Thermodynamics of Steam

Learning Outcome
When you complete this learning material, you will be able to

Perform calculations related to properties of steam.

Learning Objectives
You will specifically be able to complete the following tasks:

1. Describe the basic properties of water and steam.

2. Perform calculations involving specific enthalpy, dryness fraction, specific heat

and specific volume using steam tables.

3. Explain the principles and use of calorimeters to measure the dryness fraction of
wet steam.

4. Calculate the dryness fraction of steam based on calorimeter data.

5. Calculate the internal energy of steam under given conditions.

6. Explain the concept of entropy and the use of the temperature-entropy diagram.
Calculate the change in entropy for a particular change in enthalpy at a constant
temperature.

7. Determine steam properties using a Mollier Chart.

8. Calculate boiler thermal efficiency using test data provided

Page 35
Page 36
 Objective 1
Describe the basic properties of water and steam.

INTRODUCTION
Steam is an important working fluid for power generation and other industrial processes.
Understanding its behaviour and properties is critical to the successful operation of
steam-related equipment and processes.

The widespread use of steam is due to the availability of water and the relative safety of
steam compared to other fluids. There are some disadvantages to using water and steam
but they are minor compared to using thermodynamically superior fluids, such as
ammonia, that are much more hazardous.

WATER TO STEAM
The transition from water to steam as heat is added is dependent on pressure and
temperature conditions. The three steps to the transition, illustrated in Fig. 1, show the
behaviour of water and steam in terms of temperature and pressure as heat is added (on
the x-axis). Enthalpy is a thermodynamic quantity equal to the internal energy of a
system plus the product of its volume and pressure. Enthalpy is the amount of energy in
a system capable of doing mechanical work.

Specific enthalpy refers to the amount of heat in a unit mass of one kg. The amount of
heat added to water and steam begins at starting point A shown with an enthalpy of zero
at 0°C.

Page 37
 Figure 1
Temperature-Enthalpy Chart for Steam

The first step starts at point A as water is heated. The process follows the line AB and
applies to a situation where the pressure is atmospheric (101.325 kPa). At point B,
419.04 kJ has been added to the water, which is still in liquid form, and the temperature
is now 100°C. The added heat is called sensible heat because it causes an increase in the
temperature of the water which can be “sensed” and measured. This term sensible heat is
now replaced with the terms liquid enthalpy or enthalpy of water.

In the next stage, shown as BC in Fig. 1, the water is progressively turned into steam.
This occurs at the saturation temperature or the boiling point. The heat added is called
latent heat because it does not produce a change in temperature. For water at
atmospheric pressure, the amount of latent heat required to go from B to C is 2257
kJ/kg. Although the term latent heat is still used, it is more commonly called enthalpy
of evaporation.

Page 38
At point C, all of the water has been transformed to steam and, since there is no more
liquid, the steam is now dry and saturated and is called dry steam. In between points
B and C, the mixture of water and steam is called wet steam. The proportion of water
and steam is called the dryness fraction which increases from 0 (or 0% steam) at point
B to 1 (or 100% steam) at point C.

Once point C is reached, the addition of further heat again causes an increase in
temperature. The steam is now superheated and dry.

Referring to Fig. 1, at increased pressures, the saturation (or boiling) temperature also
increases and more sensible heat is needed to reach the higher saturation temperature. If
water is at a pressure of 1553.8 kPa, boiling occurs at 200°C and 852.45 kJ/kg of
sensible heat is required. However, less latent heat (1940.7 kJ/kg) is required to reach
the dry saturated temperature.

As the pressure is increased, a point is reached where no latent heat is required to go

from water to steam. This point is called the critical pressure and occurs at a pressure
of 22 090 kPa and a temperature of 374.136°C.

STEAM TABLES
The properties of steam are fully described in Steam Tables. Because there is no
theoretical equation for calculating the properties of steam directly, they are determined
experimentally. As the importance of steam grew both for power generation and steam
uses in industrial processing, it became crucial that accurate tables were available for
both design and operational purposes. Early tables were adequate for low pressures and
temperatures but the tables were extended as pressures and temperatures increased
substantially in the early to middle 1900s.

Although there are a variety of steam table sets available, in this course tables extracted
from Keenan, Keyes, Hill and Moore published by John Wiley and Sons Inc. are used.
Tables I and II cover the properties of steam in the saturated region and are basically the
same except that Table I begins with pressure as the starting point and Table II begins
with temperature. Table III covers the properties for superheated steam and is laid out
differently because the temperature increases again with the addition of heat. A
specialized chart called a Mollier chart which is based on enthalpy and entropy is also
included at the end of the tables.

Interpolation is used to estimate intermediate values from the tables. Because the table
cannot show all values, the same proportion is applied from one part of the table to
another to obtain intermediate values.

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 For example, Table I does not provide any values between 100 kPa and 125 kPa. To find
the enthalpy h f for a pressure of 115 kPa, the following interpolation is required:
15
h f at 115 kPa = h f at 100 kPa + (h f at 125 kPa - h f at 100 kPa)
25
15
= 417.46 kJ/kg + ( 444.32 - 417.46 ) kJ/kg
25
15
= 417.46 kJ/kg + ( 26.86 ) kJ/kg
25
= 417.46 kJ/kg + 16.12 kJ/kg
= 433.58 kJ/kg (Ans.)

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 Objective 2
Perform calculations involving specific enthalpy,
dryness fraction, specific heat and specific volume
using steam tables.

SPECIFIC ENTHALPY
Enthalpy is the quantity of heat, in kilojoules (kJ), contained in a substance. The
enthalpy at any given time depends on the temperature and pressure of the substance.
For water and steam, enthalpy is measured from a standard starting point of 0°C,
therefore, water at 0°C has an enthalpy of zero.

Steam tables record specific enthalpy for saturated or superheated steam and the units of
measure are kJ/kg. In Tables I and II, the first specific enthalpy shown, h f or sensible
heat, is for saturated liquid (for example, point B in Fig. 1) or the boiling point where
there is 100% water and no steam.

The second specific enthalpy is the enthalpy of evaporation or the latent heat, h fg . It is
the amount of heat required to go from point B to point C in Fig. 1. At the saturated
vapour stage, hg , the specific enthalpy is the sum of the sensible and latent heats so that:
hg = h f + h fg

In Table III, the specific enthalpy for superheated steam is shown for combinations of
pressure and temperature. Taking a pressure and temperature from Table I or II and
finding the equivalent (or close to it) in Table III, the value hg shows that the enthalpy
increases.

Example 1
Find the heat required to convert 10 kg of water at 15°C to saturated steam at 1400 kPa.
What is the final temperature?

Answer
From the Steam Tables, the specific enthalpies at the two conditions are:

h f at 1400 kPa = 830.30 kJ/kg

h f at 15°C = 62.99 kJ/kg

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 Therefore, the difference in specific enthalpy is:

h f at 1400 kPa − h f at 15°C = 830.30 kJ/kg − 62.99 kJ/kg

= 767.31 kJ/kg

The latent heat ( h fg ) at 1400 kPa is 1959.7 kJ/kg. Applying equation hg = h f + h fg and
multiplying by the total mass, the heat required is:

hg = h f + h fg
hg = 767.31 kJ/kg + 1959.7 kJ/kg
= 2727.01 kJ/kg ×10 kg
= 27270 kJ (Ans.)

The final temperature is the saturation temperature 195.07°C which is found in Table I.

Example 2
What is the enthalpy of 1 kg of steam at 3000 kPa when it is dry and saturated and when
it is superheated by 55°C?

Answer
The specific enthalpy ( hg ) of steam at 3000 kPa when it is dry and saturated is 2804.2
kJ/kg, found in Table I.

The saturation temperature, at 3000 kPa, is 233.9°C. With 55°C of superheat, the final
temperature is 288.9°C. To obtain the specific enthalpy at this temperature, interpolate
between the values given in Table III for 250°C and 300°C at 3000 kPa.

38.9
h at 288.9°C = h at 250°C + (h at 300°C - h at 250°C)
50
38.9
h at 288.9°C = 2855.8 kJ/kg + (2993.5 - 2855.8)
50
38.9
= 2855.8 kJ/kg + (137.70)
50
= 2855.8 kJ/kg + 107.13
= 2962.93 kJ/kg (Ans.)

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DRYNESS FRACTION
When there is a mixture of water and steam, or wet steam, the relative amounts of water
and steam are described in terms of a dryness fraction, called the steam quality. The
symbol x is used for steam quality and it is the fraction of the water and steam mixture
that is in the vapour (or steam) phase. It is used in wet steam calculations for specific
volume, enthalpy and entropy. Therefore, for any point in the wet steam phase, the
specific enthalpy is calculated using the equation:

h = h f + xh fg

Example 3
What is the specific enthalpy of 1 kg of steam at 2500 kPa with a dryness fraction of
0.8?

Answer
Using the values from Table I in the Steam Tables and the equation h = h f + xh fg , the
specific enthalpy is calculated as:

h = h f + xh fg
h = 962.11 kJ/kg + ( 0.8 × 1841.0 ) kJ/kg
h = 962.11 kJ/kg + 1472.8 kJ/kg
= 2434.91 kJ/kg (Ans.)

SPECIFIC HEAT
The specific heat of water (the amount of heat in J (Joules) needed to raise the
temperature of 1 g of water by 1°C) is 4.1894 kJ/kg/°C. This can be verified by looking
at the value for 100°C, which is 418.94 kJ/kg at atmospheric pressure, and then it
dividing by 100.

At 2000 kPa, the sensible heat ( h f ) is 908.79 kJ/kg. Dividing 908.79 kJ/kg by the
saturation temperature (212.42°C), the specific heat is 4.2783 kJ/kg/°C. The difference
increases with pressure and temperature.

The specific heat of steam varies even more although it is possible to estimate the
specific heat in a narrow range of temperature and pressure. For example, to determine
the specific heat of superheated steam at 6000 kPa between 400°C and 500°C, the
specific heat is calculated to be:

Page 43
 h at 6000 kPa and 400°C = 3177.2 kJ/kg
h at 6000 kPa and 500°C = 3422.2 kJ/kg
3422.2 - 3177.2 kJ/kg
Specific heat =
100o C
= 2.45 kJ/kg/ o C

SPECIFIC VOLUME
The specific volume is the volume per unit of mass of any substance. In the steam tables,
the specific volume v is measured in cm3/g.

Referring to the steam tables, for wet steam, the specific volume of the liquid portion is
very small compared to the specific volume for the steam component at lower pressures
and temperatures. As pressures and temperatures rise to the critical pressure and
temperature, their specific volumes eventually become equal. For many calculations, the
specific volume of the water can be ignored without significant loss of accuracy.

To calculate the specific volume for wet steam, the dryness fraction is used in the same
way as it is for enthalpy (taking into account that the tables only show vf and vg) using
the equation:
v = v f + x (v g − v f )

Example 4
What is the specific volume of 1 kg of steam at 2500 kPa with a dryness fraction of 0.8?

Answer
Using the values from Table I in the Steam Tables and equation v = v f + x(vg − v f ) , the
specific volume is calculated as:

v = v f + x (v g − v f )
v = 1.1973 cm3 /g+0.8(79.98-1.1973)cm3 /g
v = 1.1973 cm3 /g+0.8(78.78)cm3 /g
v = 1.1973 cm3 /g+63.02cm3 /g
v = 64.22 cm3 /g
v = 0.06422 m3 /kg (Ans.)

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 Objective 3
Explain the principles and use of calorimeters to
measure the dryness fraction of wet steam.

MEASURING THE DRYNESS FRACTION OF STEAM

In steam plants it is frequently necessary to measure the dryness fraction of steam, if
saturated steam is used. Steam that is overly wet (too much moisture content) causes
corrosion and erosion in equipment. Wet steam also reduces plant thermal efficiencies
and increases the risk of water hammer in piping.

A calorimeter measures the dryness fraction of wet steam and determines the amount of
heat in the steam. There are three types of calorimeter used:
• Throttling
• Separating
• Electric

THROTTLING CALORIMETERS
Throttling calorimeters, used for steam with low moisture content, are based on the
principle that when steam pressure is reduced through an orifice or constriction, the
enthalpy remains the same because there is no opportunity for the heat to be removed. If
the steam contains a moderate amount of moisture, the wet steam is converted, or
flashed, to superheated steam at a lower pressure, as shown in Fig. 2. The process is
isenthalpic, which means that there is no change in enthalpy. The pressure and
temperature at point 2 are used to determine the enthalpy from the Steam Tables. Since
the enthalpy at points 1 and 2 are the same, it can be used to calculate the dryness
fraction at the higher pressure.

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 Figure 2
Effect of Throttling on Wet Steam

Throttling calorimeters are applicable to wet steam conditions that range approximately
from 0.965 dryness fraction at 700 kPa to 0.93 at 2700 kPa. For wetter steam, a
separating calorimeter must be inserted upstream of the throttling calorimeter.

The steam sample is taken from a vertical pipe as close as possible to the engine,
turbine, or boiler tested. An example of a good sampling method is shown in Fig. 3.

Figure 3
Example of Sampling Tube

A simple throttling calorimeter that is easy to construct is illustrated in Fig. 4. The steam
is throttled through the orifice O into a chamber C. The temperature is measured with a
thermometer T and the pressure is measured with a manometer connected to valve V2.
The steam is allowed to escape to a vent through valve V1. To ensure that no heat is lost
to the surroundings, all parts of the calorimeter are insulated from the steam main.

Page 46
If the orifice is sized correctly, the steam is at atmospheric pressure after throttling and
the operation can be simplified. When taking the measurement, wait until the
temperature has reached a maximum value and then decreased slightly.

Figure 4
Example of Simple Throttling Calorimeter

SEPARATING CALORIMETERS
A separating calorimeter, used for steam with high moisture content, is inserted
upstream of the throttling calorimeter to reduce the amount of moisture so that the
throttling calorimeter can be used effectively. If the moisture content in the steam is too
high (for example, a dryness fraction of less than 96.5% at 700 kPa,) then a separating
calorimeter is used to separate most of the moisture before the steam is passed to a
throttling calorimeter. An example of a simple separating calorimeter is shown in Fig. 5.
The steam enters at point A, exits at point D, and condenses in a container. The change
in direction required as it passes through the tube with holes produces inertial forces that
cause the moisture to collect in the cavity V. The amount of liquid collected is measured
in the sight glass G.

Page 47
 Figure 5
Example of Simple Separating Calorimeter

A separating calorimeter can also be used to calculate the dryness fraction without the
use of a throttling calorimeter. In this case, the steam exiting at point D is condensed and
the mass of liquid at point D and in sight glass G is recorded for comparison.

A disadvantage of a separating calorimeter is that the resulting calculation tends to

underestimate the wetness of the steam because some of the moisture carries over with
the steam.

ELECTRIC CALORIMETERS
Electric calorimeters are also used to measure the dryness fraction of wet steam. A
measured amount of steam is heated with a known amount of electric heat until the
steam becomes superheated. The enthalpy is computed from the resultant pressure and
temperature from the Steam Tables and the enthalpy of the wet steam is calculated by
subtracting the electric heat added. This requires an accurate measurement of the steam
flow and the flow may be difficult to measure.

Page 48
 Objective 4
Calculate the dryness fraction of steam based on
calorimeter data.

MEASURING DRYNESS USING A THROTTLING CALORIMETER

The dryness of the wet steam is calculated on the basis that the enthalpy of the wet
steam is equal to the enthalpy of the throttled steam which is now superheated. Using
the equation developed for determining the dryness of wet steam, h = h f + xh fg , and
substituting the enthalpy of the superheated steam hsup , the following equation is
derived:
hsup = h f + xh fg
h f + xh fg = hsup − h f
hsup − h f
xh fg =
h fg
hsup − h f
x=
h fg

Example 5
Wet steam at a pressure of 1000 kPa is sampled in a throttling calorimeter. If the
temperature is measured at 100°C and the pressure is 100 kPa, what is the quality of the
steam?

Page 49
 Answer
From Table III in the Steam Tables, the specific enthalpy of the superheated steam is
2676.2 kJ/kg. From Table I for a pressure of 1000 kPa, the enthalpy for the saturated
liquid hf is 762.81 kJ/kg and the latent heat hfg is 2015.3 kJ/kg. The dryness of the wet
h − hf
steam is found using the equation x = sup :
h fg
hsup − h f
x=
h fg
2676.2 kJ/kg − 762.81 kJ/kg
x=
2015.3 kJ/kg
1913.39 kJ/kg
x=
2015.3 kJ/kg
x = 0.949
= 94.9% (Ans.)

MEASURING DRYNESS USING A SEPARATING CALORIMETER

Using a separating calorimeter, a rough estimate of the dryness is made for steam that is
too wet for a throttling calorimeter. If the mass of the water collected in the calorimeter
is m1 and the mass of the condensed steam is m2 , the dryness is calculated using the
equation:
m2
x=
m2 + m1

This calculation tends to underestimate the wetness of the steam because some of the
moisture carries over with the steam.

MEASURING DRYNESS USING A SEPARATING AND

THROTTLING CALORIMETER
A more accurate method of measuring dryness is to sample the steam in a throttling
calorimeter after it goes through the separating calorimeter to determine the remaining
moisture in the steam.

Fig. 6 illustrates a combined separating and throttling calorimeter.

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 Figure 6
Combined Separating and Throttling Calorimeter

If x2 is the dryness of the steam entering the throttling calorimeter, then the amount of
dry steam is x2 m2 kg. The total mass of the sample is m1 + m2 so the dryness of the
sample x is:
xm
x= 2 2
m1 + m2

In this equation, the apparent dryness of the separating calorimeter as defined in

m2
equation x = , is x1 so that the equation is:
m2 + m1
x = x1 × x2

Example 6
Wet steam at a pressure of 1400 kPa is sampled by a separating and throttling
calorimeter. The amount of water obtained from the separating calorimeter is 0.4 kg. In
the throttling calorimeter, the temperature is measured at 140°C and the pressure is 100
kPa. The mass of the condensate collected from the throttling calorimeter is 9 kg. What
is the dryness fraction of the steam?

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 Answer
The dryness of steam from the separating calorimeter is obtained using the equation
m2
x1 = :
m2 + m1
m2
x1 =
m2 + m1
9 kg
x1 =
9kg + 0.4 kg
x1 = 0.9574

From Table III in the Steam Tables, the specific enthalpy of the superheated steam in the
throttling calorimeter is calculated by interpolation:

40
h at 140°C = h at 100°C + (h at 150°C - h at 100°C)
50
40
h at 140°C = 2676.2 kJ/kg + (2776.4 - 2676.2) kJ/kg
50
40
h at 140°C = 2676.2 kJ/kg + (100.20) kJ/kg
50
h at 140°C = 2676.2 kJ/kg + 80.16 kJ/kg
h at 140°C = 2756.36 kJ/kg

From Table I for a pressure of 1400 kPa, the enthalpy for the saturated liquid hf is 830.3
kJ/kg and the latent heat hfg is 1959.7 kJ/kg. The dryness of the wet steam is found using
h − hf
the equation x = sup :
h fg
h − hf
x = sup
h fg
2756.36 − 830.3
x=
1959.7
x = 0.9828 or 98.28%

The total dryness is the product of the two dryness calculations using the
equation x = x1 × x2 :
x = x1 × x2
x = 0.9574 × 0.9828
x = 0.941
= 94.1% (Ans.)

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 Objective 5
Calculate the internal energy of steam under given
conditions.

INTERNAL ENERGY
Internal energy is another property of steam that is found in the Steam Tables. Internal
energy follows the First Law of Thermodynamics which states that work and heat are
equivalent and interchangeable. The equation associated with the First Law of
Thermodynamics states that heat added to a system causes either a change in the internal
energy or work done on the system:

Q = ∆U + W

In this equation, U represents internal energy. Q represents enthalpy, with a scale

beginning at an enthalpy of zero at 0°C. In other words, Q = h .

The above equation applies to any non-flow process. For flow processes, factors such as
velocity and elevation have to be considered and the production of steam in a boiler is a
common example. The work done on the fluid causes changes in pressure and
temperature. Therefore, the work W can be expressed as pv (pressure in kPa × specific
volume in m3/kg).

Equation Q = ∆U + W can thus be rewritten as:

h = ∆µ + pv

Note how this equation applies to a boiler. The feedwater enters the boiler at a pressure
of P kPa and a specific volume v1 so that the flow energy is Pv1 . Its internal energy at
this point is u1 . Thus the enthalpy is:
h1 = u1 + p1v1

Heat is added until the boiling point is reached. Most of the heat goes into increasing the
internal energy through an increase in temperature. The pressure is constant and there is
only a minor increase in the specific volume.

Page 53
 The enthalpy at the boiling point is:

h f = u f + p1v f

This can be verified from the Steam Tables. Taking a pressure of 2000 kPa in Table I at
the boiling point:
h f = U f + p1v f
1.1767
908.79 = 906.44 + 2000 ×
1000
908.79 = 906.44 + 2.35
908.79 = 908.79

During the next phase, the water is transformed from a liquid to a vapour. The pressure
and temperature remain constant while the specific volume increases to vg as the liquid
is turned into a vapour. Some of the heat is used to increase the internal energy to free
the molecules so that the water can be changed to a vapour and the remaining heat
increases the volume. The equation is now written as:

h fg = (u g − u f ) + p(vg − v f )

Example 7
Calculate the change in internal energy experienced in a boiler as 1 kg of feedwater at
40°C and 500 kPa is heated to produce steam with a dryness fraction of 0.97. Verify
with the internal energy column in the table.

Answer
The enthalpy of the feedwater, at 40°C, from the Steam Tables is 167.57 kJ/kg and the
specific volume is 1.0078 cm3/kg. The internal energy at 500 kPa, using the equation
h f = u f + p1v f , is:

h f = µ f + p1v f
u f = h f − p1v f
1.0078 cm3 /kg
u f = 167.57 kJ/kg − 500 ×
1000 cm3 /kg
u f = 167.57 kJ/kg − 500 × 0.0010078 cm3 /kg
u f = 167.57 kJ/kg − 500 × 0.0010078 cm3 /kg
u f = 167.57 kJ/kg − 0.5039 cm3 /kg
u f = 167.07 kJ/kg

Page 54
The enthalpy of the steam, at 500 kPa, is found using the equation h = h f + xh fg :

h = h f + xh fg
h = 640.23 kJ/kg + 0.97 × 2108.5 kJ/kg
h = 640.23 kJ/kg + 2045.25 kJ/kg
h = 2685.48 kJ/kg

The specific volume is calculated using the equation v = v f + x(vg − v f ) :

v = v f + x (vg − v f )
v = 1.0926 cm3 /g + 0.97(374.9 − 1.0926) cm3 /g
v = 1.0926 cm3 /g + 0.97(373.8074) cm3 /g
v = 1.0926 cm3 /g + 362.5932 cm3 /g
v = 363.69 cm3 /g
v = 0.36369 m3 /kg

The internal energy is:

u g = h2 − p2 v2
u g = h2 − p2 v2
u g = 2685.48 kJ/kg − 500 kPa × 0.36369 m3 /kg
u g = 2685.48 kJ/kg − 181.85 m3 /kg
u g = 2503.63 kJ/kg

Therefore, the change of internal energy is:

∆µ = u g − u f
∆µ = 2503.63 kJ/kg − 167.07 kJ/kg
∆µ = 2336.56 kJ/kg

Page 55
 The initial internal energy is read directly from the tables and is equivalent to the
calculated internal energy. The final internal energy is obtained from the tables with
allowance for the dryness fraction.
u g = u f + xu fg
u g = 639.68 kJ/kg + 0.97 × 1921.6 kJ/kg
u g = 639.68 kJ/kg + 1863.9 5kJ/kg
u g = 2503.63 kJ/kg ( Ans.)

Page 56
 Objective 6
Explain the concept of entropy and the use of the
temperature-entropy diagram. Calculate the change in
entropy for a particular change in enthalpy at a constant
temperature.

ENTROPY
A derived property called entropy is useful in calculating the effects of thermodynamic
processes. Entropy is derived from the measurable properties of heat and temperature
and can be defined as follows.

The entropy of a substance is calculated from the sum of all of the small quantities of
heat given to the substance, each divided by the absolute temperature at which it was
given.

Entropy is a property of steam that is derived from the Second Law of Thermodynamics.
This law states that work must be done to transfer heat from one system to another and
that it is impossible for heat to flow from a colder system to a hotter one without
expending energy in the form of work.

From the Second Law, the transfer of heat is a process that is dependent on the
temperature of the working fluid. Entropy is a function of the heat transferred during
parts of a thermodynamic cycle and the absolute temperature, and it serves to define the
relationship between heat flow and absolute temperature.

The symbol used for entropy is S . Change of entropy is ∆S and the units used are
kilojoule per kelvin (kJ/K). Specific entropy, which is entropy per unit mass, is
represented by the symbol s and the units used are kilojoule per kilogram kelvin
(kJ/kgK). Thus, for any small addition of heat ∆Q kJ, the increase in entropy ∆S will be

∆Q
∆S =
T

The symbol ∆ (Delta) indicates a small change.

Page 57
 TEMPERATURE –ENTROPY DIAGRAM
A temperature-entropy diagram is shown in Fig. 7. The temperature is plotted on the y-
axis and the entropy is on the x-axis. The line illustrates the conversion of water to
steam at constant pressure through the stages of water, wet steam, and superheated
steam. Notice that the areas under the curve are equal to the sensible heat h f and the
latent heat h fg .

Figure 7
Temperature-Entropy Diagram

An isothermal process is depicted as a straight horizontal line on this diagram. The most
important area of constant temperature is the wet steam phase. The calculation of
entropy for various dryness fractions is done using the familiar equation:

s = s f + xs fg

Page 58
Example 8
Calculate the specific entropy of wet steam at a pressure of 1400 kPa and a dryness of
0.96.

Answer
From the Steam Tables, the specific entropy of the saturated liquid is 2.2842 kJ/kgK and
the latent entropy is 4.1850 kJ/kgK. Using the equation 6 s = s f + xs fg , the entropy is:

s = s f + xs fg
s = 2.2842 kJ/kgK + 0.96 × 4.1850 kJ/kgK
s = 2.2842 kJ/kgK + 4.0176 kJ/kgK
s = 6.3018 kJ/kgK (Ans.)

CHANGE IN ENTROPY

Example 9
One kilogram of dry saturated steam at a pressure of 3000 kPa is throttled to a pressure
of 1000 kPa and then expanded at constant entropy. Calculate the increase in entropy.

Answer
3000 kPa hg = 2804.2 kJ/kgK sg = 6.1869 kJ/kgK
1000 kPa hg = 2778.1 kJ/kgK

Throttling process:

Enthalpy after = Enthalpy before

Enthalpy at 1000 kPa = 2804.2 kJ/kgK

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 Since the steam is superheated:

Enthalpy of superheat = 2804.2 kJ/kgK − 2778.1 kJ/kgK

= 26.10 kJ/kgK
At 1000 kPa, h = 2827.9 kJ/kgK for 200° C
h = 2778.1 kJ/kgK for 179.91° C ( Saturation temperature )
Increase h = ( 2827.9 kJ/kgK - 2778.1 kJ/kgK ) for 20.09° C
Increase h = 49.8 kJ/kgK for 20.09° C
Difference in temperature for h = 2804.2 kJ/kgK - 2778.1 kJ/kgK
h = 26.10 kJ/kgK
26.10 kJ/kgK
h= × 20.09° C
49.8 kJ/kgK
h = 0.5241 kJ/kgK × 20.09° C
h = 10.53° C
Degree of superheat at 1000 kPa = 10.53° C

Entropy at 1000 kPa, 10.5291ºC superheat:

Tsat = 179.91° C TSup = 179.91° C + 10.53° C

TSup = 190.44° C

Saturation:
1000 kPa T = 179.91° C s = 6.5865
°
T = 200 C s = 6.6940

6.6940 kJ/kgK − 6.5865 kJ/kgK

Change in entropy s = × (190.44° C − 179.91° C ) + 6.5865 kJ/kgK
200 C − 179.91 C
° °

0.1075 kJ/kgK
s= °
×10.53° C + 6.5865 kJ/kgK
20.09 C
s = 0.0054 ×10.53° C + 6.5865 kJ/kgK
s = 0.0569 + 6.5865 kJ/kgK
s = 6.6428 kJ/kgK

Increase in entropy = Change in entropy - Entropy of 3000 kPa steam

Increase in entropy = 6.6428 kJ/kgK - 6.1869 kJ/kgK
Increase in entropy = 0.4559 kJ/kgK ( Ans.)

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 Objective 7
Determine steam properties using a Mollier Chart.

MOLLIER CHART
A Mollier chart, useful for analyzing steam cycles, is provided at the end of this chapter
and can be downloaded from the Second Class Companion Website. Specific enthalpy
is on the y-axis and specific entropy is on the x-axis. The saturation line which separates
wet steam from superheated steam is shown on the chart along with lines for constant
pressure, constant temperature and constant dryness.

It is possible to use the entropy values in the Steam Tables to analyze steam conditions,
but the Mollier Chart is valuable for analyzing cycles. Throttling, which is a constant
enthalpy process, is represented by a straight horizontal line from the initial pressure and
condition to the final pressure.

During an adiabatic process, no heat transfer takes place to and from the surroundings. If
the process is reversible, it is then also isentropic (no change in entropy) and the process
is represented on the Mollier Chart by a straight vertical line.

Example 9
Steam, with a dryness of 0.96, is throttled from a pressure of 500 kPa. Using the Mollier
Chart, what is the final pressure required for the steam to be dry and saturated? What are
the enthalpies and entropies for these two points?

Answer
The starting point is found at the intersection of the pressure of 500 kPa and dryness of
0.96. From the Mollier Chart, the enthalpy is estimated as 2660 kJ/kg and the entropy as
6.61 kJ/kgK. Follow a horizontal line to the saturation line. The pressure is
approximately 70 kPa with the same enthalpy and an entropy of 7.48 kJ/kgK. These
values can be verified using Table I and finding that the enthalpy of 2660 matches that
given for a pressure close to 75 kPa.

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 Example 10
Superheated steam at a pressure of 10 000 kPa and a temperature of 700°C is expanded
isentropically to a pressure of 100 kPa. Using the Mollier Chart, what is the change in
enthalpy and the dryness fraction after expansion?

Answer
The starting point is found at the intersection of a pressure of 10 000 kPa and a
temperature of 700°C. From the Mollier Chart, the enthalpy is estimated as 3870 kJ/kg.
Follow a vertical line to a pressure of 100 kPa. The enthalpy is approximately 2610 with
a dryness of 0.97. The change in enthalpy is thus 1260 kJ/kg. These values can be
verified from the tables.

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 Objective 8
Calculate boiler thermal efficiency using test data
provided.

BOILER EFFICIENCY
When using a boiler, it is important to know the thermal efficiency at which it is
operating. A high efficiency boiler is economical and contributes to a high overall
efficiency for the whole plant. Many factors contribute to the thermal efficiency,
including the type of fuel used, the variation in the load factor of the boiler, the boiler
design and maintenance practices. Therefore, it is valuable to be able to calculate the
efficiency of a boiler to ensure economical operation.

The efficiency of a boiler is determined by taking the ratio of the heat transferred to
produce steam and the energy released by the fuel supplied to the boiler or:

Heat transferred to water and steam

Boiler efficiency =
Heat supplied by fuel

The heat energy transferred to the steam is found by taking the difference in the specific
enthalpies of the feedwater ( hw ) and the steam produced ( h1 ) and then multiplying this
difference by the amount of steam produced ( ms ) per unit time. The heat supplied by the
fuel is the amount of fuel used ( m f ) per unit time multiplied by the heating value of the
fuel ( HV f ). The efficiency is calculated using the equation:

ms (h1 − hw )
Eb =
m f HV f

If the mass of the steam and fuel are added, a variable that represents the mass of steam
produced/mass of fuel burned is obtained and the equation becomes:

msf (h1 − hw )
Eb =
HV f

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 Example 11
A small boiler generates 10.2 kg of steam per kg of fuel oil burned. The fuel oil has a
heating value of 30 200 kJ/kg. The feedwater is at 50°C and 1400 kPa. If steam is
generated with a dryness of 0.941, what is the boiler efficiency?

Answer
The enthalpy of the feedwater, at 50°C, is found in the Steam Tables, Table II (part of
the Academic Supplement) as 209.33 kJ/kg. The enthalpy of the steam, using the
equation h = h f + xh fg , is:

h = h f + xh fg
h = 830.30 kJ/kg + 0.941× 1959.7 kJ/kg
h = 830.30 kJ/kg + 1844.08 kJ/kg
h = 2674.38 kJ/kg

msf (h1 − hw )
The boiler efficiency is calculated using the equation Eb = :
HV f

msf (h1 − hw )
Eb =
HV f
10.2(2674.38 − 209.33)
Eb =
30 200
10.2(2465.05)
Eb =
30 200
25143.51
Eb =
30 200
Eb = 0.8326
Eb = 83.26 % (Ans.)

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 Chapter Questions

1. Define the following:

a) Sensible heat
b) Latent heat
c) Superheat

2. What is the enthalpy of 1 kg of steam at 2000 kPa:

a) when dry and saturated
b) when 0.96 dry
c) when superheated by 85°C

3. Describe the principle of a throttling calorimeter and explain why a separating

calorimeter sometimes has to be added.

4. A combination separating and throttling calorimeter is connected to a main steam

header. The following data was collected:
• Steam pressure – 2410 kPa
• Amount of water collected in the separating calorimeter – 0.87 kg
• Amount of condensate after the throttling separator – 12.5 kg
• Pressure of the steam in throttling calorimeter – 185 kPa
• Temperature of steam in throttling calorimeter - 135ºC

Taking the specific heat of the throttled superheated steam as 2.25 kJ/kgK, calculate
the main steam line dryness fraction.

5. One kilogram of steam at a pressure of 100 kPa and 50 percent dry, receives heat
under constant volume raising the pressure to 300 kPa absolute.
Calculate the following:
a) volume of the steam
b) quality of the steam at the end of the process
c) work done
d) change in internal energy

6. 0.6 m3 of nitrogen is contained in a cylinder at 105 kPa and 22°C. The gas is then
compressed isothermally until the pressure is 3600 kPa. Calculate the change in
entropy. (R for nitrogen = 297 Nm/kgK)

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 7. Steam with a dryness of 0.97 is throttled from a pressure of 800 kPa. Using the
Mollier Chart, what is the final pressure required for the steam to be dry and
saturated? What are the enthalpies and entropies for these two points?

8. A boiler is fed with water at a temperature of 40°C and produces 2360 kg of dry
steam per hour at a pressure of 1750 kPa and a temperature of 250°C. Heat losses are
40% of the heat supplied and the heating value of the fuel is 31 400 kJ/kg. What is
the fuel flow required?

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