Ch# 2 Properties of

Pure Substances

Objectives
Introduce the concept of a pure substance.

Discuss the physics of phase-change processes.

Illustrate the P-v, T-v, and P-T property diagrams and P-v-T surfaces of
pure substances.
Demonstrate the procedures for determining thermodynamic properties of
pure substances from tables of property data.
Describe the hypothetical substance ideal gas and the ideal-gas equation
of state.
Apply the ideal-gas equation of state in the solution of typical problems.
Introduce the compressibility factor, which accounts for the deviation of
real gases from ideal-gas behavior.
Present some of the best-known equations of state.

Pure Substance
In Chemistry you defined a pure substance as an

element or a compound
Something that can not be separated
In Thermodynamics well define it as something
that has a fixed chemical composition
throughout

Examples of Pure Substance

Water, nitrogen, helium, and carbon dioxide, for

example, are all pure substances.

A mixture of water liquid and water vapor, for
example, is a pure substance because both
phases have the same chemical composition.

Example of Non-Pure Substance

A mixture of liquid air and gaseous air, however, is

not a pure substance.

This is because different air components condense at

different temperatures at a specified pressures and

thus the composition of liquid air and gas air will be
different..

Phases of Pure Substance

A phase is identified as having a distinct molecular

arrangement.
This molecular arrangement is homogeneous
throughout the system.
The phase separated from the other phases by easily
identifiable boundary surfaces.

Solid Phase of Pure Substance

The molecules in a solid are arranged in a lattice

that is repeated throughout.

Three dimensional pattern
Large attractive forces between atoms or
molecules
The atoms or molecules are in constant motion
they oscillate in place
The higher the temperature the more vibration

Liquid Phase of Pure Substance

When a solid reaches a sufficiently high

temperature the velocity (and thus the

momentum) of the molecules reach a
point where the intermolecular forces are
partially defeated and groups of the
molecules break away (melting point)
In liquid the molecular spacing is not
much different from that of solids,
except that they can rotate and translate
freely (they are not at fixed positions
relative to each other)
Distance between molecules increase
slightly as a solid turns to liquid

Gas Phase of Pure Substance

In the gas phase, the molecules are far

apart from each other, and a molecular

order is nonexistent.
Molecules move about at random,
continually colliding with each other and
the walls of the container they are in
High kinetic energy
In order to liquefy, lots of that kinetic
energy must be released

Liquid phase to Gas Phase

Let us study what would happen when we heat a liquid phase of pure

substance at a constant pressure

Liquid Water

Piston cylinder
device
maintains
constant
pressure

T
5
2

1
v

Phase Change
Processes on a
T-v diagram

Phase Change Processes on a T-v diagram

Consider a piston-cylinder device with water

inside at 20oC and 1 atm pressure .

At this P and T, water is called compressed (or
subcooled) liquid state.
Compressed liquid means that it is not about
to vaporize.
The system is heated and the piston is allowed
to float and thus the pressure will be constant.
T and v will increase until the system reaches
100 C at which any addition of heat will cause
some of the liquid to vaporize
The temperature at which a pure substance
changes phase is called the saturation
temperature, Tsat.
At Tsat, Liquid and vapor phases are in
equilibrium.

A liquid that is about

to vaporize is called
Saturated Liquid.

 Adding more heat will cause

boiling to start. Liquid gradually

evaporates (state 3) but
temperature will remain constant,
Why?
The only change is the increase in
the specific volume (v) until it
reaches state 4 (saturated vapor).
Heating the system further, will
increase both the temperature and
specific volume (state 5). This
single-phase state is called
Superheated vapor
Repeat this experiment for higher
pressures.
Similar curves will be obtained but
at higher sat. temperature.
Note that the sat. liquid specific
volume (vsat,l ) will increase while
the sat. vapor specific volume
(vsat,g ) will decrease

A substance between
saturated liquid (state 2) and
saturated vapor (state 4) is
called saturated liquid-vapor
mixture.

A vapor that is about to

condense is called
Saturated vapor.

Saturation Temperature and Pressure

Water at a pressure of 101.325 kPa, Tsat is 100oC. Conversely, at a
temperature of 100oC, Psat is 101.325 kPa.
Latent heat: fusion and vaporization.
The magnitude of the latent heats depend on the temperature or
pressure at which the phase change occur.

Saturation Temperature and Pressure

At a given pressure, the temperature at which a

pure substance changes phase is called the
saturation temperature. Likewise the pressure.

Critical Point
The critical point is defined as the

point at which the saturated liquid

and saturated vapor states are
identical.
At the critical pressure, there will be
no distinct phase change process.
Instead, the specific volume of the
substance will continually increase
and at all times there will be only
one phase present.
The saturated liquid states can be
connected by a line called the
saturated liquid line.
The saturated vapor states can be
connected by another line, called
the saturated vapor line, to form a
phase dome.
Three main regions can be
identified.

vsat,l and vsat,g will be the same and we

speak of Pcrit, Tcrt, and vcrit.

Phase Change Processes on a P-v diagram

Decrease P gradually but

keep T constant.
Water boils at Psat
The pressure at which a

pure substance changes

phase is called the
saturation pressure Psat.
At Psat, Liquid and vapor
phases are in equilibrium.
From State 2 to 4, no
weights are removed
(P=constant) and T is kept
constant but heating
causes liquid to vaporize.

P-v diagrams with Solid Phase

P v diagram of substance that

contracts on freezing
P v diagram of substance that
expands on freezing (such as
water)

Triple point
Under some conditions all three

phases of substance coexist in

equilibrium at states along the
triple line.
The states on the triple line of
substance have the same pressure
and temperature but different v.
The triple line appears as a point
on the P-T diagram.
The triple point of water occurs
at T= 0.01 C and P=0.6113 Kpa

Property Diagrams
P-T diagram

(or Phase diagram)

The P-T diagram is often called

phase diagram since all three

phases are separated by three lines,
namely the sublimation line
(between solid and vapor regions),
the vaporization line (between
liquid and vapor regions), and the
melting line (between solid and
liquid).

P-v-T surfaces

You can plot P, T, V on a

three dimensional graph

Top view
Tem

w
e
i
v

t ur
a
r
pe

P
P

Tv
ie w

Thermodynamics Tables
The relationship among thermodynamic properties are too complex to be

expressed in simple equations and thus, properties are measured and/or

calculated and then presented in a tabulated form.
In single-phase regions, any

two properties will fix the

state.
In two phase regions, any
two properties (except P and
T) will fix the state. P and T
are dependent on each other.

Enthalpy A Combination Property

In the analysis of certain types of processes, particularly in power

generation and refrigeration, we frequently encounter the combination of

internal energy U, and pressure-volume product PV. That is

H U PV

h u p

Before 1930, h was referred to as heat content or total heat.

After 1930, it is referred to as enthalpy (from the Greek word enthalpien

which means to heat)

Saturated Liquid and Saturated Vapor States

Table A-4
Saturated liquid-vapor

mixture falls under the P-v

(or T-v) dome.
Its properties can be obtained
from Water Tables A-4 and
A-5

Saturated Liquid and Saturated Vapor States

Table A-5
In Table A-5 (page 832),

Pressure is listed in the left

column as the independent
variable.
Use whichever table is
convenient.

v fg v g v f

h fg hg h f
Enthalpy of vaporization or

latent heat
the amount of energy needed
to vaporize a unite mass of
saturated liquid at a given
temperature or pressure

Example 2-1:
Saturated Liquid and Saturated Vapor
A rigid tank contains 50 kg of saturated liquid water at 90 oC. Determine the

pressure in the tank and the volume of the tank. (Table A-4)

(Answers: 70.14 kPa, 0.0518 m)

Example 2-2:
Saturated Liquid and Saturated Vapor
A piston-cylinder device contains 2 ft3 of saturated water vapor at 50-psia pressure. Determine the temperature

of the vapor and the mass of the vapor inside the cylinder. (Table A-5E)

(Answers: 281.03oF, 0.235 lbm)

Example 2-3:
Saturated Liquid and Saturated Vapor
A mass of 200 g of saturated liquid water is completely vaporized at a

constant pressure of 100 kPa. Determine (a) the volume change and (b) the
amount of energy added to the water.

(Answers: 0.3368 m3, 451.6 kJ)

Saturated Liquid-Vapor Mixture

In the saturated liquid-vapor mixture, the mass fraction of vapor is called

the QUALITY (x) and is expresses as

m
m
x

m m m
g

Derivation:

V V f Vg
mv m f v f mg v g
( m m g )v f m g v g
v (1 x)v f xvg
v v f x (v g v f )
v v f xv fg
where v fg v g v f

total

Average Properties
In the saturated mixture region, the average value of any intensive property

y is given as:

y y f x( yg y f )
y f x y fg
where f stands for saturated liquid and g for saturated vapor. For example:

Average Properties
In the saturated mixture region, the average value of any intensive property y is
given as:

y y f x( yg y f )
yf x y

01
fg

= yg

where f stands for saturated liquid and g for saturated vapor. For example:
When x = 0 we have all liquid, and y = yf
When x = 1 we have all gas, and y = yf + yfg = yg
The average properties of the mixtures are always between the values of the
saturated liquid and the saturated vapor properties. That is

y f yavg y g

X=0

X=1

Saturated Liquid-Vapor Mixture

T Tsat at given P
P Psat at given T
v f v v g at given P or T
u f u u f at given P or T
h f h h f at given P or T

saturated mixture

Quality is an intensive property

Example 2- 4:
Saturated Liquid-vapor mixture (continued)
A rigid tank contains 10 kg of water at 90 oC. If 8 kg of water is in the

liquid form and the rest is in the vapor form, determine (a) the pressure in
the tank and (b) the volume of the tank.

(Answers: 70.14 kPa, 4.73 m3)

Example 2-5:
Saturated Liquid-vapor mixture (continued)
An 80-L vessel contains 4 kg of refrigerant 134a at a pressure of 160 kPa.

Determine a) the temperature of the refrigerant, b) the quality, c) the

enthalpy of the refrigerant, and d) the volume occupied by the vapor phase.

(Answers: -15.62oC, 0.158, 62.7 kJ/kg, 0.0777 m3)

Superheated Vapor Table A-6

In the region to the right of the saturated vapor line, a substance exists as

superheated vapor (single phase).

Superheated Vapor

T Tsat at given P
P Psat at given T
v v g at given P or T
u u g at given P or T
h h g at given P or T

superheated vapor

Compressed liquid Table A-7

In the region to the left of the saturated liquid line, a substance exists as

compressed liquid.

Compressed Liquid

T Tsat at given P
P Psat at given T
v v f at given P or T
u u f at given P or T
h h f at given P or T

compressed liquid

A general approximation

In the absence of compressed liquid data, a general approximation is to treat

compressed liquid as saturated liquid at the given temperature. Such that

yy

f @T

If the compression is moderate, the properties do not vary significantly with

pressure. But they do vary with temperature

Linear Interpolation
A

100

130

200

10

130 100 y 5

200 100 10 5

Linear Interpolation (Continued)

Now
X1=
X =
X2=

T
140
143
145

y y1

Psat
y1= 0.3615
y=?
y2= 0.4154

x x1

( y2 y1 )

x2 143
x1 140

Psat 0.3615

Psat 0.394

y y1
x x1

y 2 y1 x 2 x1

145 140
kPa

( 0.4154 0.3615)

Example 2-7
Superheated Vapor
Determine the temperature of water at a state of P = 0.5 MPa and h = 2890

kJ/kg.

(Answers: 216.4 oC)

Example on Compressed Liquid

Example 2-8:
Determine the internal energy of
compressed liquid water at 80oC
and 5 MPa using (a) data from the
compressed liquid table and (b)
saturated liquid data. What is the
error involved in the second case?
(Answers: 333.72 kJ/kg, 334.86
kJ/kg, 0.34%)

5M

263.99

80

80

pa

The Use of Steam Table to Determine

Properties
Example 2-9:
Determine the missing properties and the phase descriptions in the
following table for water.

Reference State and Reference Values

The values of u, h, and s cannot be measured directly, and they are

calculated from measurable properties using the relations between

thermodynamic properties. However, those relations give the changes in
properties, not the values of properties at specified state.
For water, the state saturated liquid at 0.01 oC is taken as the reference
state, and the internal energy and entropy are assigned zero values at that
sate.
For refrigerant 134a, the state saturated liquid at -40 oC is taken as the
reference state, and the enthalpy and entropy are assigned zero values at
that state.
In thermodynamics we are concerned with the changes in properties, and
the reference chosen has no consequences in the calculations.