Engineering Thermodynamics 65

CHAPTER 3 Properties of a Pure Substance and steam

power cycle

A pure substance is one that has homogeneous and invariable chemical composition. It may
exist in more than one phase, but chemical composition is same for all the phases. Thus, water,
mixture of water and ice and water and steam are all examples of pure substance. Sometimes a
mixture of gases e.g. air is considered as pure substance.

We have seen that two independent properties are sufficient to determine

thermodynamic state of a fluid when it is in equilibrium. Any other thermodynamic
property is a function of the chosen pair of independent properties. We shall first
consider the relation between the primary properties p, v and T, the equation expressing
this relation for any particular fluid being called the equation of state or characteristic
equation of the fluid.

p-v-T DATA OF WATER

 Engineering Thermodynamics 66

Since we have three variables to consider, the obvious procedure is to measure the
variation of one with another while the third is kept constant and repeat this for a range
of values of the third variable.

Imagine unit mass of ice below the

T(K) F freezing point, enclosed in a

cylinder by a piston under a
D constant load of 1 atmosphere (1
373.15 E atm. = 1.01325 bar = 101.325
Vapourisation
kPa). If heat is added to the
277.15 cylinder while keeping the pressure
Fusion
constant, the temperature rises
273.15 B
C and ice expands until a
A
temperature of 273.15 K (00C) is
reached (AB) as shown in Fig.
v
Further heating does not raise the
temperature of ice but causes a change to the liquid phase (BC). The change of phase
occurs at a constant temperature and by reduction of specific volume. The heat required
for this process is known as latent heat of fusion. Further heating results in a rise of
temperature of liquid and a further contraction in volume until the temperature is about
40C and subsequent expansion until a temperature of 373.15 K (1000C) is reached
(point D). At this point a second phase change occurs at constant temperature with a
large increase in volume until the liquid has been vaporised (point E). The heat required
in this case is called the latent heat of vaporisation. When vaporisation is complete,
the temperature rises again on heating (line EF). The heat transferred to a substance
while the temperature changes is sometimes referred to as sensible heat. This
constant pressure lines are called isobars.

If the pressure is reduced, there is a slight rise in the melting point and also there is a
marked drop in the boiling point of water and a marked increase in the change in
volume, which accompanies evaporation. When the pressure is reduced to 0.006113
 Engineering Thermodynamics 67

bar (0.6113 kPa), the melting point and boiling point temperatures become equal and
change of phase, ice-water-steam, are represented by a single line. The temperature at
which this occurs has been accepted internationally as a fixed point for the absolute
temperature scale and is by definition 273.16 K. Only at this temperature and pressure
of 0.6112 kPa, can ice, water and steam coexists in thermodynamic equilibrium in a
closed vessel and is known as triple point. If the pressure is reduced further, the ice,
instead of melting, sublimes directly into steam.

Consider now the behaviour at pressure above atmospheric. The shape of the curve is
similar to that of the atmospheric isobar, but there is a marked reduction in the change
in volume accompanying evaporation. At a sufficiently high pressure, this change in
volume falls to zero and the horizontal portion of the curve reduces to a point of
inflexion. This is referred to critical point. The values pressure and temperature of water
at which critical point reached are

pc = 221.2 bar = 22.12 MPa ; Tc = 647.3 K ; vc = 0.00317 m3/kg.

Engineering Thermodynamics 68
 Engineering Thermodynamics 69

The pressure at which liquid vaporises or condenses is called saturation pressure

corresponding to a given temperature. Alternately, the temperature at which this
phenomena occur is called saturation temperature corresponding to the given
pressure.

A vapour in a state lying along the saturated vapour line is also called dry saturated
vapour and the vapour lying right of this line is called superheated vapour.

IMPORTANT POINTS TO BE REMEMBERED

• Saturation temperature: Temperature at which a pure substance changes phase at a

given pressure.
• Saturation pressure: Pressure at which a pure substance changes phase at a given
temperature.
• Latent heat: The amount of energy absorbed or released during a phase-change.
 Engineering Thermodynamics 70

¾ Melting/freezing: Latent heat of fusion.

¾ Evaporation/condensation: Latent heat of vaporization.
• Temperature at which water starts boiling depends on the pressure => if the pressure
is fixed, so is the boiling temperature.

TABLE OF PROPERTIES OF WATER

(i) Saturated Table

P ts vf vg uf ug hf hg sf sg

Now how many properties do we need to know to determine the thermodynamic state?

For a single phase we need to know only two independent properties like (P, T), (T, v), etc.

For a two-phase mixture, p and T are not independent. Hence, we require defining “quality”.

mv
Quality or Dryness fraction: x=
mv + ml

Value of x varies from 0 to 1. For

saturated water, when water just
starts boiling, x = 0 and for
saturated vapour, when
vaporisation is complete, x = 1
and the vapour is called dry
saturated.

Let V be the total volume of a

liquid vapour mixture of quality x.
Vf the volume of saturated liquid
and Vg the volume of saturated vapour, the corresponding masses are m, mf, and mg
respectively.
 Engineering Thermodynamics 71

Now m = mf + mg

and V = Vf + Vg

or m v = mf vf + mg vg = (m – mg) vf + mg vg

or v=
(m − mg )
vf +
mg
vg
m m

or v = (1 – x) vf + x vg

Again, enthalpy H = Hf + Hg

or m h = mf hf + mg hg = (m – mg) hf + mg hg

or h =
(m − m ) h
g
+
mg
hg
f
m m

or h = (1 – x) hf + x hg

Similarly,

s = (1 – x) sf + x sg

where, h is the specific enthalpy an s the specific entropy. We shall discuss about these
properties in the later chapters.

Now

v = (1 – x) vf + x vg = vf + x (vg – vf) = vf + x vfg.

Similarly,

u = uf + x ufg

h = hf + x hfg

s = sf + x sfg

where, vfg = vg – vf ; ufg = ug – uf ; hfg = hg – hf etc.

ii) Superheated steam Table

 Engineering Thermodynamics 72

p
t 200 300 400 …………..
(ts)

v
15 u
(198.3) h
s

v
20 u
( )
h
s

IDEAL GAS (PERFECT GAS)

From experimental observations it has been established that the following relation can
express the p –v – T behaviour of gases at the low pressure

pv =R T

where, R is the universal gas constant, 8.3143 J/mol K and v is the molar specific
volume, m3/gmol. Dividing the equation (5.14) by the molecular weight M, we get

p v = RT

where v is the specific volume, m3/kg, and R is the characteristic gas constant. It follows
from the above equations that this equation of state can be written in terms of total
volume, V, of the gas as

pV = n R T

pV=mRT

where, n is the number of moles and m is the mass of the gas. The above equation can
be written for the two states of the gas as
 Engineering Thermodynamics 73

p1 v1 p2 v 2
=
T1 T2

The above equations s called the ideal gas equation of state. At very low pressure or
density, all gases and vapour approach ideal gas behaviour.

Summary

Ideal Gas: When is it a good approximation?

- Low density ⇒ low pressure, high temperature

Vapour Power Cycles and Processes.

About 80% of the electrical power is generated by steam power plants in which working
fluid (normally water) undergoes a cyclic change in phase from liquid state to vapour
state and back to the original liquid state. This change in phase is brought about by
transfer of heat to and from the working fluid. The analysis of such plants is based on
idealized cycle that may be closely approximated to the working of the actual plant.

THERMAL EFFICIENCY
The thermal efficiency of a cycle is defined as the ratio of the energy output to the
energy input according to the relation
Wn
ηth =
QH
where Wn is the net work output of the cycle and QH is the heat supplied to the working
fluid from the high temperature source.
In many situations, however, we like to evaluate the thermal efficiency of a certain
process, e.g. the efficiency of compression process in a compressor or the efficiency of
an expansion process in a turbine.
 Engineering Thermodynamics 74

The compressor efficiency applied to a pump or compressor is defined as the ratio of

theoretical isothermal work WT (in case of reciprocating compressor) or isentropic work
Ws (in case of rotary compressor or pump) to the actual work, Wac
WT
ηc = (for reciprocating compressor)
Wac

Ws
or ηc = (for rotary compressor or pump).
Wac
The expansion efficiency applied to a turbine is defined as the ratio of the actual work
Wac to the isentropic work Ws
Wac
ηT =
Ws

Compressor or Pump Turbine

IDEALISED STEAM POWER CYCLE (CARNOT VAPOUR CYCLE)

The efficiency of the Carnot Cycle is maximum and it does not depend on the working
fluid. It is, therefore, natural to examine if a steam power plant can be operated on
Carnot cycle.
 Engineering Thermodynamics 75

1-2 → Isentropic compression in pump.

2-3 → Constant Pressure heat addition in
boiler.
3-4 → Isentropic expansion in turbine.
4-1 → Constant pressure heat removal in
condenser.

The efficiency is given by

Wnet QH − QL Q T
ηcycle = = = 1− L = 1− L
QH QH QH TH
where QH = heat transferred to
working fluid
QL = heat transferred from working fluid
Practical Problems
The constant pressure heat addition process 2-3 can be achieved in boiler. However,
for process
I. 3-4 Turbine has to handle high moisture content. Liquid droplets can damage or
erode turbine blades.
II. 4-1 condensing process in condenser must be terminated at state 1, where the
working fluid is a mixture of liquid water and vapour. It is impossible to attain
such condensation.
III. 1-2 Pump that handles two-phase fluid is not practical.
Due to these inherent practical difficulties, Carnot Cycle remains an ideal one.
 Engineering Thermodynamics 76

RANKINE CYCLE
The simplest way of overcoming the inherent practical difficulties of Carnot Cycle
without deviating too far from it is to keep processes 2-3 and 3-4 of Carnot Cycle
unchanged and to continue the process 4-1 in the condenser until all vapour is
converted to liquid water. Water is then pumped into Boiler till its pressure is raised to

P2

P1

the pressure corresponding to state 2 and the cycle is completed. Such a cycle is
known as Rankine Cycle.

Processes:
1-2 → Isentropic (reversible adiabatic) compression in pump.
2-3 → Constant Pressure heat addition in boiler.
3-4 → Isentropic expansion in turbine.
4-1 → Constant pressure heat removal in condenser.

2’ 3

2
1 4

6 5 s
 Engineering Thermodynamics 77

If changes in kinetic and potential energies are neglected, the area under the curve 2-3
i.e. area 2-2’-3-5-6-2 represents the heat transfer to the working fluid in Boiler, which is
equal to (h3 – h2) and area under the curve 1-2 i.e. area 1-4-5-6-1 represents the heat
transferred from the working fluid in condenser, which is equal to (h4 – h1). The
difference between the two areas, namely area 1-2-2’-3-4-1, represents the work
obtained from the cycle. The thermal efficiency of the cycle is given by
Wnet area 1 − 2 − 2'−3 − 4 − 1
ηth = =
QH area 2 − 2'−3 − 5 − 6 − 2

=
(h3 − h2 ) − (h4 − h1 )
(h3 − h2 )
(h − h4 ) − (h2 − h1 ) = WT − WP
= 3
(h3 − h2 ) QH
where WT and WP are the turbine work and pump work respectively per kg of steam flow
through the cycle and h1, h2, h3, h4 are the specific enthalpies of the working fluid.
We know that the efficiency of the Carnot cycle depends only on the temperature levels
of high and low temperature reservoirs. Efficiency o the Rankine cycle similarly depends
on the average temperature at which the heat is transferred to and from the working
fluid. Any change that increases the average temperature at which heat is transferred to
the working fluid will increase the efficiency of the Rankine cycle. Similarly, any change
that decreases the average temperature at which heat is transferred from the working
fluid will increase the efficiency of the Rankine cycle.
An advantage of the Rankine cycle over all other power cycles is its low back work ratio,
which is expressed as the ratio of the pump work to the turbine work, i.e.
WP
Back work ratio =
WT

METHODS OF IMPROVING THE EFFICIENCY OF RANKINE CYCLE

The Rankine cycle efficiency is given by

ηth =
(h3 − h4 ) − (h2 − h1 ) = WT − WP
(h3 − h2 ) QH
 Engineering Thermodynamics 78

Since the pumping work is very small compared to the turbine work, it may be
neglected. Hence, the efficiency of the Rankine cycle can be approximated as

ηth =
(h3 − h4 ) = (Δh)s
(h3 − h2 ) (h3 − h2 )
It can be seen that the Rankine efficiency depends on three values, h2, h3 and turbine
expansion work (Δh)s. The enthalpy of the steam entering the turbine h3 is determined
by the pressure and temperature of the steam entering the turbine. The enthalpy of feed
water h2 is determined by the condenser pressure (as in this case h2 = h1 since the
pump work is negligible). The isentropic heat drop (Δh)s in the turbine is determined by
the pressure and temperature at the entrance of steam turbine and the pressure at the
end of expansion in the turbine. That means the Rankine efficiency depends on
pressures P1 ( i.e. P4 ) , P2 (i.e. P3 ) and temperature T3.

a) Effect of Lowering Condenser pressure

By lowering the condenser pressure we can
achieve higher efficiency as the enthalpy of
the steam leaving the turbine decreases
thereby increasing heat drop (Δh)s in the
turbine. However, there is a limit to which
the condenser pressure can be lowered and
this limit is the saturated pressure Psat
corresponding to the condenser
temperature.
 Engineering Thermodynamics 79

b) Effect of Increasing Steam pressure in the Boiler

P2’’ P2’
h P2

T3
P4
(Δhs)

(Δhs)′
(Δhs)″ x4

x4’
x4”

s
In this analysis the maximum temperature of the steam T3 as well as the exhaust
pressure P4 are held constant.
P2, P2’, P2’’ are the pressures of steam at the entrance of the turbine at temperature T3
such that P2’’ > P2’ > P2 . x4, x4’,x4’’ are the qualities of steam at he exhaust pressure P4
of the turbine, where x4>x4’>4’’ .It is evident that as pressure n the Boiler increases, the
isentropic heat drop Δh)s increases with the result that the Rankine cycle efficiency
increases.
An adverse effect resulting from increasing the steam pressure in the Boiler is the
greater amount of moisture in the steam at the end of expansion in the turbine. If the
moisture content in the turbine exceeds ~10%, the turbine blades also get eroded which
leads to serious wear of the turbine blades.
c) Effect of Superheating
of Steam in the Boiler

The moisture in the steam at the

end of the expansion can be
reduced by superheating and
 Engineering Thermodynamics 80

increasing the superheat temperature of steam, T3’. Hence, it is natural to avoid the
erosion of the turbine blades by an increase of boiler pressure accompanied by
superheating at a higher temperature. By superheating to a higher temperature, the
heat drop in the turbine is increased from (h3 – h4) to (h3’ – h4’), thereby increasing the
efficiency of the Rankine cycle. However, the maximum temperature to which the steam
can be superheated is limited by materials.

d) Effect of Superheating &Reheating of Steam in the Boiler

We have noted earlier that the efficiency of the Rankine cycle can be increased by

P3 P4

h 3 5 Constant temperature

P6
4

increasing the steam pressure in the boiler. But this increases the moisture content of
the steam in the lower stages of the turbine, which may lead to erosion of the turbine
blades. The reheat cycle has been developed to take advantage of the increased
pressure of boiler, avoiding the excessive moisture of the steam in the low pressure
stage.
In the reheat cycle, the high pressure superheated steam after expansion in the high
pressure turbine is reheated at constant pressure, usually to the entrance temperature
of the steam in the high pressure turbine. After this, it expands in the low pressure
 Engineering Thermodynamics 81

turbine to the exhaust pressure. Reheating has a two-fold advantage. Firstly, it reduces
excessive moisture in the low pressure stages of turbine, and secondly, a large amount
of work may be obtained at the cost of additional consumption of heat required for
reheating the steam. The net effect is an improvement in the thermal efficiency of the
cycle. Thus with reheat cycle, the efficiency of the cycle is increased without increase in
the maximum pressure or maximum temperature of the cycle.
The efficiency of the reheat cycle is given by

WT − WP (h3 − h4 ) + (h5 − h6 ) − (h2 − h1 )

ηth = =
QH (h3 − h2 ) + (h5 − h4 )

REAL RANKINE CYCLE: DEVIATION FROM IDEAL CYCLES

a) Turbine and pump losses

1-2s & 3-4s → Isentropic drop.

1-2 & 3-4 → irreversible drop.

b) Pump loses

a-b: friction loss → entropy increases

b-c: heat loss → entropy decreases.
 Engineering Thermodynamics 82

Example

CRITERIA FOR THE COMPARISON OF CYCLES

The choice of power plant for a given purpose is determined largely by considerations of
operating cost and capital cost. The former is primarily a function of overall efficiency
of the plant, while the latter depends mainly on its size and complexity.
The Second Law tells us that even in the best power cycle, some heat must be rejected.
The best form of cycle is one in which (i) all the heat supplied is transferred while the
working fluid is at constant temperature TH, and all the heat rejected from the working
 Engineering Thermodynamics 83

fluid is at constant temperature TL; (ii) all processes are reversible. The efficiency of the
TH − TL
such cycle is , which is known as ideal cycle efficiency or Carnot efficiency.
TH
However, all real processes are irreversible and irreversibility reduces cycle efficiency.
Hence the ratio of actual cycle efficiency to ideal cycle efficiency, i.e. the efficiency ratio
is one measure of comparison. Some cycles are more sensitive to irreversibilities than
others. That is, two cycles may have the same ideal cycle efficiencies, but allowing for
the process efficiencies, their actual cycle efficiencies may be markedly different.
Hence, Work Ratio rw is a criterion, which indicates the cycle sensitiveness to the
irreversibilities. Any cycle consists of both positive (turbine work) and negative (pump
work) work. The work ratio rw is defined as the ratio of net work to the positive work
done in the cycle. That is
WT − w P
rw =
WT
If rw is near unity, then the effect of irreversibility on the cycle efficiency is less.
However, if rw is slightly greater than zero, quite a small amount of component
inefficiencies is sufficient to reduce the network output to zero thereby reducing the
actual cycle efficiency to zero.
Hence, we can say that a high ideal cycle efficiency together with high work ratio
provides a reliable indication that a real power plant will have a good overall efficiency.
The next consideration is some criterion which will indicate the relative size of plant for a
given power output. In general, the size of component depends on the amount of
working fluid, which has to be passed through them. A direct indication of relative sizes
of steam power plant is therefore provided by the Specific Steam Consumption (ssc)
i.e. mass flow of steam required per unit power output. If W is the net work output in
kJ/kg, then ssc can be found from
1 ⎡ kg kg ⎤ ⎡ s ⎤ 3600 ⎡ kg ⎤
ssc = ⎢ or ⎥ x 3600 ⎢ ⎥ =
W ⎣ kJ kWs ⎦ ⎣h ⎦ W ⎢⎣ kWh ⎥⎦