ENGINEERING

THERMODYNAMICS
CHAPTER TWO
PROPERTIES OF PURE SUBSTANCE

BY HANAN E.
 Learning Objectives

1. Introduce the concept of a pure substance.

2. Discuss the physics of phase-change processes.
3. Illustrate the P-v, T-v, and P-T property diagrams and P-v-T
surfaces of pure substances.
4. Demonstrate the procedures for determining thermodynamic
properties of pure substances from tables of property data.
5. Describe the hypothetical substance "ideal gas" and the ideal-gas
equation of state.
6. Apply the ideal-gas equation of state in the solution of typical
problems.
7. Introduce the compressibility factor, which accounts for the
deviation of real gases from ideal-gas behavior.
8. Present some of the best-known equations of state.
 2-1 Pure Substance
Pure Substance
• A substance that has a fixed chemical composition throughout
• Single chemical compound or element
• A mixture of various chemical compounds may also qualify as a
pure substance, so long as it remains homogeneous
e.g. air, NOT good for oil / water mixtures
• A mixture of two or more phases of a pure substance is still a pure
substance as long as the chemical composition of all phases is the
same
 2-2 Phases of Pure Substances
Phase
• A distinct molecular arrangement that is homogeneous throughout
and separated from others by easily identifiable boundary surfaces
• All substances exist in different phases at room temperature and
pressure
E.g. Copper-solid
Mercury-liquid
Nitrogen-gas
water-liquid
But when the temperature and pressure changes, each of the above
pure substances changes accordingly

• Intermolecular bonds are strongest in solids and weakest in

gases. One reason is that molecules in solids are closely packed
together, whereas in gases they are separated by relatively large
distances.
 2-2 Phases of Pure Substances
Solid (crystalline)
• Molecules are arranged in a three dimensional pattern (lattice) that
is repeated throughout space
• Molecules continually oscillate about their equilibrium positions
because of the small distances between molecules in a solid, the
attractive forces of molecules on each other are large and keep the
molecules at fixed positions
• The velocity of molecules depends on the temperature

Microscopic view
 2-2 Phases of Pure Substances
Liquid
• Unlike a solid, molecules are not at fixed
positions relative to each other and they
can rotate and translate freely
• Molecular spacing is similar to that in
solids
• In general, distances between molecules
are larger in a liquid than in a solid (water Microscopic view
is a notable exception)

Gases
• Molecules are far apart from each other
and molecular order is nonexistent
• Molecules move about at random,
continually colliding with each other and
the walls of the container they are in
Microscopic view
 2-2 Phases of Pure Substances
• Most liquids have a quite simple behavior when they are cooled (at a
fixed pressure): they shrink.
• Water is one of the few exceptions to this behavior. When liquid
water is cooled, it contracts like one would expect until a
temperature of approximately 4 degrees Celsius is reached. After
that, it expands slightly until it reaches the freezing point, and then
when it freezes it expands.

ice
liquid water

• It is this open solid structure that causes ice to be less dense than
liquid water. That is why ice floats on water, for which we should all
be thankful because if water behaved "normally" many bodies of
water would freeze solid in the winter, killing all the life within them.
 2-3 Phases Change Processes of Pure Substances

Q. What is the importance of studying the

pressure/volume/temperature (PVT) behavior of pure substances?

It is important because:-
Thermodynamic properties, such as internal energy and enthalpy,
from which one calculates the heat and work requirements of
industrial processes, are often evaluated from volumetric data

Moreover, pressure/volume/temperature (PVT) relations are

themselves important for such purposes as the metering of fluids and
the sizing of vessels and pipelines
 2-3 Phases Change Processes of Pure Substances
Working Example
• water is used to demonstrate the basic principles
involved but all substances exhibit the same
general behavior
• Consider a piston-cylinder device containing water
• We will start at a temperature of 20 oC and a
pressure of 1 atm and examine what happens to the
substance as it is heated at 1 atm

1. Compressed Liquid (subcooled liquid)

• Not about to vaporize
• Heat transfer to the system causes the temperature
to rise and the fluid to expand
• Any heat loss from the system causes the
temperature to decrease and the fluid to contract
 2-3 Phases Change Processes of Pure Substances
2. Saturated Liquid
• A liquid that is about to vaporize
• A phase change, from liquid to vapor, is
about to take place
• Any heat addition will cause some of the
liquid to vaporize
• Any heat loss from the system causes the
temperature to decrease and the fluid to
contract

3. Saturated Liquid-Vapor Mixture

• Liquid and vapor phases coexist in
equilibrium
• Any addition of heat causes more liquid to
vaporize
• Any heat loss causes vapor to condense
 2-3 Phases Change Processes of Pure Substances
4. Saturated Vapor
• A vapor that is about to condense
• Any heat loss from the system will cause
some of the vapor to condense to form a
liquid phase
• Any heat addition will cause the temperature
to rise and the system to expand

5. Superheated Vapor
• A vapor that is NOT about to condense
• Any addition of heat will cause an increase
in the temperature and the system will
expand
• Any removal of heat will cause the
temperature to drop and the vapor to
contract, but no condensation will take place
 2-3 Phases Change Processes of Pure Substances

T-v diagram for the heating process of water at constant pressure(1atm.)

 2-3 Phases Change Processes of Pure Substances
• “water boils at 100°C” is incorrect.
The correct statement is “water boils at 100°C at 1 atm(101.42kpa)
pressure.
• If the pressure were raised to 500kPa by adding weights on top of
the piston, water would start boiling at 151.8°C.
Saturation Temperature and Saturation Pressure
• The temperature at which a liquid starts boiling depends on the
pressure; therefore if the pressure is fixed, so is the boiling
temperature

Saturation Temperature ( Tsat)

• At a given pressure, the temperature at which a pure substance
changes phase

Saturation Pressure ( Psat)

• At a given temperature, the pressure at which a pure substance
changes phase
 2-3 Phases Change Processes of Pure Substances
Liquid-Vapor Saturation Curve
• A plot of Tsat vs. Psat or vice versa
• Tsat  f  Psat  or Psat  g Tsat 
• Tsat and Psat are NOT independent quantities
 2-3 Phases Change Processes of Pure Substances
Latent Heat
• The amount of energy absorbed or released during a phase
change process

Latent Heat of Fusion

• The amount of energy absorbed during melting
• equivalent to the amount of energy released during freezing.

Latent Heat of Vaporization

• Amount of energy absorbed during vaporization
• Equivalent to the energy released during condensation
 2-4 Property Diagrams for Phase-Change Processes
The T-v Diagram
• T-v diagram of constant-pressure phase change processes of a
pure substance at various pressures
As the pressure is increased
further, this saturation line
continues to shrink, as
shown in Fig. and it becomes
a point when the pressure
reaches 22.06 MPa for the
case of water. This point is
called the critical
Point.
The critical-point properties of
water are Pcr-22.06 MPa,
Tcr-373.95°C, and vcr-
0.003106m3/kg.
 2-4 Property Diagrams for Phase-Change Processes
Critical Point
• The point at which the saturated liquid
and saturated vapor states are identical
• At the critical point, 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 properties of this state are referred
to as the critical-point properties
 Critical temperature = Tcr
 Critical pressure = Pcr
 Critical specific volume = vcr
 2-4 Property Diagrams for Phase-Change Processes
Saturated Liquid Line
• A line formed by the
saturated liquid states

Saturated Vapor Line

• A line formed by the
saturated vapor states

Saturated Liquid-Vapor Mixture Region (wet region)

• All states that involve both liquid and vapor phases in equilibrium
• The saturated liquid and vapor lines meet at the critical point,
forming a dome, within which states exist in liquid-vapor
equilibrium
 2-4 Property Diagrams for Phase-Change Processes
Compressed Liquid Region
• All the compressed liquid
states located in the region
to the left of the saturated
liquid line

Superheated Vapor Region

• All the superheated vapor
states located to the right of
the saturated vapor line
 2-4 Property Diagrams for Phase-Change Processes
The P-v Diagram
• Same general shape as the T-v diagram, but the T = constant
lines have a downward trend
 2-4 Property Diagrams for Phase-Change Processes
Including the Solid Phase

Triple Line
• The line representing the conditions under which all three phases
of a pure substance coexist in equilibrium

P-v diagram of a substance that P-v diagram of a substance that

contracts on freezing expands on freezing (such as water)
 2-4 Property Diagrams for Phase-Change Processes
Triple Point
• The projection of the triple line found
on a T-v or P-v diagram onto a P-T
diagram
• Vapor, liquid, and solid phases coexist

Sublimation
• A phase change in which a substance
passes directly from the solid phase to
the vapor phase
e.g., solid CO2 (dry ice)
 2-4 Property Diagrams for Phase-Change Processes
The P-T diagram
• Often called the phase diagram since all three phases are
separated from each other by three lines
 Sublimation line (solid-vapor)
 Vaporization line (liquid-vapor)
 Melting line (solid-liquid)
• All three lines meet at the triple point
 2-4 Property Diagrams for Phase-Change Processes
The P-v-T surface
• Single phase regions are curved surfaces
• Two-phase regions appear as surfaces perpendicular to the P-T
plane
• Can be expressed as P  f T , v 

P-v-T surface of a substance that P-v-T surface of a substance that

contracts on freezing expands on freezing (like water)
 2-4 Property Diagrams for Phase-Change Processes
Generalization (T-y diagrams)
• T-u, T-h, and T-s diagrams have the same general qualitative
aspects as T-v diagrams
T

v, u, h, or s
 2-4 Property Diagrams for Phase-Change Processes
Generalization (P-y diagrams)
• P-u, P-h, and P-s diagrams have the same general qualitative
aspects as P-v diagrams
P

v, u, h, or s
 2-5 Property Tables
Property Tables
• For most substances, the relationships among thermodynamic
properties are too complex to be expressed by simple equations
• As a result, properties are frequently presented in the form of tables
• Often, properties are listed in multiple tables
e.g., superheated vapor, compressed liquid, and saturated regions

Enthalpy – A Combination Property

• We frequently encounter the combination of properties U and PV
• This combination is defined as a new property, enthalpy, denoted H

Extensive: H  U  PV
Intensive: h  u  Pv
 2-5 Property Tables
Saturated Liquid and Vapor States
• For water, tables A-4 and A-5
• A-4: temperature as independent variable
• A-5: pressure as independent variable

• Subscripts
f → properties of a saturated liquid
g → properties of a saturated vapor
fg → difference between the saturated liquid and vapor

• Example
vf → specific volume of saturated liquid
vg → specific volume of saturated vapor
vfg → difference between vg and vf, i.e.,
vfg = vg – vf

hfg → enthalpy of vaporization, latent heat of vaporization

2-5 Property Tables
 2-5 Property Tables
Examples – Take two minutes to locate the following properties:
1. Vapor pressure of water at T = 65 oC
2. Specific volume of the saturated vapor at T = 40 oC
3. Enthalpy of vaporization at T = 5 oC
 2-5 Property Tables
EXAMPLE 1 - Pressure of Saturated Liquid in a Tank
A rigid tank contains 50 kg of saturated liquid water at 90°C. Determine
the pressure in the tank and the volume of the tank.
 2-5 Property Tables
EXAMPLE 2- Volume and Energy Change during Evaporation
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 transferred to the water.
2-5 Property Tables
 2-5 Property Tables
Saturated Liquid-Vapor Mixture
• A system consisting of both saturated liquid
and saturated vapor

Quality (x)- the proportions of the liquid and vapor

phases in the mixture.The ratio of the mass vapor
to the total mass of the mixture
mvapor
x
mtotal
m total  m liquid  m vapor  m f  m g
• Quality has meaning only for saturated
systems
• Takes on values between 0 and 1
x = 0 → saturated liquid
x = 1 → saturated vapor
 2-5 Property Tables
Average Values
• It is often useful to consider the
average values of a liquid-vapor
mixture
• As an example, consider the volume
V  V f  Vg
m  m f  mg
V  mv, V f  m f v f , Vg  mg v g
mf mg
v vf  vg
m m
Recall, x  m g m and 1  x  m f m
 2-5 Property Tables
v  1  x v f  xv g
v  v f  x v g  v f 
v  v f  xv fg
•From this we obtain,
v  vf
x
v fg
•This is referred to as the
Lever Rule
•General to any property, y,
(e.g. v, u, h, s)

y  yf
y  y f  xy fg x
y fg
 2-5 Property Tables
Example- Pressure and Volume of a Saturated Mixture
A rigid tank contains 10 kg of water at 90°C. If 8 kg of the 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- Properties of Saturated Liquid–Vapor Mixture

An 80-L vessel contains 4 kg of refrigerant-134a at a pressure of
160 kPa. Determine (a) the temperature, (b) the quality, (c) the
enthalpy of the refrigerant, and (d) the volume occupied by the
vapor phase.
 2-5 Property Tables
Superheated Vapor
• On a T-v or P-v diagram, the region to the right of the saturated
vapor line and at temperatures above the critical point temperature
• For water, table A-6
• Pressure and temperature are independent variables

• Compared to saturated vapor, superheated vapor is characterized by

 Lower pressures ( P < Psat at a given T)
 Higher temperatures ( T > Tsat at a given P)
 Higher specific volumes ( v > vg at a given P or T)
 Higher internal energies ( u > ug at a given P or T)
 Higher enthalpies ( h > hg at a given P or T)
2-5 Property Tables
 2-5 Property Tables
Compressed liquid
• On a T-v or P-v diagram, the region to the left of the saturated
liquid line
• Tables not as common as for the superheated vapor
• For water, table A-7
• Pressure and temperature are independent variables

• Compressed liquid is characterized by

 Higher pressures ( P > Psat at a given T)
 Lower temperatures ( T < Tsat at a given P)
 Lower specific volumes ( v < vg at a given P or T)
 Lower internal energies ( u < ug at a given P or T)
 Lower enthalpies ( h < hg at a given P or T)
 2-5 Property Tables
Approximation for Compressed Liquids
• Treat the compressed liquid as a saturated liquid at the given
temperature
• Properties depend on temperature much more strongly than they do
pressure
• For specific volume, internal energy and enthalpy use,
y  yf @ T or y  y f @T
 2-5 Property Tables
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
• In thermodynamics we are interested in changes in properties not
the values of properties at specified states
• As a result, we choose a convenient reference state and assign it a
value of zero
e.g., water – reference state is saturated liquid at 0.01 oC
uf = 0
sf = 0

• Sometimes different tables use different reference states

• Always use a single consistent set of tables
 2-5 Property Tables
Examples – Take two minutes to determine the following:
1. Specific volume of water at T = 80 oC and P = 5 MPa from Table
A-7
2. Same thing using the saturated liquid approximation
 2-5 Property Tables
Linear Interpolation
• Used when states encountered in
solving a problem do not fall exactly on
the grid of values provided by the
property tables
• Assume that the properties vary linearly
between two known points
• Known (X1, Y1) and (X2, Y2)
• Want to find Y3 for X3

X Y Y  mX  b  Y2  Y1 
Y3  Y1   X 3  X 1 
X1 Y1  Y2  Y1   X 2  X1 
m 
X3 Y3  X 2  X1 
 Y3  Y1   X 3  X1 
X2 Y2 b  Y1  m X 1   
 Y2  Y1   X 2  X1 
 2-5 Property Tables
EXAMPLE -The Use of Steam Tables to Determine Properties
Determine the missing properties and the phase descriptions in the
following table for water: