CHAPTER TWO

PROPERTIES OF PURE SUBSTANCES

Substances of fixed chemical composition throughout are known as pure substances. That is,
pure substances have homogenous and invariable chemical composition irrespective of the phase
or phases in which they exist. Water, helium, carbon dioxide, nitrogen are examples.

A pure substance does not have to be of a single element or compound. 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. Air, for example, is a mixture of several gases, but it is often considered to
be a pure substance because it has a uniform chemical composition. However, a mixture of oil
and water is not a pure substance. Since oil is not soluble in water, it will float on top of the
water, forming two chemically dissimilar regions. 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.
A mixture of ice and liquid water, for example, is a pure substance because both phases have the
same chemical composition. A mixture of liquid air and gaseous air, however, is not a pure
substance since the composition of liquid air is different from the composition of gaseous air,
and thus the mixture is no longer chemically homogeneous. This is due to different components
in air condensing at different temperatures at a specified pressure.
Phases of a Pure Substance
A pure substance may exist in different phases. There are three principal phases: solid, liquid,
and gas. A phase is defined as having a distinct molecular arrangement that is homogenous
throughout and separated from others (if any) by easily identifiable boundary surfaces. A
substance may have several phases within a principal phase, each with a different molecular
structure. For example, carbon may exist as graphite or diamond in the solid phase, and ice may
exist in seven different phases at high pressure. Molecular bonds are the strongest in solids and
the weakest in gases.
Solid: the molecules are arranged in a three‐dimensional pattern (lattice) throughout the solid.
The molecules cannot move relative to each other; however, they continually oscillate about their
equilibrium position.
Liquid: the molecular spacing in liquid phase is not much different from that of the solid phase
(generally slightly higher), except the molecules are no longer at fixed positions relative to each
other.

28
Gas: the molecules are far apart from each other, and a molecular order does not exist. Gas
molecules move randomly and continually collide with each other and the walls of the container
they are in. Molecules in the gas phase are at a considerably higher energy level than they are in
liquids or solid phases.

Phase Transformation
Consider a unit mass of ice heated steadily at a constant pressure of 1 atm. Let the initial

temperature be -30OC. If heat is applied, the temperature increases to 0oC (Fig 2-1). At 0OC ice
starts melting, until the entire mass of ice becomes water; at this stage the temperature remains
constant. Heat added during this phase change is known as latent heat of fusion.

Fig 2-1: T- s diagram for the heating process of water at constant pressure.

Further heating increases the temperature of water. This continues until it reaches 100OC.

At 100oC evaporation of water into steam takes place. Temperature once again remains constant

at 100oC until complete conversion of water into steam occurs. Heat added during this phase
change is known as latent heat of evaporation. Temperature of steam continues to increase
afterwards.

P –T diagram of a Pure Substance

Figure 2-2 shows the P-T diagram of a pure substance. This diagram is often called the phase
diagram since all the three phases are separated from each other by three lines. The sublimation
line separates the solid and the vapor regions; the vaporization line separates the liquid and the

29
vapor regions, and the melting (or fusion) line separates the solid and the liquid regions. These
three lines meet at the triple point, where all three phases coexist in equilibrium. The
vaporization line ends at the critical point because no distinction can be made between liquid and
vapor phases above the critical point. Substances that expand and contract on freezing differ only
in the melting line on the P-T diagram.

Fig 2-2: P-T diagram of a Pure Substance

For simplicity let us consider only the liquid and vapour phases, which are commonly
encountered in most of the engineering applications. Let a system of unit mass of water be
heated at constant pressure. 1-2-3-4 in Fig 2-3 shows the T-v variations at constant pressure.

Fig 2-3: T- v diagram for the heating process of water at constant pressure.

30
From 1 to 2, heat addition increases the temperature with a very small increase in volume. State
of water between 1 and 2 is known as subcooled liquid or compressed liquid because for a
given pressure it is at a temperature lower than the saturation temperature (or) for a given
temperature it is at a pressure higher than saturation 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. At a pressure of 101.325 kPa, Tsat is 100°C. Conversely, at a
temperature of 100°C, Psat is 101.325 kPa.) The state of water at 2 is known as saturated liquid.
Temperature at this state is equal to the saturation temperature. Any further addition of heat
causes evaporation of water.

From 2-3 evaporation is taking place. During this phase change, temperature remains
constant and increase in volume is high. At state 3, the entire mass is in the form of vapour
known as dry saturated vapour.

From 3 to 4, heating causes increase in both temperature and volume. State of steam in this
region is called super-heated state.

As mentioned earlier, at higher pressure evaporation occurs at higher temperature and at

lower pressure evaporation occurs at lower temperature. Latent heat of evaporation decreases
with increase in pressure. For a particular pressure, it becomes zero so that the change from
liquid to vapour phase occurs suddenly without a distinct intermediate state. This pressure is
known as critical pressure. This state on a property diagram is known as critical point. By
connecting the saturated liquid state at different pressures, a line called saturated liquid line is
obtained. In the same way, by connecting the saturated vapour states, saturated vapour line is
obtained. It can be observed that the saturated liquid and vapour lines meet at critical point. Fig
2-4 shows all these lines and various regions on a T- v diagram.

The region between saturated liquid line and saturated vapour line is known as wet region,
consisting of both liquid and vapour. The percentage of composition or quality of this wet steam
is expressed in terms of dryness fraction which is defined as the ratio of mass of vapour to the
mass of the mixture. Specific volume of wet steam is expressed as

v = xvg + (1 - x) vf

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 = vf + x (vg - vf)

= vf + xvfg (2-1)

Where vf - specific volume of the saturate liquid at the given Pressure or Temperature

vg - specific volume of sat. vapour at the given Pressure or Temperature

x - dryness fraction.

Since vf<<vg

v = vf + xvg (2-2)

Fig 2-4: T – v diagram of constant-pressure phase-change processes of a pure substance.

In the compressed liquid region, specific volume may be regarded as a function of temperature
alone since the liquid is incompressible.
v ≅ vf at the given temperature.
In the superheated region, v is a function of both temperature and pressure.

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T – s Diagram for a Pure Substance

Similar to T- v diagram, T-s diagram can also be drawn for a pure substance. Fig 2-.5
shows various regions on a T-s diagram. The salient features of this diagram are:

Temperature is taken on Y-axis and entropy is taken on X-axis

There are three distinct regions: to the left of the saturated liquid line is the liquid
region; between saturated liquid and saturated vapour line is wet region, and to the right
of saturated vapour line is superheated region

Constant pressure lines coincide with the constant temperature lines in the wet region.
These lines becomes curved in the superheated region

Slope of the saturated liquid line is less compared to that in T-v diagram.

Fig 2-5 T – s diagram of constant-pressure phase-change processes of a pure substance.

Entropy of a fluid at saturated liquid state, s = sf @ the given p or T

33
 for saturated vapour state, s = sg at the given p, T
for wet state
s = sf + xsfg (2-3)
where sf and sfg are functions of p or T.

P – v diagram of a Pure Substance

Figure 2-6 shows the P - v diagram of a pure substance. The saturated liquid and saturated-
vapour curves meet at the critical point. The region to the left of the saturated-liquid line is
compressed liquid, and the region to the right of the saturated-vapour line is superheated vapour.
In between the two lines is the two-phase liquid-vapour region. Several isotherms are shown in
the figure. The critical isotherm has an inflection point and a zero slope at the critical point.
Isotherms below the critical point experience two discontinuities in slope as they cross the
saturated-liquid and saturated-vapour lines. In between these two lines, the slope of the
isotherms is zero, and a state in this region can be entirely saturated liquid, entirely saturated
vapour, or a combination of the two.

Fig 2-6: P - v diagram of a pure substance.

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Extending p-v Diagram for a Pure Substance to Solid Phase
The basic principles discussed in conjunction with the liquid–vapor phase-change process apply
equally to the solid–liquid and solid–vapor phase-change processes. Most substances contract
during solidification (i.e., freezing) process. Others, like water, expand as they freeze. The P-v
diagrams for both groups of substances are given in Figs. 2–7 and 2–8. These two diagrams
differ only in the solid–liquid saturation region. The T-v diagrams look very much like the P-v
diagrams, especially for substances that contract on freezing.

Fig 2-7: P-v Diagram of a substance that contracts on freezing.

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Fig 2-8: P - v diagram of a substance that expands on freezing (such as water).

The fact that water expands upon freezing has vital consequences in nature. If water contracted
on freezing as most other substances do, the ice formed would be heavier than the liquid water,
and it would settle to the bottom of rivers, lakes, and oceans instead of floating at the top. The
sun rays would never reach these ice layers, and the bottoms of many rivers, lakes, and oceans
would be covered with ice year round, seriously disrupting marine life.
We are all familiar with two phases being in equilibrium, but under some conditions all three
phases of a pure substance coexist in equilibrium (Fig. 2–9). On P - v or T – v diagrams, these
triple-phase states form a line called the triple line. The states on the triple line of a substance
have the same pressure and temperature but different specific volumes. The triple line appears as
a point on the P-T diagrams and, therefore, is often called the triple point. Various substances
have different triple-point temperatures and pressures. For water, the triple-point temperature and
pressure are 0.01°C and 0.6113 kPa, respectively. That is, all three phases of water will exist in
equilibrium only if the temperature and pressure have precisely these values. No substance can
exist in the liquid phase in stable equilibrium at pressures below the triple-point pressure. The
same can be said for temperature for substances that contract on freezing. However, substances
at high pressures can exist in the liquid phase at temperatures below the triple-point temperature.

36
For example, water cannot exist in liquid form in equilibrium at atmospheric pressure at
temperatures below 0°C, but it can exist as a liquid at -20°C at 200 MPa pressure. Also, ice
exists at seven different solid phases at pressures above 100 MPa. There are two ways a
substance can pass from the solid to vapor phase: either it melts first into a liquid and
subsequently evaporates, or it evaporates directly without melting first. The latter occurs at
pressures below the triple point value, since a pure substance cannot exist in the liquid phase at
those pressures (Fig. 2–10). Passing from the solid phase directly into the vapor phase is called
sublimation. For substances that have a triple-point pressure above the atmospheric pressure
such as solid CO2 (dry ice), sublimation is the only way to change from the solid to vapour phase
at atmospheric conditions.

Fig 2-9: At triple-point pressure and temperature, a substance exists in three phases in
equilibrium.

Fig 2-10: At low pressures (below the triple point value), solids evaporate without melting first
(sublimation).

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P – v – T Surface
The state of a simple compressible substance is fixed by any two independent, intensive
properties. Once the two appropriate properties are fixed, all the other properties become
dependent properties.
All the points on the surface represent equilibrium states. All states along the path of a quasi-
equilibrium process lie on the P-υ-T surface (figs 2-11 and 2-12) since such a process must pass
through equilibrium states. The single-phase regions appear as curved surfaces on the P-v-T
surface, and the two-phase regions as surfaces perpendicular to the P-T plane. This is expected
since the projections of two phase regions on the P-T plane are lines.
All the two-dimensional diagrams we have discussed so far are merely projections of this three-
dimensional surface onto the appropriate planes. A P-υ diagram is just a projection of the P-v-T
surface on the P-v plane, and a T-υ diagram is nothing more than the bird’s-eye view of this
surface. The P-v-T surfaces present a great deal of information at once, but in a thermodynamic
analysis, it is more convenient to work with two-dimensional diagrams such as the P-v and T-v
diagrams.

Fig 2-11: P-υ-T surface of a substance that contracts on freezing.

38
Fig 2–12: P-υ-T surface of a substance that expands on freezing (like water).

USE OF STEAM TABLES

As mentioned earlier to define the thermodynamic state of a given substance, any two
independent intensive properties are sufficient. Once the state is fixed, all other properties can be
computed. Tables giving the property values of saturated liquid and saturated vapour with
respect to temperature and pressure are available along with the properties of superheated steam.
These tables can be made use of in the calculation of properties at any state. For refrigeration
application, fluids like Ammonia and R134a are used. Properties of these fluids are also available
in the form of tables.

For most substances, the relationships among thermodynamic properties are too complex to be
expressed by simple equations. Therefore, these properties are frequently presented in the form
of tables. Some thermodynamic properties can be measured easily, but others cannot and are
calculated by using the relations between them and measurable properties. The results of these
measurements and calculations are presented in tables in a convenient format.

39
In addition to the temperature, pressure, and specific volume data, tables contain data for the
specific internal energy u, the specific enthalpy h, and the specific entropy s. In thermodynamics
analysis, we will encounter the combination of properties U + PV frequently. For simplicity this
combination is defined as a new property called enthalpy.
H =U + PV (kJ)
The enthalpy per unit mass is
h = u + Pv (kJ/kg) (2-4)

Saturated Water Tables

Since temperature and pressure are dependent properties using the phase change, two tables are
given for the saturation region. One has temperature as the independent property and the other
has pressure as the independent property. These two tables contain the same information.
The subscript fg used in the tables refers to the difference between the saturated vapor value and
the saturated liquid value region.
That is,
u fg = u g − u f
h fg = h g − h f
s fg = s g − s f
(2-5)
The quantity h fg is called the enthalpy of vaporization (or latent heat of vaporization). It

represents the amount of energy needed to vaporize a unit of mass of saturated liquid at a given
temperature or pressure.

Quality and Saturated Liquid-Vapor Mixture

State 2 to 3 in Fig 2-3 is a constant pressure heat addition process for water which contains a
mixture of saturated liquid and saturated vapour, to determine the properties at any point
between these states, there is need for a new parameter called the quality x (which) is defined as:
mg
x=
m f + mg
(2-6)
Where mg is the mass of saturated vapor
mf + mg is the total mass

40
The quality is zero (0) for the saturated liquid and one (1) for the saturated vapor (0 ≤ x ≤ 1). The
average specific volume at any state between 2 and 3 is given in terms of the quality as follows.
Consider a mixture of saturated liquid and saturated vapor. The liquid has a mass mf and
occupies a volume Vf. The vapor has a mass mg and occupies a volume Vg.
Since
V = V f + Vg

m = m f + mg

V = mv , V f = mv f , V g = mv g

mv = m f v f + m g v g

mf vf mg vg
v= +
m m
Using the definition of the quality x
mg mg
x= =
m m f + mg

Then
mf m − mg
= =1− x
m m
Note, quantity 1- x is often given the name moisture. The specific volume of the saturated
mixture becomes
v = (1 − x )v f + xv g

The form that is most often used is

v = v f + x (v g − v f )

It is noted that the value of any extensive property per unit mass in the saturation region is
calculated from an equation having a form similar to that of the above equation. Let Y be any
extensive property and let y be the corresponding intensive property, Y/m, then

= y f + x(y g − y f )
y
y=
m
y = y f + xy fg
(2-7)
where y fg = y g − y f

41
The term yfg is the difference between the saturated vapor and the saturated liquid values of the
property y; y may be replaced by any of the variables v, u, h, or s.
The above equation is used to determine the quality x of a saturated liquid-vapor state.
The following application is called the Lever Rule:
y − yf
x=
y fg
(2-8)
The Lever Rule is illustrated in the following figures.

Fig 2-13

Superheated Water Table

A substance is said to be superheated if the given temperature is greater than the saturation
temperature for the given pressure. State 4 in Fig 2-3 is a superheated state.
In the superheated water table, T and P are the independent properties. The value of temperature
to the right of the pressure is the saturation temperature for the pressure. The first entry in the
table is the saturated vapor state at the pressure.
Superheated vapor is characterized by:
Lower pressure (P < Psat at a given T)
Higher temperature (T > Tsat at a given P)

42
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)

Compressed Liquid Water Table

A substance is said to be a compressed liquid when the pressure is greater than the saturation
pressure for the temperature. It is now noted that state 1 in Fig 2-3 is called a compressed liquid
state because the saturation pressure for the temperature T1 is less than P1.
Data for water compressed liquid states are found in the compressed liquid tables.
At pressures below 5 MPa for water, the data are approximately equal to the saturated liquid data
at the given temperature. The intensive parameter y, that is v, u, h, and s data is approximated as
y ≅ y f @T (2-9)

The enthalpy is more sensitive to variations in pressure; therefore, at high pressures the enthalpy
can be approximated by
h ≅ h f @ T + v f (P − Psat )
(2-10)
At this level, the compressed liquid enthalpy may be approximated by
h ≅ h f @T
(2-11)
Compressed liquid is characterized by:
Higher pressure (P > Psat at a given T)
Lower temperature (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)

How to Choose the Right Table

The correct table to be used to find the thermodynamic properties of a real substance can always
be determined by comparing the known state properties to the properties in the saturation region.
Given the temperature or pressure and one other property from the group v, u, h, and s, the
following procedure is used. For example if the pressure and specific volume are specified, three
questions are asked: For the given pressure,

43
 is v < v f ?

is v f < v < v g ?

is v > v g ?

The answer to one of these questions must be yes. If the answer to the first question is yes, the
state is in the compressed liquid region, and the compressed liquid tables are used to find the
properties of the state. If the answer to the second question is yes, the state is in the saturation
region, and either the saturation temperature table or the saturation pressure table is used to find
the properties. Then the quality is calculated and is used to calculate the other properties, u, h,
and s. If the answer to the third question is yes, the state is in the superheated region and the
superheated tables are used to find the other properties.
Some tables may not always give the internal energy. When it is not listed, the internal energy is
calculated from the definition of the enthalpy as
u = h − Pv (2-12)

Worked Example
1. A rigid tank with a volume of 2.5 m3 contains 5 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-υ diagram with
respect to saturation lines.
Solution: A rigid tank that is filled with saturated liquid-vapor mixture is heated. The
temperature at which the liquid in the tank is completely vaporized is to be determined, and the
T-v diagram is to be drawn.
Analysis This is a constant volume process (v = V/m = constant), and the specific volume is
determined to be H2O

75°C
V 2.5 m 3
v= = = 0.5 m 3 /kg
m 5 kg

When the liquid is completely vaporized the tank will contain saturated vapor only. Thus,
T
v2 = vg = 0.5 m / kg
3
2

The temperature at this point is the temperature that corresponds

1

v
44
to this vg value,

T = Tsat @ v = 140.7 ο C
g = 0.5 m 3 /kg

2. A rigid vessel contains 2 kg of refrigerant-134a at 900 kPa and 80°C. Determine the
volume of the vessel and the total internal energy.
Solution: A rigid vessel is filled with refrigerant-134a. The total volume and the total internal
energy are to be determined.
Properties The properties of R-134a at the given state are (From Table).
P = 900 kPa  u = 288.87 kJ/kg
T = 80 ο C  v = 0.02861 m 3 /kg R-134a

2 kg
Analysis The total volume and internal energy are determined from 900 kPa

V = mv = (2 kg)(0.02861 m 3 /kg) = 0.05722 m 3 80°C

U = mu = (2 kg)(288.87 kJ/kg) = 577.74 kJ

3. A 0.5-m3 vessel contains 10 kg of refrigerant-134a at -20°C. Determine (a) the pressure,

(b) the total internal energy, and (c) the volume occupied by the liquid phase.
Solution: A rigid vessel contains R-134a at specified temperature. The pressure, total internal
energy, and the volume of the liquid phase are to be determined.

Analysis (a) The specific volume of the refrigerant is

V 0.5 m 3
v= = = 0.05 m 3 /kg
m 10 kg

At -20°C, vf = 0.0007361 m3/kg and vg = 0.1464 m3/kg. Thus the tank contains saturated liquid-
vapor mixture since vf < v < vg , and the pressure must be the saturation pressure at the specified
temperature,

P = Psat @ − 20 οC = 132.99 kPa

(b) The quality of the refrigerant-134a and its total internal energy are determined from

45
 v − vf 0.05 − 0.0007361
x= = = 0.338
v fg 0.1464 − 0.0007361
u = u f + xu fg = 24.17 + 0.338 × (215.84 − 24.17) = 88.95 kJ/kg
R-134a
U = mu = (10 kg)(88.95 kJ/kg) = 889.5 kJ
10 kg
(c) The mass of the liquid phase and its volume are determined from
-20°C

m f = (1 − x)mt = (1 − 0.338) × 10 = 6.62 kg

V f = m f v f = (6.62 kg)(0.0007361 m 3 /kg) = 0.00487 m 3

4. A piston-cylinder device initially contains 50 L of liquid water at 25°C and 300 kPa. Heat
is added 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-υ diagram with respect to saturation lines.
Solution: A piston-cylinder device that is initially filled with water is heated at constant pressure
until all the liquid has vaporized. The mass of water, the final temperature, and the total enthalpy
change are to be determined, and the T-v diagram is to be drawn.

Analysis Initially the cylinder contains compressed liquid (since P > Patm @ 25°C) that can be
approximated as a saturated liquid at the specified temperature,
T
v1 ≅ v f @ 25οC = 0.001003 m /kg3

h1 ≅ h f @ 25οC = 104.89 kJ/kg 2 H2O

1
25°C
(a) The mass is determined from
v
V1 0.050 m 3
m= = = 49.85 kg
v1 0.001003 m 3 /kg

(b) At the final state, the cylinder contains saturated vapor and thus the final temperature must be
the saturation temperature at the final pressure,

T = Tsat @300 kPa = 133.55ο C

(c) The final enthalpy is h2 = hg @ 300 kPa = 2725.3 kJ/kg. Thus,

46
 ∆H = m ( h2 − h1 ) = (49.8 5 kg)(2725.3 − 104.89) kJ/kg = 130,627 kJ

5. 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-υ diagram.
(b) Find the final temperature.
(c) Determine the volume change.
Solution: Superheated steam in a piston-cylinder device is cooled at constant pressure until half
of the mass condenses. The final temperature and the volume change are to be determined, and
the process should be shown on a T-v diagram.

Analysis (b) 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,

T = Tsat@1 MPa = 179.91 ο C

(c) The quality at the final state is specified to be x2 = 0.5. H2O

300°C
The specific volumes at the initial and the final states are

P1 = 1.0 MPa 
 v1 = 0.2579 m /kg
3
T1 = 300 ο C 
T
P2 = 1.0MPa  1
 v 2 = v f + x 2 v fg
x 2 = 0 .5  = 0.001127 + 0.5 × (0.19444 − 0.001127)
2
= 0.0978 m 3 /kg

Thus, v

47