CHAPTER TWO

PROPERTIES OF PURE SUBSTANCES

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 (Homogeneous)
• Single chemical compound or element
• A mixture of various chemical compounds may also qualify as a
pure substance, as long as it remains homogeneous
e.g. air
NOT good for oil / water mixtures
• A mixture of two or more phases
e.g. ice and liquid water
 2-2 Phases of Pure Substances
Phase
• A distinct molecular arrangement that is homogeneous throughout
and separated from others by easily identifiable boundary surfaces

1. Solid (crystalline)
• Molecules are arranged in a three dimensional pattern (lattice) that
is repeated throughout space
• Molecules continually oscillate about their equilibrium positions
• The velocity of molecules depends on the temperature

Microscopic view
 2-2 Phases of Pure Substances
2. 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)

3. 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
 2-3 Phases Change Processes of Pure Substances
Working Example
• 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
• All substances exhibit the same general
behavior

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
 2-3 Phases Change Processes of Pure Substances
Saturation Temperature and Saturation Pressure
Is the statement “water boils at 100°C” correct?
 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
 During a phase-change process, pressure and temperature are
obviously dependent properties,
 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

 It is clear from Fig. that

Tsat increases with Psat.
 Thus, a substance at
higher pressures boils at
higher temperatures.
 Eg. pressure cooker
 2-3 Phases Change Processes of Pure Substances
Latent Heat
• The amount of energy absorbed or released during a phase
change

Latent Heat of Fusion

• The amount of energy absorbed during melting

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
• To generate a compete T-v diagram, we repeat the earlier
experiment for a series of pressures

The critical-point properties

of water are:
 Pcr = 22.06 MPa,
 Tcr = 373.95°C, and
 vcr = 0.003106 m3/kg
 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
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
The critical-point properties
of water are:
 Pcr = 22.06 MPa,
 Tcr = 373.95°C, and
 vcr = 0.003106 m3/kg
 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
• For water, the triple-point temperature
and pressure are 0.01°C and 0.6117 kPa,
respectively

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
• The tables contain properties such as entropy internal energy ‘u’,
specific enthalpy ‘h’ and specific entropy ‘s’
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
1. 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: 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?
 2-5 Property Tables
2. Saturated Liquid-Vapor Mixture
• A system consisting of both saturated liquid and saturated vapor
• To analyze this mixture properly, we need to know the proportions
of the liquid and vapor phases in the mixture

Quality (x)
• The ratio of the mass of vapor to the total mass of the mixture
mvapor
x=
mtotal
mtotal = mliquid + mvapor = m f + mg
• 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 = mg 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
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

• 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)

Example: Determine the temperature of water at a state of

P= 0.5 MPa and h = 2890 kJ/kg.
2-5 Property Tables
 Interpolation
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 − mX1  = 
 Y2 − Y1   X 2 − X1 
 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; the only table for compressed liquid
• 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. Increasing the pressure 100 times often causes properties
to change less than 1 percent
• 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
• In thermodynamics we are interested in changes in properties
• 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 = 40 oC and P = 5 MPa from Table
A-7
2. Same thing using the saturated liquid approximation
 Problem 3-121
A 10 kg mass of superheated refrigerant-134a at 1.2 MPa
and 70 oC is cooled at constant pressure until it exists as a
compressed liquid at 20 oC.

a. Show the process on a T-v diagram with

respect to saturation lines.
b. Determine the change in volume.
c. Find the change in total internal energy.
 Problem 3-51
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. Determine the temperature at which
the liquid in the tank is completely vaporized. Also, show the
process on a T-v diagram with respect to saturation lines.

Note: Rigid tank is constant volume process.

 2-6 The Ideal-Gas Equation of State
Equation of State
• Any equation that relates the pressure, temperature, and specific
volume of a substance
e.g., P = f (T , v ) or v = g (T , P )
• More generally, property relations that involve other properties of a
substance at equilibrium states
e.g., u = f (T , v ) or h = g (T , P )

Ideal Gas
• A model substance of infinitely small particles (point masses) that
do not interact
• The equation of state for such a substance is,
T
P=R
v

Pv = RT
 2-6 The Ideal-Gas Equation of State
Variables
• R → gas constant
• P → absolute pressure
• T → absolute temperature
• v → specific volume

The Gas Constant

• As used above, R takes on a different
value for each gas
• R can be expressed in terms of the
universal gas constant, Ru
Ru
R=
M

• Ru → universal gas constant

• M → molar mass (molecular weight)
 2-6 The Ideal-Gas Equation of State
Mass versus Moles
• Specific properties can be defined on
a per unit mass or per unit mole basis
Y Y
y= y=
m N
• N → mole number
• The mass and mole number are related
through the molar mass M
m = MN y = yM
• The ideal gas equation of state can
also be written on a molar basis

PV = NRuT or Pv = RuT
 2-6 The Ideal-Gas Equation of State
Property Ratios
• By writing the ideal-gas equation of state twice for a fixed mass
and simplifying, the properties of an ideal gas at two state points
can be related as follows,

P1v1 P2 v2
=
T1 T2

When is the ideal-gas equation of state valid?

• The ideal gas is an imaginary substance
• The ideal-gas approximation is most valid at
 Low densities
 Low pressures
 High temperatures
2-6 The Ideal-Gas Equation of State
 2-7 Compressibility Factor
Compressibility Factor
• The behavior of real gases deviates from that of an ideal gas
• This deviation can accurately be accounted for by the introduction
of a correction factor called the compressibility factor, denoted Z

Pv
Z= or Pv = ZRT
RT

• For an ideal gas, Z = 1

• The term Z – 1 can be positive or negative
• The greater |Z – 1|, the more the gas deviates from ideal-gas
behavior
Z = Vactual/Videal;

Videal=RT/P
 2-7 Compressibility Factor
Principle of Corresponding States
• Gases behave differently at a given temperature and pressure, but
they behave very much the same at temperatures and pressures
normalized with respect to their critical temperatures and pressures
• The compressibility factor, Z, for all gases is approximately the
same at the same reduced temperature and reduced pressure

T P
TR = and PR =
Tcr Pcr
 2-7 Compressibility Factor
Generalized Compressibility Chart
• A general chart for obtaining the compressibility factor for real
gases based on the reduced properties of a substance

Characteristics of Generalized Compressibility Chart

1. At very low pressures (PR << 1), gases behave as an ideal gas
regardless of the temperature
2. At high temperatures, (TR >> 2), ideal gas behavior can be
assumed with good accuracy regardless of pressure
(except when PR >> 1)
3. The deviation from ideal gas behavior is greatest in the vicinity
of the critical point
2-7 Compressibility Factor
 2-7 Compressibility Factor

Example: (3-84)

Determine the specific volume of superheated water vapor at 10 MPa

and 400°C, using:
(a) the ideal-gas equation,
(b) the generalized compressibility chart, and
(c) the steam tables.
Also determine the error involved in the first two cases.

The gas constant, the critical pressure, and the critical temperature
of water are determined from Table A1 to be:

R= 0.0815 kPa.m3/kg.K
Pcr= 4.059 MPa
Tcr = 374.2 K
 2-8 Other Equations of State
Why do we Need Other Equations of State?
• The ideal-gas equation of state is very simple, but its range of
applicability is limited
• It is desirable to have equations of state that represent the P-v-T
behavior of substances accurately over a large region without
restrictions

van der Waals Equation of State

 P + a (v − b ) = RT RT a
 2 
or P (T=
,v) − 2
 v  v −b v

• b → accounts for volume occupied by molecules

• a / v2 → accounts for intermolecular attraction forces
• a and b can be related to the critical properties of a substance
 2-8 Other Equations of State
Other Popular Equations of State
• Beattie-Bridgeman
• Benedict-Webb-Rubin
• Redlick-Kwong
• Peng-Robinson

Virial Equation of State

• The equation of state of a substance can also be expressed in a
series form as,

RT a (T ) b (T ) c (T )
P (T , v ) = + 2 + 3 + 4 + ...
v v v v

• a(T), b(T), c(T), … are called virial coefficients