CHAPTER 4

PURE SUBSTANCE

1. PURE SUBSTANCE
A pure substance is a system which is
 “Homogeneous in composition” means that the composition of each part of the
system is the same as the composition of every other part. “Composition
means the relative proportions of the chemical elements into which the sample
can be analysed. It does not matter how these elements are combined.
 “Homogeneous in chemical aggregation” means that the chemical elements
must be combined chemically in the same way in all parts of the system.
 “Invariable in chemical aggregation” means that the state of chemical
combination of the system does not change with time. Thus a mixture of
hydrogen and oxygen, which changed into steam during the time that the
system was under consideration, would not be a pure substance.

2. PRESSURE-TEMPERATURE (P-T) DIAGRAM for a PURE SUBSTANCE

Pressure-Temperature (P-T) diagram is a diagram that shows the phases (solid, liquid
or gas) of a substance. The diagram is divided into three areas, which represent the
solid, liquid, and gaseous states of the substance.
An example of a phase diagram, which summarizes the effect of temperature and
pressure on water as shown in Fig. 4.1. Every point in this diagram represents a
possible combination of temperature and pressure for the system.
 Sublimation curve is the curve that separates the solid and vapor phases.
 Fusion curve is the curve that separates the solid and liquid phases.
 Vaporization curve is that separates liquid and solid phases.
 Triple point is the point of intersection of sublimation and vaporization curves. On
a P-T diagram, the triple point represented by a point.

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 Fig. 4.1 Pressure-Temperature Diagram for Water

3. P-V-T (PRESSURE-VOLUME-TEMPERATURE) SURFACE

A detailed study of the heating process reveals that the temperature of the solid rises
and then during the change of phase from solid to liquid (or solid to vapor) the
temperature remains constant. This phenomenon is common to all phase changes.
Since the temperature is constant, pressure and temperature are not independent
properties and cannot be used to specify state during a change of phase. The
combined picture of change of pressure, specific volume and temperature may be
shown on a three dimensional state model. Fig. 4.2 illustrates the equilibrium states
for a pure substance which expands on fusion. Water is an example of a substance
that exhibits this phenomenon.

Fig. 4.2 Pressure-Volume-Temperature (P-V-T) Surface

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4. PHASE CHANGE TERMINOLOGY and DEFINITIONS
 Critical point is the point where the vaporization line ends. At temperatures and
pressures greater than those at the critical point, no substance can exit as a liquid
no matter how great pressure is exerted upon it.
 Critical pressure. The pressure at the critical point.
 Critical temperature. The temperature at the critical point.
 Gas. A vapor whose temperature is greater than the critical temperature.
 Saturation temperature. The phase change temperature corresponding to the
saturation pressure. Sometimes called the boiling temperature.
 Saturation pressure. The phase change pressure.
 Compressed/ sub-cooled liquid. Liquid whose temperature is lower than the
saturation temperature.
 Saturated liquid. Liquid at the saturation temperature corresponding to the
saturation pressure.
 Saturated vapor. A term including wet and dry vapor.
 Dry (saturated) vapor. Vapor which has just completed evaporation. The pressure
and temperature of the vapor are the saturation values.
 Wet vapor. The mixture of saturated liquid and dry vapor.
 Superheated vapor. Vapor whose temperature is greater than the saturation
temperature corresponding to the pressure of the vapour.
 Degree of superheat. The term used for the numerical amount by which the
temperature of a superheated vapor exceeds the saturation temperature.
 Vaporization. The change in phase liquid to vapor.
 Evaporation. The process of generating vapour at the free surface of the liquid.
 Condensation. The change in phase gas to liquid.
 Sublimation. The change in phase solid to gas.
 Deposition. The change in phase liquid to vapor.

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 Fig. 4.3 Pressure-Volume (P-V) Diagram

5. PROPERTY DIAGRAMS in COMMON USE

Besides P-V diagram which is useful because pressure and volume are easily
visualized and the T-s chart which is used in general thermodynamic work, there are
other charts which are of practical use for particular applications. The specific
enthalpy-specific entropy chart is used for steam plant work and the pressure-
specific enthalpy chart is used in refrigeration work. Sketches of these charts are
shown. These charts are drawn for H2O (water and steam) and represent the correct
shape of the curves for this substance.

Fig. 4.4 Property Diagrams in Common Use

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 Fig. 4.5 Graphical Representation of Formation of Steam

6. IMPORTANT TERMS RELATING STEAM FORMATION

Sensible heat of water (hf). The quantity of heat absorbed by 1 kg of water when it is
heated from 0°C (freezing point) to boiling point. It is also called total heat (or
enthalpy) of water or liquid heat invariably. It is reckoned from 0°C where sensible
heat is taken as zero. If 1 kg of water is heated from 0°C to 100°C the sensible heat
added to it will be 4.187 × 100 = 418.7 kJ but if water is at say 20°C initially then
sensible heat added will be 4.187 × (100 – 20) = 335 kJ. This type of heat is denoted
by letter hf and its value can be directly read from the steam tables.
Note: The value of specific heat of water may be taken as 4.187 kJ/kg K at low
pressures but at high pressures it is different from this value.
Latent heat or hidden heat (hfg). The amount of heat required to convert water at a
given temperature and pressure into steam at the same temperature and pressure. It
is expressed by the symbol hfg and its value is available from steam tables. The value
of latent heat is not constant and varies according to pressure variation.

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Dryness fraction (x). The term dryness fraction is related with wet steam. It is defined
as the ratio of the mass of actual dry steam to the mass of steam containing it. It is
usually expressed by the symbol ‘x’.
If ms = Mass of dry steam contained in steam considered, and
mw = Weight of water particles in suspension in the steam considered,
𝐦s
Then, x=
𝐦s + 𝐦w
Thus if in 1 kg of wet steam 0.9 kg is the dry steam and 0.1 kg water particles then x =
0.9. Note. No steam can be completely dry and saturated, so long as it is in contact
with the water from which it is being formed.
Total heat or enthalpy of wet steam (h). It is defined as the quantity of heat required
to convert 1 kg of water at 0°C into wet steam at constant pressure. It is the sum of
total heat of water and the latent heat and this sum is also called enthalpy. In other

words, h = hf + xhfg
If steam is dry and saturated, then x = 1 and

hg = hf + hfg
Superheated steam. When steam is heated after it has become dry and saturated, it
is called superheated steam and the process of heating is called superheating.
Superheating is always carried out at constant pressure. The additional amount of
heat supplied to the steam during superheating is called as ‘Heat of superheat’ and
can be calculated by using the specific heat of superheated steam at constant
pressure (Cp), the value of which varies from 2.0 to 2.1 kJ/ kg-K depending upon
pressure and temperature.
If Tsup, Ts are the temperatures of superheated steam in K and wet or dry steam, then
(Tsup – Ts) is called ‘degree of superheat’. The total heat of superheated steam is given

by hsup = hf + hfg + Cp (Tsup – Ts)

Superheated steam behaves like a gas and therefore it follows the gas law PVn = C.

The value of n for this type of steam is 1.3.

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 Volume of wet and dry steam. If the steam has dryness fraction of x, then 1 kg of this
steam will contain x kg of dry steam and (1 – x) kg of water. If Vf is the volume of 1 kg
of water and vg is the volume of 1 kg of perfect dry steam (also known as specific
volume), then volume of 1 kg of wet steam = volume of dry steam + volume of water.

= xVg + (1 – x)Vf
Volume of superheated steam. As superheated steam behaves like a perfect gas its
volume can be found out in the same way as the gases.
𝐏 𝐕g 𝐏 𝐕sup
=
𝐓s 𝐓sup

𝐕g 𝐓sup
Vsup =
𝐓s
where:
Vg = Specific volume of dry steam at pressure P
Ts = Saturation temperature in K
Tsup = Temperature of superheated steam in K
Vsup = Volume of 1 kg of superheated steam at pressure P,

7. THERMODYNAMIC PROPERTIES of STEAM and STEAM TABLES

For any fluid which is used as working fluid, the six basic thermodynamic properties
required are: P (pressure), T (temperature), v (volume), u (internal energy), h
(enthalpy) and s (entropy). These properties must be known at different pressure for
analyzing the thermodynamic cycles used for work producing devices. The values of
these properties are determined theoretically or experimentally and are tabulated in
the form of tables which are known as ‘Steam Tables’. The properties of wet steam
are then computed from such tabulated data. Tabulated values are also available for
superheated steam. Steam has only one saturation temperature at each pressure.

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Thermodynamic Properties of Steam which are Tabulated in the form of Table

External Work Done During Evaporation

When water is evaporated to form saturated steam, its volume increases from Vf to
Vg at a constant pressure, and thus external work is done by steam due to increase in
volume. The energy for doing the work is obtained during the absorption of latent
heat. This work is called external work of evaporation and is given by P(Vg – Vf).
Internal Latent Heat
The latent heat consists of true latent heat and the work of evaporation. This true
latent heat is called the internal latent heat and may also be found as follows:

Internal latent heat = hfg – PV

Internal Energy of Steam
It is defined as the actual energy stored in the steam. As per previous articles, the
total heat of steam is sum of sensible heat, internal latent heat and the external work
of evaporation. Work of evaporation is not stored in the steam as it is utilized in
doing external work. Hence the internal energy of steam could be found by
subtracting work of evaporation from the total heat.

h = PV + u
where:
u = internal energy of 1 kg of steam at pressure

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Entropy of Water
Consider 1 kg of water being heated from temperature T1 to T2 at constant pressure.
The change in entropy will be given by

Integrating both sides, we get

If 0°C is taken as datum, then entropy of water per kg at any temperature T above
this datum will be

Entropy of Evaporation
The change of entropy (ds) is given by,

When water is evaporated to steam completely the heat absorbed is the latent heat
and this heat goes into water without showing any rise of temperature. Then

However, in case of wet steam with dryness fraction x the evaporation will be partial
and heat absorbed will be xhfg per kg of steam. The change of entropy will be

Entropy of Wet Steam

The total entropy of wet steam is the sum of entropy of water (s f) and entropy of
evaporation(sfg).

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 In other words,

8. ENTHALPY-ENTROPY (h-s) CHART OR MOLLIER DIAGRAM

Dr. Mollier, in 1904, conceived the idea of plotting total heat against entropy, and his
diagram is more widely used than any other entropy diagram, since the work done on
vapor cycles can be scaled from this diagram directly as a length; whereas on T-s
diagram it is represented by an area. An Enthalpy-Entropy diagram, also known as h-s
chart or Mollier diagram.

Fig. 4.6 Sketch of the h-s Chart

– Lines of constant pressure are indicated by P1, P2 etc., lines of constant
temperature by T1, T2, etc.
– Any two independent properties which appear on the chart are sufficient to define
the state
(eg., P1 and x1 define state 1 and h1 can be read off the vertical axis).

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– In the superheat region, pressure and temperature can define the state
(e.g. P3 and T4 define the state 2, and h2 can be read off).
– A line of constant entropy between two state points 2 and 3 defines the
properties at all points during an isentropic process between the two states.

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9. SOLVED PROBLEMS
1. Past ME Board Problem
Steam enters a throttling calorimeter at a pressure of 1.03 MPa. The calorimeter
downstream pressure and temperature are respectively 0.100 MPa and 125°C.
What is the percentage moisture of the supply steam?
Properties of steam:
@ 1.03 MPa
hg = 2779.25 kJ/kg hfg = 2010.7 kJ/kg
@ 0.100 MPa & 125°C
h = 2726.6 kJ/kg
A. 2.62 C. 3.15
B. 5.21 D. 1.98
SOLUTION:
Let y = percentage moisture
y = 100 – x
Solve for quality of steam, x:
For throttling process:
h1 = h2
hf1 + x1 hfg1 = h2
[(2779.25 kJ/kg – 2010.7 kJ/kg) + x(2010.7 kJ/kg)] = 2726.6 kJ/kg
x = 0.97382
∴ y = 1 – 0.97382 = 0.02618
y = 2.62 % (ANS. A)

2. Past ME Board Problem

Calculate the entropy of steam at 60 psia with a quality of 0.60.
Properties of steam:
@ 60 psia
Sf = 0.4274 Btu/lb-°R Sfg = 1.2172 Btu/lb-°R

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 A. 0.4274 Btu/lb-°R C. 0.7303 Btu/lb-°R
B. 1.1577 Btu/lb-°R D. 0.896 Btu/lb-°R
SOLUTION:
S = Sf + xSfg
= 0.4247 Btu/lb-°R + (0.60)(1.2172 Btu/lb-°R)
S = 1.1577 Btu/lb-°R (ANS. B)
3. Past ME Board Problem
Steam at 2 MPa and 250°C in a rigid cylinder is cooled until the quality is 30%. Find
the heat rejected from the cylinder.
Properties of steam
@ 2 Mpa and 250°C:
υ = 0.11144 m3 /kg
u = 2679.6 kJ/kg
@ 2 Mpa, (saturated):
υf = 0.0011767 m3 /kg υg = 0.09963 m3 /kg
uf = 906.44kJ/kg ug = 1693.8 kJ/kg
A. -423.23 kJ/kg C. -1265.02 kJ/kg
B. -926.26 kJ/kg D. 1082.34 kJ/kg
SOLUTION:
Q = u2 – u1
Solve for u2:
u2 = uf2 + ufg2 = 906.44 + (0.30)(1693.8) = 1414.58 kJ/kg
∴ Q = 1414.58 – 2679.6 = –1265.02 kJ/kg (ANS. C)

4. Past ME Board Problem

Find the enthalpy of 1 kg of wet saturated steam at a pressure of 0.20 bar and
dryness fraction of 0.85. At 0.20 bar, hf = 251 kJ/kg, hg = 2358 kJ/kg
A. 2200 kJ/kg C. 2255.30 kJ/kg
B. 2525.30 kJ/kg D. 2000 kJ/kg

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SOLUTION:
h = hf + xhfg
h = 251 kJ/kg + (0.85)(2358 kJ/kg)
h = 2255.30 kJ/kg (ANS. C)

5. Past ME Board Problem

Find the heat transferred required to convert 5 kg of water at a pressure of 20 bar
and temperature of 21°C into steam of dryness fraction 0.90 at the same pressure.
Properties of steam:
@ 20 bar
hf = 909 kJ/kg hfg = 1890 kJ/kg
Note: for water@ 21°C
h = 88 kJ/kg
A. 10 610 kJ C. 12 610 kJ
B. 11 610 kJ D. 15 610 kJ
SOLUTION:
Q = mΔh = m (h2 – h1)
Solve for h2:
h2 = hf2 + x2 hfg2
h2 = 909 kJ/kg + 0.90(1890 kJ/kg) = 2610 kJ/kg
∴ Q = 5 kg( 2610 kJ/kg – 88 kJ/kg)
Q = 12 610 kJ (ANS. C)

6. Supplementary Problem
Determine the heat added during the process where a mixture at a pressure of
500 kPa with 70% quality is heated at constant temperature to a pressure of 300
kPa. Find the heat added during the process.
@ 600 kPa: sf = 1.8607 kJ/kg-K sfg = 4.9606 kJ/kg-K
@ 300 kPa and 151.86°C: s = 7.0888 kJ/kg-K

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 A. 745.92 kJ/kg C. 982.44 kJ/kg
B. 535.16 kJ/kg D. 765.34 kJ/kg
SOLUTION:
Q = TΔs
Solve for s:
s1 = sf1 + xsfg1 = 1.8607 kJ/kg-K + (0.70)( 4.9606 kJ/kg-K) = 5.333 kJ/kg-K
‫ ؞‬Q = (151.86 +273)K(7.0888 kJ/kg-K - 5.333 kJ/kg-K)
Q = 745.92 kJ/kg (ANS)

7. Supplementary Problem
A 1 kg container of water consisting of liquid and vapor in equilibrium at 1000 kPa.
Find the enthalpy of the contents of the container if the container contains one-
third liquid and two-thirds vapor of the volume.
@ 1MPa:
υf = 0.0011273 m3/kg υfg = 0.19444 m3/kg
hf = 762.81 kJ/kg hfg = 2015.3 kJ/kg
A. 644.40 kJ/kg C. 785.92 kJ/kg
B. 774.40 kJ/kg D. 435.29 kJ/kg
SOLUTION:
Let V = volume of the tank
Solve for mass of liquid, mliq:
mliq = Vliq/υliq = V/(3)(0.0011273) = 295.69 V
Solve for mass of vapor,mv:
mv = Vv/υv = 2V/(3)(0.1944) = 3.429 V
Solve for quality of water, x:
x = mv/(mliq + mv) = 3.429 V/(295.69 V + 3.429 V) = 0.01146
Solve for enthalpy
h = hf + xhfg = 762.81 kJ/kg + (0.01146)(2015.3 kJ/kg)
h = 785.92 kJ/kg (ANS)

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