Ch# 3 Pure

Substances and Its

Properties
 Pure Substance
 In Chemistry pure substance defined as it is an
element or a compound
Air N2
 Something that can not be separated
 In Thermodynamics we’ll define it as something that
has a fixed chemical composition throughout
 A mixture of various chemical elements or
compounds also qualifies as a pure substance as long
as the mixture is homogeneous.
Water
Examples of Pure Substance vapor
 Water, nitrogen, helium, and carbon dioxide, for
example, are all pure substances. Water
 A mixture of two or more phases of a pure substance liquid
is still a pure substance as long as the chemical
composition of all phases is the same Pure substance
 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 Air Gas

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

not a pure substance.
Air
liquid
 This is because different air components condense at
different temperatures at a specified pressures and
Not a Pure
thus the composition of liquid air and gas air will be
substance
different..

Phases of Pure Substance

 A phase is identified as having a distinct molecular vapor
arrangement.
 This molecular arrangement is homogeneous
throughout the system. liquid
 The phase separated from the other phases by easily
identifiable boundary surfaces. Solid
 Solid Phase of Pure Substance
 The molecules in a solid are arranged in a lattice
that is repeated throughout.
 Three dimensional pattern
 Because of the small distances between molecules
in a solid, Large attractive forces exists between
atoms or molecules and keep the molecules in a
fixed position.
 The atoms or molecules are in constant motion –
they oscillate in place
 The velocity of the molecules during these (a) molecules are at
oscillations depends on the temperature. relatively fixed positions in
a solid,
 The higher the temperature – the more vibration
 At sufficiently high temperatures, the velocity (and thus the momentum) of the
molecules may reach a point where the intermolecular forces are partially
overcome and groups of molecules break away.
 This is the beginning of the melting process (i.e. liquid formation)
 Liquid Phase of Pure Substance
 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)
 In a liquid, the intermolecular forces are weaker
relative to solids, but still relatively strong compared
with gases.
 Distance between molecules increase slightly as a
solid turns to liquid.
 Water being a notable exception. (b) Groups of molecules
move about each other in
 In ice, the crystalline lattice is dominated by a regular
the liquid phase,
array of hydrogen bonds which space the water
molecules farther apart than they are in liquid water.
 This is why ice float on water due to hydrogen bond
 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
 Collisions are the only mode of interaction
between the molecules.
 High kinetic energy
 Molecules in the gas phase are at a considerably (C) Molecules move about at
higher energy level than they are in the liquid or random in the gas phase.
solid phases.
 In order to liquefy, lots of that kinetic energy
must be released
PHASE-CHANGE PROCESSES
OF PURE SUBSTANCES
 There are many practical situations where two phases
of a pure substance coexist in equilibrium.
 For instance water exists as a mixture of liquid and
vapor in the boiler and the condenser of a steam
power plant.

Liquid Water
 Let us study what would happen when we heat a
liquid phase of pure substance at a constant pressure

Piston cylinder device – maintains constant pressure

T Phase Change
Processes on a
5 T-v diagram

2 3 4

1
v
 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 A liquid that is about
to float and thus the pressure will be constant. to vaporize is called
Saturated Liquid.
 T and v will increase until the system reaches
100 0C at which any addition of heat will
cause some of the liquid to vaporize
 At a given pressure 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 substance between
saturated liquid (state 2) and
 Adding more heat will cause saturated vapor (state 4) is
called saturated liquid-vapor
boiling to start. Liquid gradually mixture.
evaporates (state 3) but
temperature will remain constant,
Why?
 The only change is the increase in
the specific volume (v) until it A vapor that is about to
reaches state 4 (saturated vapor). condense is called
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.
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

The liquid–vapor saturation curve of a pure substance

(numerical values are for water).
 It takes a large amount of energy to melt a solid or vaporize a
liquid.
 The amount of energy absorbed or released during a phase-
change process is called the latent heat.
 More specifically, the amount of energy absorbed during
melting is called the latent heat of fusion and is equivalent to
the amount of energy released during freezing.
 Similarly, the amount of energy absorbed during vaporization
is called the latent heat of vaporization and is equivalent to the
energy released during condensation.
 The magnitudes of the latent heats depend on the temperature
or pressure at which the phase change occurs.
Saturation Temperature and Pressure
 At a given pressure, the temperature at which a pure substance changes phase is
called the saturation temperature Tsat.
 Likewise, at a given temperature, the pressure at which a pure substance changes
phase is called the saturation pressure Psat.
 The T-v diagram for different pressure value
 At higher pressure water has a somewhat smaller specific volume
than it does at 1 atm pressure.
 Water starts boiling at a much higher temperature
 Note that the sat. liquid specific volume (vsat,l ) will increase
while the sat. vapor specific volume (vsat,g ) will decrease
 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, as shown in the diagram, and it becomes a point when
the pressure reaches 22.06 MPa for the case of water.
 This point is called the critical point.
 vsat,l and vsat,g will be the same and we
Critical Point speak of Pcrit, Tcrt, and vcrit.

 The critical point is defined as the

point at which the saturated liquid and
saturated vapor states are identical.
 Pressure above 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.
Phase Change Processes on a P-v diagram
 Decrease P gradually but State 3 State 4 State 5
keep T constant. State 1 State 2
T = 150 C T = 150 C T = 150 C
T = 150 C T = 150 C
 Water boils at Psat
 The pressure at which a
pure substance changes
phase is called the 1
saturation pressure Psat.
 At Psat, Liquid and vapor
phases are in equilibrium.
 From State 2 to 4, no 2 3 4
weights are removed
(P=constant) and T is kept 5
constant but heating
causes liquid to vaporize.
P-v diagrams with Solid Phase
P – v diagram of substance that P – v diagram of substance that
contracts on freezing 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

vapor

liquid

Solid

P-T diagram of pure substances.

 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
1. sublimation line (between
solid and vapor regions),
2. the vaporization line (between
liquid and vapor regions), and
3. the melting line (between
solid and liquid).
 T
P-v-T surfaces
You can plot P, T, V on a
three dimensional graph

Top view

ur e
v
at
per
Tem

P ie w P
v
 v P
P Tv
iew

v T
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

Compresse Liquid
two properties will fix the

Table A7
state.
 In two phase regions, any
6
A d )
two properties (except P and l e ate por
b e a
Ta erh r v
T) will fix the state. P and T Saturated liquid-
p (o
Su ter
a
are dependent on each other. vapor region w
Table A4 T entry
Table A5 P entry

Table A8
Saturated ice-vapor
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  pυ
 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

T
t.
ns
co
=
P

vf vg
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 90oC. Determine
the pressure in the tank and the volume of the tank. (Table A-4)
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)
 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.

Solution: Saturated liquid water is

vaporized at constant pressure. The volume
change and the energy transferred are to be
determined.
Analysis (a) The process described is
illustrated on a P-v diagram in Fig.
The volume change per unit mass during a
vaporization process is vfg, which is the
difference between vg and vf. Reading these
values from Table A–5 at 100 kPa and
substituting yield.
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  g g

m m m
f g total
 Derivation:
Gas
V  V f  Vg P or T mg vg

mv  m f v f  mg v g Liquid
mf v f
 ( 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 f  f    g g 
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 )
0
 yf  x y fg = yf
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
T  Tsat at given P
t.
ns
co
P=

T
Tsat P  Psat at given T
v f  v  v g at given P or T
vf vg v v
u f  u  u f at given P or T
P
h f  h  h f at given P or T
Psat T=
co
          
n
P
st . saturated mixture

vg v v
Quality is an intensive property
Example 2- 4:
Saturated Liquid-vapor mixture (continued)
 A rigid tank contains 10 kg of water at 90oC. 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.
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).

T=
co
ns
t.

vg v v
 Superheated Vapor
T
Compared to saturated vapor, superheated

.
st
vapor is characterized by
con
T P=
Tsat T  Tsat at given P
P  Psat at given T
vf vg v v v  v g at given P or T
P u  u g at given P or T
h  h g at given P or T
Psat T=
co
ns
        
P t. superheated vapor

vg v v
 Compressed liquid Table A-7
 In the region to the left of the saturated liquid line, a substance exists as
compressed liquid.

v
 Compressed Liquid
In general, a compressed liquid is
characterized by

T T  Tsat at given P

.
st
P  Psat at given T
n
co
P=

T
v  v f at given P or T
Tsat
u  u f at given P or T
h  h f at given P or T
        
compressed liquid
vf vg v v
 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

T Acceptable
P Wrong

.
pa
5M
P=
264
5 Mpa T=2
64
80
T=
80

v vf v
Approximate value v vf v
Precise value Wrong value
Precise value

y y f @T
 If the compression is moderate, the properties do not vary significantly with pressure.
But they do vary with temperature
Linear Interpolation

A B

100 5

130 y
200 10

130  100 y  5

200  100 10  5
Linear Interpolation (Continued)
Now
T Psat
y  y1 x  x1
X1= 140 y1= 0.3615 
X = 143 y=? y 2  y1 x 2  x1
X2= 145 y2= 0.4154
x  x1
y  y1   ( y2  y1 )
x2  x1
143  140
Psat  0.3615  ( 0.4154 0.3615)
145  140

Psat  0.394 kPa

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
pa
and 5 MPa using (a) data from the
5M
compressed liquid table and (b)
saturated liquid data. What is the 263.99
error involved in the second case? 80
(Answers: 333.72 kJ/kg, 334.86
kJ/kg, 0.34%)

80
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 0.01oC 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 -40oC 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.
Example
 Determine the missing properties and the phase descriptions in the
following table for water:

T,OC P,kpa v, m3/kg Phase description

550 Saturated liquid

125 750

500 0.14
 A piston–cylinder device contains 0.8 kg of steam at 300°C and 1 MPa.
Steam is cooled at constant pressure until one-half of the mass condenses.
(a) Show the process on a T-v diagram.
(b) Find the final temperature.
(c) Determine the volume change.
Solution
At the final state the cylinder contains saturated liquid-vapor mixture, and thus
the final temperature must be the saturation temperature at the final pressure,
Quiz
A piston–cylinder device initially contains 50 L of liquid water at
40°C and 200 kPa. Heat is transferred 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.