CHAPTER 3

Properties of Pure Substances

Lecture 1

1
 DEFINITION – PURE
SUBSTANCE

Pure substance: A
substance that has a fixed
chemical composition
throughout.
 H2O is a pure substance whether
A mixture of liquid and gaseous water
it is only a gas or a mixture of (i.e. steam) is a pure substance, but a
liquid and gas mixture of liquid and gaseous air is not
 Air is a mixture of several gases; (@1atm Tsat, N2≈ -196°C; Tsat O2≈ -183°C)
.
it is considered to be a pure
substance only if it a gas. (why?)

2
Phases of a Pure
Substance
 A pure substance can exist in different phases depending
on the arrangement of its molecules
 Solid: molecules are at relatively fixed positions
 Liquid: groups of molecules move about each other
 Gas: molecules move about at random

Solid Liquid Gas

3
PROPERTY DIAGRAMS --
Phase Change Process

Experiment: Isobaric heating of a pure

substance
Water initially at 20°C and 1 atm is to be
heated at constant pressure

4
Isobaric Phase Change
Process of a Pure Substance

Compressed liquid (or

“subcooled liquid”):
A substance that is not
about to vaporize.
 At 1 atm pressure and 20°C,
water exists in the liquid phase
(compressed liquid).

5
Isobaric Phase Change
Process of a Pure Substance

Saturated liquid: A liquid that

is about to vaporize.
 At 1 atm pressure and 100°C,
water exists as a liquid that is ready
to vaporize (saturated liquid).

6
Isobaric Phase Change
Process of a Pure Substance

Saturated liquid–vapor
mixture: The state at which
the liquid and vapor phases
coexist in equilibrium
 As more heat is transferred, a
larger fraction of the saturated
liquid vaporizes
 “T” remains constant as long as
“P” is kept constant
(saturated liquid–vapor
mixture)
7
Isobaric Phase Change
Process of a Pure Substance

Saturated vapor:
A substance is at the end
of vaporization.
 At 1 atm pressure, the
temperature remains
constant at 100°C until all
the liquid is vaporized
(saturated vapor).

8
Isobaric Phase Change
Process of a Pure Substance

Superheated vapor:
A vapor that is not about to
condense (i.e., Temp is
higher than that for
saturated vapor).
 As more heat is transferred,
the temperature of the vapor
starts to rise above the boiling
point (superheated vapor).

9
 = 1 atm

Specific Volume

Isobaric Phase Change Process of a Pure Substance

10
 The T-v Diagram -- Isobaric
Process
 1 2: Compressed Liquid
 Both T & v increase with heat addition until the boiling
point (saturation temp) is reached
 Liquid at state “2” is “saturated liquid”

 2 4: Saturated (Liquid-vapor)Mixture
 T remains constant while v increases with heat addition
 State 3 is a saturated mixture of liquid and vapor P = Constant
 Mass fraction of vapor increases until all “saturated
liquid” is converted to “saturated vapor” (state 4)

 4 5: Superheated Vapor
 Both T & v increase with further heat addition

11
The T-v Diagram -- Isobaric
Process

 If the process is reversed

by cooling the superheated
vapor (state 5), the water
will go back to state 1
along the same path
 The water will release the
same amount of heat it
gained during the heating
process from state 1 to
state 5. P = Constant

12
Boiling Temperature
versus Boiling Pressure
 The temperature at which a
pure substance starts boiling
depends on the pressure

 For a given pure substance,

the boiling temperature
depends only on pressure.
Water
 Water boils at 100C at
1 atm; it boils at 159C at
6 atm

13
Saturation Temperature &
Saturation Pressure
 Saturation temperature
Tsat: The temperature at which
a pure substance changes
phase at a given pressure.

 Saturation pressure Psat:

The pressure at which a pure
substance changes phase at a Water; Liquid/Vapor
given temperature. Transition

14
Saturation Temperature &
Saturation Pressure

The atmospheric pressure,

and thus the boiling
temperature of water,
decreases with elevation.

15
Latent Heat
 Latent heat: The amount of energy absorbed or released during a
phase-change process.
 Latent heat of vaporization: The amount of energy absorbed
during vaporization. It is equal to the energy released during
condensation.
 Latent heat of fusion: The amount of energy absorbed during
melting. It is equal to the amount of energy released during
freezing.
 The magnitudes of the latent heats depend on the temperature (i.e.
pressure) at which the phase change occurs.
 At 1 atm pressure, the latent heat of vaporization of water is
2256.5 kJ/kg and the latent heat of fusion is 333.7 kJ/kg.

16
CHAPTER 3

Lecture 2

17
 The T-v Diagram -- Isobaric
Processes
 As pressure increases:
 Tsat increases
 v of saturated liquid increases
 v of saturated vapor decreases
 Latent heat of vaporization
decreases

 At the Critical Point:

 22.06 MPa and 373.95 °C for water
 No distinction between liquid and
vapor phases
 Latent heat of vaporization = zero

18
 The T-v Diagram – Key
Features
 Saturated Liquid Line
 Saturated Vapor Line
 Critical Point (Pc,Tc)
 Point at which saturated liquid
and saturated vapor states
are identical
 Table A-1 lists Pc and Tc for
various substances
 Compressed (“subcooled”)
liquid region
 Saturated liquid-vapor mixture
region (“wet region”)
 Superheated vapor region

19
The T-v Diagram
(Supercritical Pressures)

At supercritical pressures

(P > Pcr), there is no
distinct phase-change
(boiling) process.

20
The P-v Diagram --
Isothermal Process

 Experiment: Isothermal
reduction of pressure
 Water initially at 1 MPa and 150°C
 Pressure is to be gradually
decreased while the temperature is
kept constant
 Heat exchange with the
surroundings is allowed to maintain
The pressure in a piston–
constant temperature cylinder device can be
reduced by reducing the
weight of the piston.

21
 The P-v Diagram --
Isothermal Process
 At 1 MPa, Tsat for water = 179.9°C
 At 1 MPa and 150°C, water is
compressed liquid (State 1)
 When pressure reaches 476.2 kPa, water
becomes saturated liquid (State 2)
 Pressure remains constant at 476.2 kPa -
1 .
heat is added until liquid is fully
converted to saturated vapor (State 4)
2 . .
3 4 .
 As pressure is decreased below 476.2 5 .
kPa, vapor becomes superheated since
Tsat < 150°C (State 5).
 Reverse process: start from State 5
and increase pressure until State 1 is
reached following the same path

22
 The P-v Diagram --
Isothermal Process .
1

2. 3. 4.
 1 2: Compressed Liquid 5 .
 As P decreases, v increases while T is kept constant
 Pressure can be decreased until liquid becomes “saturated”
 P2 is the “saturation pressure” corresponding to temperature T

 2 4: Saturated (liquid-vapor) mixture

 P & T remain constant while v increases with heat addition
 Add latent heat of vaporization to completely convert “saturated liquid” to
“saturated vapor” (point 4)
 Point “3” is a “saturated mixture” of liquid and vapor

 4 5: Superheated Vapor
 P decreases and v increases while T is kept constant
Same path is followed if process is reversed 5 to 4 to 3 to 2 to 1
23
The P-v Diagram – Key
Features
 Saturated Liquid Line
 Saturated Vapor Line
 Critical Point (Pc,vc)
 Compressed (subcooled) liquid
region
 Saturated liquid-vapor mixture
region (wet region)
 Superheated vapor region
 Note difference between
“Isothermal” processes on
P-v Diagram and “Isobaric” P-v Diagram for a pure substance
processes on T-v Diagram

24
Extending the P-v Diagram
to include the Solid Phase

. .

. .
.

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

contracts on freezing (most substances). expands on freezing (such as water).

25
The Triple Line (Triple Point)
 All three phases exist in equilibrium
along the “Triple Line”
 Same pressure and temperature but
different specific volumes (depending
on mass fractions of phases)

 Triple Line appears as a point on P-T Diagram

(The Triple Point)

26
The P-T Diagram
 At low pressures (below the
triple-point value), solids
evaporate (sublime) without
melting first
 Sublimation: transition
from the solid phase directly
to the vapor phase.

P-T diagram of pure substances.

27
The P-v-T Surface

Substance that contracts on freezing Substance that expands on freezing

(most substances) (like water)

28
CHAPTER 3

Lecture 3

29
 Evaluation of
Thermodynamic Properties

 Thermodynamic analysis of systems requires quantitative

knowledge of their properties
 Example: Application of the First Law of Thermodynamics
(Qin + Win + Emass,in) – (Qout + Wout + Emass,out) = DEsystem

DU = U2 – U1 = m2 u2 – m1 u1
DKE = m2 V22 / 2 – m1 V12 / 2
DPE = m2 g z2 – m1 g z1

30
Evaluation of
Thermodynamic Properties

 Recall -- The State Postulate: “The equilibrium

state of a simple system is completely specified by
any two independent intensive properties”
 If we know two independent intensive properties (for
a given state), how do we determine the rest of the
properties?
 One option is to use an “Equation of state”
 For example, the ideal gas equation of state: P v = R T

31
 Property Tables

 For most substances, the relationships among

thermodynamic properties (the equations of state) are
too complex to be expressed by simple equations.
 Properties are frequently presented in the form of
tables.
 Tables in this textbook include the following properties:
 Temperature, pressure, specific volume, specific
internal energy, specific enthalpy, and specific entropy.

32
Enthalpy
 The combination [u + P v] often appears in
thermodynamic analyses of control volumes (open
systems)
 Since u, P, and v are all properties, then [u + P v] must
also be a property -- called “specific enthalpy”
 Units: (kJ/kg) -- Intensive property
 Total enthalpy H = m h = U + P V (kJ)

 Entropy (denoted by S ) will be discussed

separately in Chapter 7

33
PROPERTY TABLES
 Saturated Liquid and Saturated Vapor
 Known Tsat [Tables A-4 (water); A-11 (R134a)]
 Known Psat [Tables A-5 (water); A-12 (R134a)]
 The same tables can be used to find properties within the
saturated liquid-vapor mixture region
 Superheated Vapor
 Tables A-6 (water); A-13 (R134a)
 Compressed (subcooled) Liquid
 Table A-7 (water)
 Approximations using saturated liquid values

34
PROPERTY TABLES --
Saturated Liquid & Saturated Vapor

 Provide Properties of Saturated liquid (subscript

“f”) and Saturated Vapor (Subscript “g”)
 Since Tsat and Psat are uniquely related, one needs to
specify only one or the other
 Table A-4 (water); A-11 (Refrigerant 134a)
 Given Tsat: Table gives Psat, vf, vg, uf, ug, ufg, hf, hg, hfg, sf,
sg, sfg
 Table A-5 (water); A-12 (Refrigerant 134a)
 Given Psat: Table gives Tsat, vf, vg, uf, ug, ufg, hf, hg, hfg, sf,
sg, sfg

35
Saturated Liquid &
Saturated Vapor States

36
PROPERTY TABLES --
Saturated Liquid & Saturated Vapor

vfg = vg – vf

ufg = ug – uf

hfg = hg – hf

sfg = sg – sf

37
PROPERTY TABLES --
Saturated Liquid & Saturated Vapor

 Table A-4 (Water) -- Examples:

 For Tsat = 50°C:
 Psat = 12.352 kPa; vf = 0.001012 m3/kg; vg= 12.026 m3/kg;
uf = 209.33 kJ/kg; ug= 2442.7 kJ/kg; ufg=2233.4 kJ/kg; etc.
 For Tsat = 100°C:
 Psat = 101.42 kPa; vf = 0.001043 m3/kg; vg= 1.6720 m3/kg;
uf = 419.06 kJ/kg; ug= 2506.0 kJ/kg; ufg=2087.0 kJ/kg; etc.
 For Tsat = 373.95°C:
 Psat = 22.064 MPa; vf = 0.003106 m3/kg; vg= 0.003106 m3/kg;
uf = 2015.7 kJ/kg; ug= 2015.7 kJ/kg; ufg=0 kJ/kg; etc.

38
PROPERTY TABLES --
Saturated Liquid & Saturated Vapor

39
PROPERTY TABLES --
Saturated Liquid & Saturated Vapor

 Table A-5 (Water) -- Examples:

 For Psat = 75 kPa:
 Tsat = 91.76 °C; vf = 0.001037 m3/kg; vg= 2.2172 m3/kg;
uf = 384.36 kJ/kg; ug= 2496.1 kJ/kg; ufg,=2111.8 kJ/kg; etc.
 For Psat = 2.00 MPa:
 Tsat = 212.38 °C; vf = 0.001177 m3/kg; vg= 0.099587 m3/kg;
uf = 906.12 kJ/kg; ug= 2599.1 kJ/kg; ufg,=1693.0 kJ/kg; etc.
 For Psat = 22.064 MPa:
 Tsat = 373.95 °C; vf = 0.003106 m3/kg; vg= 0.003106 m3/kg;
uf = 2015.7 kJ/kg; ug= 2015.7 kJ/kg; ufg= 0 kJ/kg; etc.

40
PROPERTY TABLES --
Saturated Liquid & Saturated Vapor

Enthalpy of Vaporization, hfg (Latent heat

of vaporization): The amount of energy
needed to vaporize a unit mass of saturated
liquid at a given temperature (or pressure)
hfg = hg - hf
The enthalpy of vaporization decreases as the
pressure and temperature increase, until it
becomes zero at the critical point.

41
CHAPTER 3

Lecture 4

42
Saturated Liquid-Vapor
Mixture

 During boiling, at a given pressure, the temperature of a

pure substance remains the same.
 This means that pressure and temperature are not
independent during this period.
 Therefore, pressure and temperature cannot be used to
specify the state in this case.
 Another independent property (in addition to T or P) is
needed to specify the state, e.g. v, u, or h
 How do we find v, u, or h?

43
 Saturated Liquid-Vapor Mixture
Definition: “Mixture Quality”

 Quality: Mass fraction of x = 2/(2 + 8) = 0.20 or 20%

vapor present in a saturated
liquid/vapor mixture
 x ≡ mg/mmixture
= mg/(mg + mf)

 For saturated liquid x = 0

 For saturated vapor x = 1.0
(100%)
 For saturated liquid-vapor
mixture 0 < x < 1.0

44
Saturated Liquid-Vapor
Mixture – Evaluation of Properties

 Specified Temperature (Tsat) and Quality (x)

 Use Saturated Tables [Table A-4 (water); A-11
(Refrigerant 134a)] to determine properties of
saturated liquid and saturated vapor
 Use quality + properties of saturated liquid and
saturated vapor to determine “average” properties
of the mixture
 Specified Pressure (Psat) and Quality (x)
 Same as above using saturated pressure tables
[Table A-5 (water); A-12 (Refrigerant 134a)]

45
Saturated Liquid-Vapor
Mixture -- “Average” Properties

 Consider a saturated liquid-vapor mixture

mf = mass of saturated liquid in the mixture
mg = mass of saturated vapor in the mixture
mt = total mass of the mixture = mf + mg
 Quality:
x  (mg/mt) = [mg/(mf + mg)]
1- x = (mf/mt) = [mf/(mf + mg)]
 Let “Y” be any extensive property of the
mixture (e.g. V, U, H)
46
Saturated Liquid-Vapor
Mixture -- “Average” Properties

 Extensive property of the mixture is the sum of

extensive properties of saturated liquid and
saturated vapor in the mixture
Y = Yf + Yg
mt y = mf yf + mg yg
[y, yf, and yg are corresponding specific properties]
y = (mf/mt) yf + (mg/mt) yg
y = (1-x) yf + x yg
 Knowing “yf” & “yg” from saturated tables & quality “x”,
calculate the average specific mixture property “y”
47
Saturated Liquid-Vapor Mixture
Example: Evaluation of Average Specific Volume

48
Saturated Liquid-Vapor Mixture
Example: Evaluation of Average Specific Volume

vavg = (1 – x) vf + x vg = vf + x (vg – vf)

≡ vfg

vavg = vf + x vfg

49
Saturated Liquid-Vapor
Mixture – Evaluation of Properties

50
 Saturated Liquid-Vapor
Mixture – Evaluation of Properties

Important observation
 The properties of the
saturated liquid are the same
whether it exists alone or in a
mixture with a saturated
vapor.
 When an “overall” v, u, or h
is found for the mixture, it is
an average value.

51
Average Saturated Mixture
Properties -- Examples

 Example: Saturated water liquid-vapor mixture

 Known: T = 150 °C and x = 0.70 (70%)
 Determine v, and u
 Table A-4 for Tsat = 150 °C :
 vf = 0.001091 m3/kg ; vg = 0.39248 m3/kg
v = vf + x vfg= 0.001091 + 0.70 (0.39248 - 0.001091)
= 0.2751 m3/kg
 uf = 631.66 kJ/kg ; ufg = 1927.4 kJ/kg
u = uf + x ufg = 631.66 + 0.70 (1927.4) = 1980.8 kJ/kg

52
QUESTION

 Recall the State Postulate: “The equilibrium state of a

simple system is completely specified by any two
independent intensive properties”
 What are the two independent intensive properties used
to evaluate the properties of the saturated liquid-vapor
mixture in the above example?
The quality of a saturated liquid-vapor mixture
in equilibrium is an intensive thermodynamic
property

53
CHAPTER 3

Lecture 5

54
PROPERTY TABLES --
Superheated vapor

State is fixed by specifying any two

independent intensive properties
For superheated vapor, Temperature and
Pressure are independent
Tables A-6 (water) and A-13 (R134a):
Properties (v, u, h and s) are given as
functions of (T&P)

55
PROPERTY TABLES --
Superheated vapor (Table A-6)

Copyright Hany A. Al-Ansary and

S. I. Abdel-Khalik (2014) 56
 Superheated Vapor

 The superheated region is T & P are independent

characterized by:
 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) vg v > vg v

57
PROPERTY TABLES --
Superheated vapor
Example: Water (superheated vapor) at
200 °C and 0.1 MPa
Table A-6:
v = 2.1724 m3/kg
u = 2658.2 kJ/kg
h = 2875.5 kJ/kg
s = 7.8356 kJ/kg K

58
PROPERTY TABLES --
Superheated vapor

 How do we know that H2O is superheated

vapor at 200 °C and 0.1 MPa?
 P < Psat at a given T [@ 200 °C, Psat = 1.5549 MPa]
 T > Tsat at a given P [@ 0.1 MPa, Tsat = 99.61 °C]
 v > vg at a given P or T [@ 200 °C, vg = 0.12721 m3/kg;
@ 0.1 MPa, vg = 1.6941 m3/kg]
 u > ug at a given P or T [@ 200 °C, ug = 2594.2 kJ/kg;
@ 0.1 MPa, ug = 2505.6 kJ/kg]
 h > hg at a given P or T [@ 200 °C, hg = 2792.0 kJ/kg;
@ 0.1 MPa, hg = 2675.0 kJ/kg]

59
PROPERTY TABLES --
Compressed Liquid

State is fixed by specifying any two

independent intensive properties
For compressed (“subcooled”) liquid,
Temperature & Pressure are independent
Tables A-7 (water):
Properties (v, u, h and s) are given as
functions of (T&P)

60
Compressed Liquid

 The compressed liquid T & P are independent

region is characterized by:
 Lower temperatures
(T < Tsat at a given P)
 Lower specific volumes
(v < vf at a given P or T)
 Lower internal energies
(u < uf at a given P or T)
 Lower enthalpies vv vf v
(h < hf at a given P)

61
PROPERTY TABLES --
Compressed Liquid

Example: Compressed
Liquid Water at 200 °C
and 10 MPa
Table A-7:
v = 0.0011482 m3/kg
u = 844.32 kJ/kg
h = 855.80 kJ/kg
s = 2.3174 kJ/kg K
62
PROPERTY TABLES --
Compressed Liquid
 How do we know that H2O is compressed
liquid at 200 °C and 10 MPa?
 P > Psat at a given T [@ 200 °C, Psat = 1.5549 MPa]
 T < Tsat at a given P [@ 10 MPa, Tsat = 311.00 °C]
 v < vf at a given P or T [@ 200 °C, vf = 0.0.001157 m3/kg;
@ 10 MPa, vf = 0.001452 m3/kg]
 u < uf at a given P or T [@ 200 °C, uf = 850.46 kJ/kg;
@ 10 MPa, uf = 1393.3 kJ/kg]
 h < hf at a given P [@ 10 MPa, hf = 1407.8 kJ/kg]
Note: @ 200 °C, hf = 852.26 kJ/kg vs. 855.80 kJ/kg for compressed liquid at P >> Psat

63
APPROXIMATE PROPERTIES --
Compressed Liquid

 Properties of compressed liquids can be well

approximated using saturated liquid values
at the same temperature
 v (T, P)  vf@T
 u(T, P)  uf@T
 h(T, P)  hf@T + vf (P - Psat) or h(T, P)  hf@T
 Percent error in v , u, and h values for previous
example (200 °C and 10 MPa) < 1%

64
Compressed Liquid
Properties

 Compressed Liquid Water at 200 °C and 10 MPa

Property Table A-7 Approx. value % Error
v (m3/kg) 0.0011482 0.001157 0.77
u (kJ/kg) 844.32 850.46 0.73
h (kJ/kg) 855.80 862.03 0.73
or h ≈ hf = 852.26 - 0.41

65
CHAPTER 3

Lecture 6

66
EXAMPLE

2.0 kg of water in a piston-cylinder

assembly
Initial state: P1 = 300 kPa; T1 = 200 °C
Heat is added at constant pressure until
temperature reaches 400 °C
Determine DV, DU, DH
Sketch process on P-v and T-v Diagrams

67
Example

Problem statement:
Initial state: P1 = 300 kPa; T1 = 200 °C
Process: Constant pressure heat addition
Final state: P2 = 300 kPa; T2 = 400 °C
Solution: First step is to determine the
phase(s) at states “1” and “2”
For water at P = 300 kPa, Table A-5 gives:
Tsat = 133.52 °C
Both states “1” & “2” must be superheated vapor
68
Solution - Continued

Table A-6 (Superheated water vapor)

P = 0.30 MPa (133.52°C)

T(°C) v (m3/kg) u (kJ/kg) h (kJ/kg) s (kJ/kg K)

200 0.71643 2651.0 2865.9 7.3132

400 1.03155 2966.0 3275.5 8.0347

69
Solution -- Continued

DV = V2 - V1 = m (v2 - v1)

= 2 (kg) [1.03155 - 0.71643] (m3/kg) = 0.63024 m3
DU = U2 - U1 = m (u2 - u1)
= 2 (kg) [2966.0 - 2651.0] (kJ/kg) = 630.0 kJ
DH = H2 - H1 = m (h2 - h1)
= 2 (kg) [3275.5 - 2865.9] (kJ/kg) = 819.2 kJ

70
Solution -- Process T-v
Diagram
Pc = 22.064 MPa
P = 0.3 MPa
Isobar
2 . T2 > Tc

.
1
Superheated
Vapor
P = 101.42 kPa
Liquid-Vapor
Mixture

100°C

71
Solution -- Process P-v
Diagram

P1 = P2 < Pc
Pressure

Critical Point
Pc

1
. .. 2 T >T >T
2 c 1

Isotherms

vc Specific Volume
(Changes are highly exaggerated)

72
Identification of Phase

If P and T are given

Find Tsat corresponding to P
If T >Tsat: superheated vapor
If T < Tsat: compressed liquid
If T = Tsat: saturated (but additional
information is needed) Why?

73
Identification of Phase

If P (or T) and v are given

Find vf and vg corresponding to P (or T)
If v > vg: superheated vapor
If v < vf: compressed liquid
If vf < v < vg: saturated liquid vapor
mixture
Similar procedure applies if u or h is given (instead of v)

74
EXAMPLE

Fill in the missing information for water

75
EXAMPLE

Fill in the missing information for water

120.21 0.88578 Saturated Vapor

270.28 0.43463 1959.3
200 1.54934 Superheated Vapor
0.001004 125.74 Compressed Liquid
?? ?? Need to specify mixture quality

76
Property Tables for Other
Pure Substances

There are property tables for substances other

than water and refrigerant 134a (R-134a)
Tables for other substances can be found in the
literature.

77
CHAPTER 3

Lecture 7

78
The “Ideal Gas” Equation
of State

What is an “Equation of State”?

 Equation of state: Any equation that relates the
pressure, temperature, and specific volume of a
substance in an equilibrium state.
 In general – any relation between three independent
intensive properties at equilibrium states is referred to
as an Equation of State (e.g. f(P, v, u) = 0)
 The simplest and best-known equation of state for
substances in the gas phase is the ideal-gas equation
of state.

79
The “Ideal Gas” Equation
of State
 What is an “ideal gas”?
An “imaginary” substance that obeys the relation
Pv =RT
Collisions between molecules are elastic
No attraction or repulsion forces between molecules
The volume of molecules is neglected

Ideal gas relation closely approximates behavior of

real gases at low density

80
The “Ideal Gas” Equation
of State
P v = R T
P = Absolute pressure (kPa)
v = Specific volume (m3/kg)
T = Absolute temperature (K)
R = Gas constant (kPa m3/kg K) or (kJ/kg K)
 Gas Constant: R = Ru/M
Ru = Universal gas constant
= 8.314 kPa m3/kmole K) = 8.314 kJ/kmole K
M = molar mass (molecular weight) (kg/kmole)
= mass of 1 kmole in kg or 1 mole in g

81
The “Ideal Gas” Equation
of State

Values of “M” and “R” for different gases

are given in Table A-1

Avogadro’s number
Av = 6.02252 x 1023 molecules/g-mole
= 6.02252 x 1026 molecules /kg-mole
= 2.73177 x 1026 molecules /lb-mole
82
Other Expressions for the
Ideal Gas EOS

Mass = Molar mass  number of Moles

83
Applicability of the Ideal
Gas Equation of State

Is the ideal gas EOS always applicable for

gases?
Real gases behave as an ideal gas at low densities
(i.e., low pressure, high temperature).
At low densities, collisions among molecules are
insignificant
Often, the ideal-gas relation is NOT applicable to
real gases
Care should be taken when using it.
84
 Is Superheated Water Vapor
an Ideal Gas?
 At pressures below 10 kPa,
superheated water vapor can be
treated as an ideal gas,
regardless of its temperature,
with negligible error (less than
0.1 percent).

 At higher pressures, however,

the ideal gas assumption yields
unacceptable errors, particularly
in the vicinity of the critical point
and the saturated vapor line.

% error = ([|vtable - videal|/vtable] 100)

85
Actual Gases

 Ideal gas P-v-T relation is very simple and

convenient to use; however,
 Gases deviate significantly from ideal gas behavior at
states near the saturation region and critical point.
 Deviation can be accounted for by introducing a
correction factor – the compressibility factor, Z
P v = Z R T
 Z = 1 for ideal gas

86
Actual Gases --
Compressibility Factor

P v = Z R T
 Z = vactual /videal
 Deviation of Z from unity is a measure of deviation
from ideal gas behavior
 Experimental data shows that for different
substances, Z is a function of “reduced
pressure” & “reduced temperature”
 Z = f(PR, TR); PR = P/PC & TR = T/TC

87
 Generalized
Compressibility Chart

 For all gases, Z depends only on the reduced Pressure PR and reduced temperature TR
 Principle of Corresponding States 88
 Generalized
Compressibility Chart

vR ≡ v / (R Tcr / Pcr)

89
 Figure A-15 also includes vR, which is called pseudo reduced volume
Ideal Gas Criteria

PR << 1 (for any TR)

TR > 2 (for any PR, except PR >> 1)
Deviation from ideal gas behavior is
greatest near critical point (PR & TR =1)
Should never use ideal gas approximation
except for “highly superheated vapors” at
low pressures; use property tables instead

90
Other Equations of State

Van der Waals EOS

 Accounts for Intermolecular

attraction forces (a/v2) and volume
occupied by molecules (b)
 Constants (a) and (b) determined
from critical properties (Table A-1)
 Model accuracy is often inadequate

Relations describing critical temperature

isotherm used to determine “a” and “b”

91
Other Equations of State
(Contd.)

Beattie-Bridgeman EOS

 Constants A0, a, B0, and b are given in Table 3-4

 Equation is reasonably accurate for densities up to 0.8 ρcr

92
Other Equations of State
(Contd.)

Benedict-Webb-Rubin EOS

 Eight Constants are given in Table 3-4

 Equation is reasonably accurate for densities up to 2.5 ρcr
 Equation further extended by Strobridge (16 constants)

93
Other Equations of State
(Contd.)

Virial Equation of State

 “Virial Coefficients” a(T), b(T), c(T), etc. are functions of

temperature alone
 Determined either experimentally or from Statistical Mechanics
 All virial coefficients vanish as pressure approaches zero

94
 Accuracy of Alternate
Equations of State
 As EOS complexity increases
(i.e. number of constants
increases), the P-v-T
behavior of gases is more
accurately represented over
a wider range.
 Graph shows % of error for
various EOS for nitrogen

95