1

Chapter 3
Properties of Pure Substances
3.1

Pure Substance

Pure substance = a substance with fixed chemical composition throughout (e.g. water, nitrogen)

3.2

A mixture of various chemical elements or compounds is a pure substance as long as the

mixture is homogeneous. Air is a mixture of several gases, is considered a pure substance
because it has uniform chemical composition. Oil and water mixture is not a pure substance
since the insoluble oil collects on top of the water, forming two dissimilar regions.
A mixture of two or more phases of a pure substance is still a pure substance provided that the
chemical composition of all phases is the same.
Phases of a Pure Substance

There are three principal phases solid, liquid, and gas.

A substance may also have several phases within a principal phase each with a different molecular
structure, e.g. carbon may exist as graphite or diamond in the solid phase. Helium has two liquid
phases; iron has three solid phases. Intermolecular bonds are strongest in solids and weakest in gases.
3.3

Property Diagrams for Phase-change Processes

Property variations during phase-change processes can be shown on property diagrams.

3.3.1

The T-v Diagram

Consider a piston-cylinder device which contains water at 20 oC and 1 atm (state 1). The water exists
in the liquid phase and it is called : compressed liquid or subcooled liquid. As heat is transferred to
the water, its temperature rises, the liquid expands slightly (specific volume increases) and the piston
rises. As more heat is transferred, the temperature keeps rising to 100 oC, where the liquid starts to
vaporize (boil). A liquid that is about to vaporize is called a saturated liquid state 2.
Once boiling starts, with heat addition the temperature remains constant (at constant pressure) and the
volume increases. At state 3 the cylinder is filled with a mixture of liquid and vapor. Further heat
addition converts more liquid to vapor and at state 4, all liquid is converted to vapor. At state 4, any
heat loss causes some of the vapor to condense (phase change from vapor to liquid). Thus, state 4 is a
saturated vapor state.
A substance at states between 2 and 4 is called saturated liquid-vapor mixture a two phase region.
From state 4, further heat addition increases the temperature and the volume. Beyond state 4, the vapor
is called superheated vapor.
The experiment can be repeated with different pressures inside the cylinder, by varying the mass of the
piston since,

2
P Patm

mg
A

T
( C)
o

P = 1 atm
300

5
saturated liquid
superheated vapor

100

saturated
mixture

compressed
liquid
saturated vapor
20

v = V/m

1
.
.

bubbles formed
onset of boiling

heating process
A complete T-v diagram is obtained by performing the experiment at different pressures.
T, oC
.
.
.
.
.
.
.
.
.
.

critical point
constant pressure lines
saturated liquid line
compressed liquid
or subcooled
liquid
region

P2 > P1

superheated
vapor region

P1
saturated liquid-vapor region
or
wet region
saturated vapor line

3
Critical Point = point at which the saturated liquid and saturated vapor states are identical.
For water at critical point:
Critical temperature Tcr = 373.95 oC
Critical pressure Pcr = 22.06 MPa
Critical specific volume vcr = 0.003106 m3/kg
At pressures above the critical pressure, there is no distinct phase-change process, and at all times there
is only one phase present. The point where liquid becomes vapor is not precisely known. Above the
critical state, it is referred to as superheated vapor at T > Tcr and as compressed liquid at T < Tcr .
3.3.2

The P-v Diagram

Consider a piston-cylinder device that contains liquid water at 1 MPa and 150 oC (compressed liquid
state). Removing some weights on top the piston, the pressure inside the cylinder is reduced, the
volume is increased slightly. The water exchanges heat with the surroundings such that its temperature
remains constant. With more weight reduction, the water boils at the saturation-pressure of 0.4762
MPa at 150 oC. When boiling starts, further addition of heat and without removing any more weights,
the volume increases further but the temperature remains constant a constant pressure phase-change
process. At state 4, the last liquid has vaporized (saturated vapor state), and further weight removal
with some heat addition increases the volume and reduces the pressure in the superheated vapor
region.
P
MPa
1
150 oC
1
compressed
liquid
saturated vapor
0.4762

saturated
mixture

saturated liquid
superheated

vapor
5

v = V/m

1
.
.

bubbles formed
onset of boiling

heating process

4
A complete P-v diagram is obtained by performing the experiment at different temperatures
P, MPa

critical point

.
.

saturated vapor line

saturated liquid line

.
.
.

superheated
vapor region

.
.
.
.
.
.
.

compressed or
subcooled liquid
region

T2 > T1
constant T lines

saturated liquid-vapor region

or
wet region

T1

Saturation temperature Tsat = 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 given
temperature.

3.3.3

The P-T Diagram

The P-T diagram is often called the phase diagram since all three principal phases are separated from
each other by three line.
.

Substances that contract

on freezing

Critical point
.

Substances that expand

on freezing

LIQUID
Melting

Vaporization

SOLID

Triple point
VAPOR

Sublimation

T
Triple point = all three phases coexist in equilibrium

5
The P-v-T Surface
The P-v-T surfaces provide a great deal of information at a glance. In thermodynamics it is more
convenient to work with 2-dimensional diagrams, such as the P-v and T-v diagrams. (consult textbook
on P-v-T diagram).
3.4 Property Tables
Thermodynamic properties are usually presented in the form of tables, which can be used easily when
doing manual calculations.
3.4.1

Saturated Liquid and Saturated Vapor States

Properties of saturated liquid and saturated vapor for water are listed in Tables A-4 and A-5.
subscript f denotes properties of saturated liquid
subscript g denotes properties of saturated vapor
subscript fg denotes difference between saturated vapor and saturated liquid values
For example,
vf = specific volume of saturated liquid
vg = specific volume of saturated vapor
vfg = vg vf
hfg is called the enthalpy of vaporization (or latent heat of vaporization). It is the energy needed to
vaporize a unit mass of saturated liquid at a given temperature or pressure. It decreases as the
temperature or pressure increases, and becomes zero at the critical point.

Example
A rigid tank contains 10 kg of saturated liquid water at 90 oC. Determine the pressure in the tank and
the volume of the tank.
T
o

At saturation, T = 90 C = Tsat
Thus, P = Psat @ 90C = 70.183 kPa
v = vf @ 90C = 0.001036 m3/kg
V = mv = 10 (0.001036)
= 0.01036 m3

Saturated
liquid

P = 70.183
Psat = 70.183 kPa

90 C

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Example
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.
P, kPa

100

vf

vg

v, m3/kg

The process must have taken place in a piston cylinder device !

(a) State 1 is saturated liquid while state 2 is saturated vapor, both at Psat = 100 kPa.
From table, vg vf = 1.6941 0.001043 = 1.6931 m3/kg.
Thus, V2 V1 = mvfg = (0.2 kg)(1.6931 m3/kg) = 0.3386 m3.
(b) The energy needed to vaporize a unit mass of substance at a given pressure is the enthalpy of
vaporization, hfg = 2257.5 kJ/kg for water at 100 kPa.
Thus, the energy transferred is,
mhfg = (0.2 kg)(2257.5 kJ/kg) = 451.5 kJ
3.4.2

Saturated LiquidVapor Mixture

In the saturated liquidvapor (or mixture) region, the proportion of the liquid and vapor phases in the
mixture is given by a property called the quality x defined as the ratio of the mass of vapor to the
total mass of the mixture.
x

where :

m vapor
mtotal

mtotal m liquid m vapor m f m g

quality has significance for saturated mixtures only

its value is between 0 (saturated liquid) and 1 (saturated vapor)
0 x 1

A two-phase system can be treated as a homogeneous mixture for convenience.

saturated vapor

vg

saturated liquid vapor

mixture

saturated liquid

vf

vavg

7
Imagine that the saturated liquid and saturated vapor are mixed well, forming a homogeneous mixture.
The volume occupied by saturated liquid is Vf and the volume occupied by saturated vapor is Vg. The
total volume V is the sum of the two :
V = Vf + Vg
But

mtotal v avg m f v f m g v g

V = mv

m total v avg mtotal m g v f m g v g

m f mtotal m g

Dividing by mtotal yields :

v avg 1 x v f xv g

v avg v f x v g v f v f xv fg

or

The analysis can be repeated for specific internal energy, specific enthalpy and specific entropy to give
u avg u f xu fg
havg h f xh fg

s avg s f xs fg

These can be summarized in a single equation:

where y is v, u, h, or s.
y f y avg y g

and it is obvious that :

y avg y f xy fg

The subscript avg (for average) is usually dropped out for brevity !

Example
A rigid tank contains 10 kg of water at 90 oC. If 8 kg of the water is in the liquid form and the
remaining is in the vapor form, determine (a) the pressure in the tank and (b) the volume of the tank.
(a) Since there are two phases of water in the tank, the mixture is at saturation temperature of 90 oC
and the pressure is the saturation pressure at 90 oC
P = Psat@90 C = 70.183 kPa
(b) At Tsat = 90 oC, vf = 0.001036 m3/kg and vg = 2.3593 m3/kg

saturated vapor
Vg

vg

V = Vf + Vg = m f v f m g v g = 8(0.001036) + 2(2.3593) = 4.73 m3.

.

saturated liquid

OR

mg
mtotal

2
0 .2
10

v v f xv fg =

0.001036 + 0.2(2.3593 0.001036) = 0.473 m3/kg

V = mv = 10(0.473) = 4.73 m3

Vf

vf

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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.
(a)
The state postulate states that 2 independent intensive properties are needed to completely specify the
state of a system. We are only given pressure P . The other intensive property is
v

V 80 / 1000

0.02 m3/kg
m
4

At 160 kPa, vf = 0.0007437 m3/kg,

v f v vg

Therefore :

vg = 0.12348 m3/kg.

i.e. the refrigerant is in the saturated mixture region.

The temperature is the saturation temperature at 160 kPa:

(b) x

v vf
v fg

T = Tsat, 160 kPa = 15.60 oC.

0.02 0.0007437
= 0.157
0.12348 0.0007437

(c) At 160 kPa, hf = 31.21 kJ/kg and hg = 209.90 kJ/kg. Thus

h h f xh fg = 31.21 + 0.157(209.90 31.21) = 59.26 kJ/kg
(d) Mass of vapor, m g xmtotal = 0.157(4) = 0.628 kg
Thus, V g m g v g = 0.628 (0.12348) = 0.0775 m3 (or 77.5 L).
Of course Vf = 80 77.5 = 2.5 L
3.4.3

Superheated Vapor

Superheated vapor is single phase, and thus T and P are independent properties. Properties must be
obtained from the superheated tables. It is characterized by :
(a) T Tsat
(b) P Psat
(c) y y g

at a given P (when given P, T )

at a given T (when given P, T )
at a given T or P (when given P,y or T,y )

(a) .Given P, T
T
Pgiven

(b) . Given P, T
P
Tgiven

Tgiven
Psat
Tsat

Psat

Tsat
Pgiven

also

v
u, h, s

9
(c) Given P, y

(c) Given T, y

P
Pgiven

Tgiven

Psat
Tsat

Psat

Tsat
Pgiven

yg

yg

ygiven
Example
Determine the internal energy of water at 200 kPa and 300 oC.
Let
Psat = 200 kPa
Tsat = 120.21 oC.
Since Tgiven > Tsat the phase is superheated vapor.
Or draw a T-v diagram:
T, oC

200 kPa

Tgiven = 300
Psat =200 kPa
Tsat = 120.21

v
From superheated vapor table, u = 2808 kJ/kg.
Example
Determine the temperature of water at P = 0.5 MPa and h = 2890 kJ/kg.
Let Psat = P = 0.5 MPa From saturated table, hg = 2748.1 kJ/kg.
Since h > hg the phase is superheated vapor.
From superheated vapor table

T, oC
200
T=?
250

h , kJ/kg
2855.8
2890
2961.0

By linear interpolation
T = 200 +

2890 2855.8 250 200

2961 2855.8

= 216.3 oC

ygiven

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3.4.4

Compressed liquid

Compressed liquid properties are largely independent of pressure increasing P by 100 times results
in property change of less than 1 % ! This explains the reason why compressed liquid tables are not
commonly available.
A generally accepted approximation is to treat compressed liquid as saturated liquid at the given
temperature . This is so because compressed liquid properties are more dependent on temperature
than they do on pressure. That is
y y f @T

where y = v, u, h or s
In general, a compressed liquid is characterized by:
(a) T Tsat
(b) P Psat
(c) y y f

at a given P (when given P, T )

at a given T (when given P, T )
at a given T or P (when given P,y or T,y )

(a) .Given P, T
T

(b) . Given P, T
P
Pgiven
Pgiven

Tsat
Psat

Psat

Tsat

Tgiven

Tgiven

also

v
u, h, s

(c) Given P, y

v
(c) Given T, y

P
Pgiven
.
Psat

Tsat
Tgiven

ygiven

v
yf

ygiven yf

11
Example
Determine the internal energy of compressed liquid water at 80 oC and 5 MPa, using (a) data from
compressed liquid table and (b) saturated liquid data. What is the error involved ?
Let Tsat = 80 oC for which Psat = 47.416 kPa.
Since 5 MPa > Psat the phase is compressed liquid.
(a) From compressed liquid table, u = 333.82 kJ/kg
(b) Using the approximation approach,
u u f ,80C = 334.97 kJ/kg an error of 0.34 %
Reference State and Reference Values
The properties u, h, and s cannot be measured directly, but calculated from measurable properties
using the appropriate thermodynamic equations. These equations give changes in properties, not the
values of properties at specified states.
Therefore, a convenient reference state is chosen, and zero value is assigned for a convenient property
or properties at that state.

For water, the state of saturated liquid at 0.01 oC is the reference state, where u = 0, s = 0
For refrigerant-134a, the reference state is for saturated liquid at 40 oC, where h = 0, s =0

Because of the reference state chosen, some property values can be negative !
In thermodynamics, we are concerned with changes in property values, not their absolute values.

3.5 The Ideal-Gas Equation of State

Equation of state = any equation that relates the pressure, temperature, and specific volume of a
substance
In 1622, Robert Boyle observed that during experiments with a vacuum chamber the pressure of
gases is inversely proportional to their volume. In 1802, Charles and Gay-Lussac experimentally
showed that at low pressures the volume of a gas is proportional to its temperature. Combining these
two empirical observations, we have the so called ideal-gas equation of state (or ideal-gas relation) :
T
T
R
v
v

which is usually written as

Pv RT

where P is the absolute temperature, T is the absolute temperature, and v is the specific volume. A gas
that obeys this relation is called an ideal gas.
R = gas constant

12
The gas constant R is different for each gas, is calculated from
R

Ru
M

.. (kJ/kg.K or kPa.m3/kg.K)

Ru = universal gas constant

M = molar mass (or molecular weight)

Ru is the same for all substances, where

Ru = 8.31447 kJ/kmol.K
= 8.31447 kPa.m3/kg.K
The molar mass M is defined as the mass of one mole (or gram-mole [gmol]) of a substance in
grams or the mass of one kmol (kilogram-mole [kgmol]) in kilograms. For nitrogen, M = 28
which means that the mass of 1 kmol of nitrogen is 28 kg.
The mass of a system is simply the product of its molar mass and the mole number N :
m = MN

(kg)

The ideal-gas equation can also be written in other forms :

V = mv
mR = ( MN) R = NRu

PV = mRT
PV = NRuT

It has been experimentally observed that the ideal-gas relation closely approximates the P-v-T
behavior of real gases at low densities which occur at low P and high T.
Familiar gases such as air, nitrogen oxygen, hydrogen, helium, argon, krypton, and heavier
gases such as CO2 can be treated as ideal gases with negligible errors (< 1 %)
Dense gases such water vapor in power plants and refrigerant vapors in refrigerators should not
be treated as ideal gases instead use property tables.

Example
Determine the mass of the air in a room with dimensions 4 x 5 x 6 m at 100 kPa and 25 oC.
V= 4x5x6 = 120 m3
R = 0.287 kJ/kg.K
T = 25 + 273 = 298 K
Assuming air is an ideal gas,

PV
100120

= 140.3 kg
RT 0.287 298

Water Vapor an Ideal Gas ?

The answer is yes and no.
At pressure below 10 kPA, it can be treated as one, regardless of its temperature, with errors less than
0.1 %. Thus, in air-conditioning applications, the water vapor can be treated as an ideal gas with
almost no error since the vapor pressure is very low. However, in steam power plants, the pressures are
usually very high ideal-gas relations are no longer valid !

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3.6

Compressibility Factor, Z

The ideal-gas relation can be used for real gases by including a correction factor called the
compressibility factor Z in the ideal-gas relation, where
Z

or

Pv
RT

Pv = ZRT

Z also be written as,

v actual
v ideal

where v ideal

RT
P

For ideal gases, Z = 1. The farther away Z is from unity, the more the gas deviates from idealgas behavior.

Normalization process: Define the following parameters

reduced pressure,
reduced temperature,

P
Pcr
T
TR =
Tcr

PR =

Principle of corresponding states = the Z factors for all gases is approximately the same at the same
reduced pressure and temperature
By curve-fitting all data for many different type of gases, we obtain the generalized compressibility
chart that can be used for all gases. These observations can be made for the chart :

At low pressures ( PR << 1 ), gases behave as an ideal gas regardless of temperature

At high temperatures ( TR > 2 ), ideal-gas behavior is observed regardless of pressure (except
when PR >> 1 ).
Deviation of a gas from ideal-gas behavior is greatest in the vicinity of the critical point

Example
Determine the pressure of water vapor at 350 oC and 0.035262 m3/kg, using
(a) steam tables, (b) ideal-gas relation, and (c) the generalized compressibility chart
For water vapor, R = 0.4615 kJ/kg.K, Pcr = 22.06 kPa, Tcr = 647.1 K
(a) From tables, at 350 oC and 0.035262 m3/kg,
(b) Using ideal-gas assumption,
(c) compressibility chart, v R
TR =

P = 7 MPa (most accurate)

RT 0.4615 623

= 8.15 MPa (16.4 % error)

v
0.035262

v actual
0.035262 22.064

= 2.605
RTcr / Pcr
0.4615 647.1
T
623

= 0.96
Tcr
647.1

14
From chart, PR = 0.31. Therefore, P = PR Pcr = 0.31 (22.06) = 6.84 MPa (2.3 % error)
3.7

Other Equations of State

The ideal-gas relation is very simple, with limited range of applicability. Several more complex
equations have been proposed to extend the range of applicability.
Van der Waals Equation of State
Proposed in 1873 with two constants :

a
v b RT
v2

where,
27 R 2 Tcr2
64 Pcr
RTcr
b
8 Pcr
a

i.e. the constants a and b can be obtained for any substance from the critical-point data alone.
The accuracy is often inadequate, but has historical significance as it pioneered the attempts at
modeling the behavior of real gases. Greater accuracy is obtainable from other more complex
equations of state such as : Beattie-Bridgeman, Benedict-Webb-Rubin and Virial Eqn. Of State.