0.35442 m3/kg)

= 33.11 m3
f) Generate the process on a P-v diagram with
respects to saturation lines.
EXERCISE

Water is contained in a rigid vessel of 5 m3 at a quality

of 0.8 an a pressure of 2 MPa. The pressure is reduced
to 400 kPa by cooling the vessel.

a)What is the initial specific volume of water?

b)What is the final specific volume of water?
c)Calculate the total mass of water.
d)Find the mass of vapor.
e)Find the mass of liquid.

(Dec 2013)
a) What is the initial specific volume of water?

Initial phase = saturated mixture

v1 = vf + xvfg

= 0.001177 m3/kg + (0.8)(0.099587 0.001177) m3/kg

= 0.07991 m3/kg
b) What is the final specific volume of water?

Since the vessel is rigid, the final specific volume does

not change.

So, the final specific volume of water:

v2 = v1

= 0.07991 m3/kg
c) Calculate the total mass of water.

Total mass of water, m = V

v

= 5 m3
0.07991 m3/kg

= 62.57 kg
d) Find the mass of vapor.

x = v - vf
vfg

= (0.07991 - 0.001084) m3/kg

(0.46242 0.001084) m3/kg

= 0.17

Mass of vapor, mg = xmtotal

= (0.17)(62.57 kg)

= 10.64 kg
e) Find the mass of liquid.

Mass of liquid, mf = mass total mass of vapor

= 62.57 kg 10.64 kg

= 51.93 kg
EXERCISE

A rigid tank with a volume of 2.5 m3 contains 15 kg of

saturated liquid-vapor mixture of water at 75 C. Now
the water is slowly heated.

a)Calculate the initial specific volume of water.

b)Determine the temperature at which the liquid in the
tank is completely vaporized.
c)Show the process on a T-v diagram with respect to
saturation lines.
a) Calculate the initial specific volume of water.

v1 = V
m

= 2.5 m3
15 kg

= 0.1667 m3/kg
b) Determine the temperature at which the liquid in the
tank is completely vaporized.

When the liquid is completely vaporized the tank

will contain saturated vapor only.

So, final phase = saturated vapor

v2 = v1
= 0.1667 m3/kg
From Table A4, find v2 = vg = 0.1667 m3/kg

T vg

185 0.17390
T 0.1667
190 0.15636

T 185 C = (0.1667 0.17390) m3/kg

(190 185) C (0.15636 - 0.17390 m3/kg

T 185 = -7.2 x 10-3

5 -0.01754

T = 187.05 C
EXERCISE

A piston-cylinder device initially contains 50 L of liquid

water at 25 C and 300 kPa. Heat is added to the water
at constant pressure until the entire liquid is vaporized.

(a)What is the mass of the water?

(b)What is the final temperature?
(c)Determine the total enthalpy change.
(d)Show the process on a T-v diagram with respect to
saturation lines.
 CRITICAL PROPERTIES
At higher temperatures and/or higher pressures the
difference between a gas and a liquid eventually
disappears, and a supercritical fluid is formed.

The point at which the saturated liquid and saturated

vapor state are identical is called the critical point.
 The highest temperature at which a species
can coexist as a liquid and a vapor is termed
its critical temperature, Tc.

The highest pressure at which a species can

coexist as a liquid and a vapor is termed its
critical pressure, Pc.
 GAS EQUATION OF STATE
Equation of state:
Any equation that relates the pressure, temperature
and volume of a substance.

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.

Ideal gas equation of state:

PV = nRT
 IDEAL GAS

IDEAL GAS equation:

PV = nRT
where;
P = pressure, atm or Pa
V = volume, L
n = number of moles
R = ideal gas constant
= 8.314 J/mol.K if used Pa for pressure units
= 0.0821 L.atm/mol.K if used atm units for pressure
T = temperature, K
Assumptions of ideal gas:

1.An ideal gas can be considered as a point mass. It

simply means that the particle is extremely small where
its mass is almost zero. Ideal gas particle, therefore,
does not have volume.

2.The collision or impact between the particles are said

to be elastic. In other words, there is neither attractive
nor repulsive energy included throughout the collision
of particles. Since there is lack of inter-particle energy
the kinetic forces will remain unchanged in gas
molecules.
 When is a gas is not an ideal gas?
If either or both assumptions are invalid.

If a gas isnt ideal, what is it?

A gas which is not ideal is called a REAL GAS.
EXAMPLE

What is the mass of air contained in a cubical room with

5 m wall, if the pressure and temperature constant at
100 kPa and 20 C respectively? Given that the ideal gas
constant R = 8.314 m3Pa/mol and molar mass of
air = 28.97 kg/mol.

(JAN 2013)
 REAL GAS
Assumptions of real gas:
a) Gas particle does have significant volume
b) Collisions are non-elastic
Most commonly used equation of real gas law is Van
der Waals equation.

Van der Waals equation:

P = nRT - n2a
V nb V2

nb term is the corrections for volume of molecules

n2a is the correction for molecular attraction
V2
 Ideal gas Real gas

Particles have no mass Particles have mass

Particles have no Particles have volume

volume
Collision are elastic Collision are non-elastic
There are no attractive There are very small
or repulsive forces attractive or repulsive
between particles. forces between
particles.
EXERCISE

Define the meaning of the term equation of

state. Explain how the Van der Waals gas
equation gives a better approximation of a real
gas compared to the ideal gas equation.
 OTHER EQUATIONS OF STATE
Beattie-Bridgeman Equation of State
The constant are given in
Table 34 for various
substances. It is known to
be reasonably accurate for
densities up to about 0.8 cr.

Benedict-Webb-Rubin Equation of State

The constants are given in Table 34. This equation can handle
substances at densities up to about 2.5 cr.

Virial Equation of State

The coefficients a(T), b(T), c(T), and so on, that are functions of
temperature alone are called virial coefficients. 106
EXERCISE

Calculate the pressure exerted by 1 mole of N 2 gas

occupying 5.0 L at 50 C using:

i)Ideal gas equation.

ii)Van der Waals equation.
(a = 1.39 atm.L2/mol2, b = 0.0391 L/mol)
EXERCISE

Calculate the pressure exerted by two mole of Krypton

gas at a temperature of 400 K and a volume of 20 L
using:

i)Ideal gas equation.

ii)Van der Waals equation.
(a = 2.325 L2.bar/mol2, b = 0.0391 L/mol)
THE END