MODULE NO.

2
PROPERTIES OF PURE SUBSTANCES

OVERVIEW

Thermodynamics is the science of energy and entropy; it deals with heat and work
and these properties of substances that bear a relation to heat and work.

In this module, you will learn the properties of pure substances. Illustrative
problems were provided before the end of this module.

LEARNING OUTCOMES

At the end of this module, you should be able to explain the various
phases; solid, liquid and vapor of a substance

LEARNING PLAN

PURE SUBSTANCE

2.1. Phase

A phase is any homogenous part of a system, which is physically distinct and is

separated from other of the system by distinct bounding surface. The three different
phases of pure substance are solid, liquid, and vapor or gas. Ice, liquid water vapor
constitutes three different phases of water, since each form is homogenous and physically
different from the others and is clearly defined by distinct boundaries existing between
them. A liquid solution constitutes a single phase no matter if it is homogenous. For
example, sugar and water (assuming that sugar is dissolved in water). If additional
amounts of sugar are added until sugar no longer dissolves in water, then this constitutes
two different phases sugar solution and solid sugar. The same thing goes for solid and
vapor solution. Even if solid or liquid is composed of several substances as long as
solution is homogenous then the substance is said to be a single phase.

2.2. Definition of Pure Substance

A pure substance is one that is chemically homogenous and invariable in

chemical composition. It may exist in more than one phase, as long as the chemical
composition is the same then it is said to be a pure substance. For example, a mixture of
liquid water and water vapor (steam) or, a mixture of ice and liquid water are both pure
substances since every phase have the same chemical composition. Air which is a
mixture of (mainly) oxygen, and nitrogen is considered a pure substance provided there
is no change of phase. It is also because the chemical composition of liquid air is different
from that gaseous air and therefore the mixture of liquid and gaseous air is no longer pure
substance (liquid air has higher fraction of nitrogen than gaseous air).

2.3. Phase Diagrams

Two phases of pure substance can coexist in equilibrium at a given temperature

only if the pressure is a particular value that corresponds to the pressure. These
corresponding values of pressure and temperature are called saturation temperatures
and saturation pressures. Remember that there is only one saturation temperature for
a given saturation pressure and vice versa. The condition under which two or more
phases of a pure substance can exist together in equilibrium is called saturation
condition.

A phase diagram is a pressure-temperature diagram showing more than one of

the saturation lines (liquid-vapor, liquid-solid, solid-vapor, or other) of a pure substance.
A phase diagram for water (a substance which contracts on freezing) is shown in figure
1. any portion on a saturation line of a phase diagram represents conditions of pressure
and temperature under which two phases exist in equilibrium. The three lines called
saturation lines namely solid-liquid, solid-vapor, and liquid-vapor lines. All points not on a
saturation line represent conditions under which only one phases of the pure substance
can exist. Points between solid-liquid and liquid-vapor lines represent liquid states, and
these lines represent solid states, and the region is called solid region. Points to the right
of the solid-vapor and liquid-vapor lines represent vapor states, and the region is now
called vapor region. Liquid whose temperature is lower than its saturation temperature
at the same pressure is called subcooled liquid. The other term for subcooled liquid is
compressed liquid since the actual pressure of liquid is higher than its saturation
pressure at the actual temperature. Therefore, all points in the liquid region and not on
the liquid-vapor saturation line represents states of subcooled liquids. Vapor at a
temperature higher than its saturation temperature at the same pressure is called
superheated vapor. The intersection of the vaporization line (line bd), fusion line (bc),
and sublimation line (line ab) on a pT diagram represents the conditions under which
three phase can coexist in equilibrium and is called triple point (point b). To the end of
the liquid-vapor line is point d known as the critical point. At pressures or temperatures
higher than the critical point, there is no distinct whether the substance is liquid or vapor
and the specific volume of liquid and vapor are equal.
 Fig. 1. Temperature-Pressure Diagram for Water

Source: expii.com

Fig. 2. Phase Change Diagram

Q1 = f(∆T)
Q2 = f(phase)
Q3 = f(∆T)
Q4 = f(phase)
Q5 = f(∆T)
Note: there is an error in using the value of cp
Use integral, cp = ∫ f(T)dt

A = subcooled solid
B = saturated solid
C= pure liquid
D = saturated liquid
E = saturated vapor
F = superheated vapor

Let us look at the pressure-volume diagram for water and examine the important
states and different phases of the substance. Line ab as in the previous figure is called
saturated solid, which is a series of saturation points at different points. A point to the left
of this line is at a higher pressure than the saturated pressure at the same temperature.
Line bc is called solid-liquid line or fusion line. This is when solid is slowly forming into
liquid.
For example, ice when exposed to the sun melts while at constant temperature of
0 oC. The heat involved after the complete changed from solid to liquid is called heat of
fusion. All the points to the right of line ab and to the left of line gh are called mixture of
solid and vapor. This happens during the process of sublimation where solid is directly
changed into vapor without passing the liquid phase. This happens at a relatively low
pressure such as for carbon dioxide (dry ice).

Line ce is called saturated liquid, which is a series of saturation points at different

temperatures. To the left of this line and to the right of the solid-liquid line is called
subcooled line. Line df is called vapor line. This is when liquid turn into vapor at
unchanging temperature. For example, liquid water when heated at constant pressure will
vaporize at 100 oC. The heat involved during the process is called heat of vaporization.
The area enclosed by line def is called liquid-vapor region. Point e is the critical point
mentioned previously. Line eh is called saturated vapor line, which is series of saturation
points at different temperatures. To the right of this line is called superheated vapor
region where the temperature of vapor is higher than its saturation temperature at the
same pressure.

Ice at a temperature lower than 0 oC when heated will increase its temperature to
its melting temperature, 0 oC. Further addition of heat will result to melting of ice while the
temperature remains constant. Water at 0 oC when heated will increase its temperature
to 100 oC and it’s only at this point when liquid will change into vapor until it becomes
saturated vapor.
 e

f
d

g
a b c

Figure 3. pv diagram for water LearnThermo.com

Figure 4 shows a more detailed picture of processes and changed of states of

water in the three dimensions using pressure (p), temperature (t), and specific volume
(v).

Figure 4. pѵT diagram for water

2.4. Quality of Mixture

Quality, denoted by the symbol, x, is define as the fraction by mass of vapor in a

mixture of liquid and vapor. The term quality is not used for subcooled liquid and
superheated vapor. The limiting values of quality are 1.0 for saturated liquid and 0 for
saturated liquid (meaning pure liquid) or 100 percent for saturated vapor and 0 percent
for saturated liquid. Saturated vapor is often called “dry saturated vapor or dry steam” and
a mixture of vapor and liquid as “wet vapor”.

Looking at figure 5, which is detailed picture of the t - ѵ diagram for liquid and vapor
alone shows ѵf and ѵg. These two symbols are for the specific volumes of saturated liquid
and saturated vapor, respectively. Point c is a mixture of liquid and vapor whose specific
volume is known as ѵfg which is the difference between the specific volumes of saturated
vapor and saturated liquid (ѵfg = ѵg – ѵf).

Figure 5. pѵ diagram for water showing the transformation

The specific volume of mixture, ѵx is seen from figure 4. Depend on the amount of
vapor present in the mixture of liquid and vapor. An equation can be derived using the
definition of quality showing that ѵx is function of saturated vapor and saturated liquid, vfg.

Let mf be the mass of liquid and mg be the mass of vapor. Vf and Vg stands for the
total volumes of the liquid and vapor present in the mixture, respectively.

Using the definition of quality

𝑉 V𝑓 + V𝑔
ѵ𝑥 = =
𝑚 𝑚𝑓 + 𝑚𝑔

Knowing that,
 𝑉
ѵ=
𝑚

it follows that

𝑉 = ѵm

So, the quality can be written as

𝑚𝑓 ѵ𝑓 + 𝑚𝑔 ѵ𝑔
ѵ𝑥 =
𝑚𝑓 + 𝑚𝑔

separating the two terms, we have

𝑚𝑓 𝑚𝑔
ѵ𝑥 = ѵ𝑓 + ѵ
𝑚𝑓 + 𝑚𝑔 𝑚𝑓 + 𝑚𝑔 𝑔
𝑚𝑔
And from the definition of quality (𝑥 = 𝑚 ) , the equation can be written as
𝑓 +𝑚𝑔

𝑚𝑓 +𝑚𝑔 𝑚𝑓 𝑚𝑔
ѵx = (1 – x)ѵf + ѵgx, since = 1, then it follows that, + =1
𝑚𝑓 +𝑚𝑔 𝑚𝑓 +𝑚𝑔 𝑚𝑓 +𝑚𝑔
= ѵf – xѵf + xѵg
= ѵf + x(ѵg – ѵf)
ѵx = ѵf + xѵfg

This shows that when x = 50%, the point represents the state of the mixture
midway between f and g.

Summary:

If: ѵg > ѵact > ѵf - mixture of liquid and vapor

ѵg < ѵact - superheated
ѵf > ѵact - compressed or subcooled
*These holds true to enthalpy and internal energy

Tact < Tsat @ the same temperature – the substance is a subcooled substance
pact > psat @ the same temperature - the substance is a compressed substance
Tact > Tsat @ the same pressure – the substance is a superheated substance
pact < psat @ the same temperature – the substance is a superheated substance
Illustrative Problems

1. Determine whether water at each of the following states is compressed liquid

(subcooled liquid), a superheated vapor, saturated liquid, saturated vapor or a
mixture of liquid and vapor.
a. T = 100 oC, p = 101.325 kPa
b. T = 200 oC, p = 1000 kPa

Solution:

a. look at the saturation pressure at a temperature of 100 oC from table A.5

(Saturated Steam Temperature Table). For 100 oC, the saturation pressure
is 101.33 kPa. Since this is also the actual pressure of water, then the water
is saturated liquid.

b. look at the saturation pressure at a temperature of 200 oC from table A.5

(Saturated Steam Temperature Table). For 200 oC, the saturation pressure
is 1,554.7 kPa. Since the actual pressure is greater than the saturation
pressure [Pact (1,554.7 kPa) > Psat1,000 kPa)], then the water is in the form
of superheated vapor.

Or look at the saturation temperature at a pressure of 1,000 kPa from table

A.6 (Saturated Steam Pressure Table). For 1,000 kPa, the saturation
temperature is 179.88 oC. Since the saturation temperature is less than the
actual temperature [Tsat (179.88 oC) < Tact (200 oC)], then the water is in the
form of superheated vapor.

2. Calculate the following specific volumes:

a) water at T = 100 oC, x = 50%

b) Ammonia at T = 0 oC, x = 20%
c) Freon-12 at T = 5 oC, x = 80%

Solution:

All these three items will make use of the equation below:

ѵx = ѵf + xѵfg

a. From table A.5 (Saturated Steam Temperature Table); ѵf = 0.0010436

m3/kg and ѵg = 1.6722 m3/kg, substituting these values to the equation
above gives;

ѵx = 0.0010436 m3/kg + 0.5(1.6722 m3/kg – 0.0010436 m3/kg) = 0.837 m3/kg

 b. From table A.9 (saturated Ammonia Table), ѵf = 0.001566 m3/kg and ѵfg =
0.2879 m3/kg substituting these values to the equation above gives;

ѵx = 0.001566 m3/kg + 0.2(0.2879 m3/kg) = 0.059146 m3/kg

c. From table A.11 (Saturated Refrigerant-12 Table), ѵf = 0.000724 m3/kg and

ѵfg = 0.046761 m3/kg substituting these values to the equation above gives;

ѵx = 0.000724 m3/kg + 0.8(0.046761 m3/kg) = 0.0381 m3/kg

3. Determine the quality if saturated or temperature if superheated vapor or subcooled

liquid.

a. water, T = 200 OC, ѵ = 0.1 m3/kg

b. Ammonia, p = 100 kPa, ѵ = 1.416 m3/kg

Solution:

a. From table A.5 (Saturated Steam Temperature Table) at 200 oC, ѵf = 0.0011562
m3/kg and ѵg = 0.12729 m3/kg. Since the actual specific volume of water is lower
than ѵg and higher than ѵf, that is, ѵf (0.0011562 m3/kg) < ѵact (0.1 m3/kg) < ѵg
(0.12729 m3/kg), then the water is a mixture of liquid and vapor.

So,

ѵ𝑥 = ѵ𝑓 + 𝑥ѵ𝑓𝑔

ѵ𝑥 − ѵ𝑓
𝑥=
ѵ𝑓𝑔

ѵ𝑥 − ѵ𝑓
𝑥=
ѵ𝑔 − ѵ𝑓

Substituting values, we have,

3 3
0.1 𝑚 ⁄𝑘𝑔 − 0.0011562 𝑚 ⁄𝑘𝑔
𝑥= 3 3
0.12729 𝑚 ⁄𝑘𝑔 − 0.0011562 𝑚 ⁄𝑘𝑔

= 0.78 or 78%

b. From table A.10 (Superheated Ammonia Table) at p = 100 kPa, Tsat = -33.61 oC
and from table A.9 (Saturated Ammonia Table) at T = -34 oC (which is
approximately equal to Tsat or if you wish to get the exact value use T = -33.61 o C)
ѵg = 1.1579 m3/kg which is lower than the actual specific volume of ammonia and
 so it must be in the form of superheated vapor. From table A.10 again at psat = 100
kPa and ѵg = 1.416 m3/kg the actual temperature is 20 oC.

4. A storage container of 0.4 m3 capacity contains 2 kg ammonia at 2 oC. a) find the

percentages of liquid and vapor in container on a mass basis. b) determine the
percentages of liquid and vapor on a volume basis also.

Solution:

The actual specific volume can be computed given the total volume and total mass of
ammonia. That is,

𝑉 0.4 𝑚3 3
ѵ𝑎𝑐𝑡 = = = 0.2 𝑚 ⁄𝑘𝑔
𝑚 2 𝑘𝑔
a) From table A. 9 (Saturated Ammonia Table) at 2 oC, ѵf = 0.001573 m3/kg and ѵg =
0.2698 m3/kg. since the actual specific volume of ammonia is lower that ѵg and
higher than ѵf the ammonia is a mixture of liquid and vapor. That is,

ѵf (0.001573 m3/kg) < ѵact (0.2 m3/kg) < ѵg (0.2698 m3/kg)

solving for percentages of liquid and vapor,

ѵ𝑥 = ѵ𝑓 + 𝑥ѵ𝑓𝑔

ѵ𝑥 − ѵ𝑓
𝑥=
ѵ𝑓𝑔

ѵ𝑥 − ѵ𝑓
𝑥=
ѵ𝑔 − ѵ𝑓

0.2 − 0.001573
𝑥=
0.2698 − 0.001573

= 0.7398 𝑜𝑟 73.97%

Therefore,

The percentage vapor by mass is 73.97%

The percentage liquid by mass is 26.03%

b) the percentage vapor by volume is

𝑚𝑔 ѵ𝑔
𝑉𝑔 /𝑉𝑇𝑜𝑡𝑎𝑙 =
𝑉𝑇𝑜𝑡𝑎𝑙
 3
(0.7396)(2 𝑘𝑔)(0.2698 𝑚 ⁄𝑘𝑔 )
= = 0.9977 0𝑟 99.77%
0.4 𝑚3

The percentage liquid by volume is 0.0023 or 0.23%

STUDENTS’ ACTIVITY

LEARNING EXERCISE 2

1. Determine for R 12 the following:

(a) h if T=85°C and p = 1000 kPa.
(b) x if h = 100 kJ/kg and T= 0 oC.
(c) u if T = 100 °C and p = 800 kPa.
(d) p if T = 20°C and ѵ = 0.001 020 m3/kg.

2. Complete the following table for ammonia.

T (oC) p (kPa) x (%) h (kJ/kg) u (kJ/kg) ѵ (m3/kg state

a 10 1225.5
b 50 700
c 752.79 80
d 12 1000
e 0 90
f 1554.3 80

Indicate for each state whether it is subcooled liquid, saturated liquid, mixture,
saturated vapor, or superheated vapor.

3. Determine the volume occupied by 2 kg of steam at 1000 kPa and 500°C.

4. Steam has a quality of90% at 200°C. Determine (a) the enthalpy; (b) the specific
volume.

SUGGESTED READINGS

David Burghardt, Engineering Thermodynamics with Applications, 2nd ed.

Robert T. Balmer, Modern Engineering Thermodynamics
Merle C. Potter and Craig W. Somerton, Theory and Problems of Thermodynamics for
Engineers (Schaum’s Outline Series)
REFERENCES

M. David Burghardt & James A. Harbach, Engineering Thermodynamics, 4th ed.

Jessie C. Elauria, Lecture Note in AEng 201