KYAMBOGO UNIVERSITY

FACULTY OF ENGINEERING

DEPARTMENT OF MINING, CHEMICAL, AND

PETROLEUM ENGINEERING.

COURSE CODE: SCE1103 CHEMICAL ENGINEERING THERMODYNAMICS

SEMESTER: ONE

LECTURER: MS MERCY KITIMBO

TASK: ASSIGNMENT

NAME: ECODU JOHN PATRICK

REG NO: 23/U/CHD/14480/GV

DATE: 7/11/2023

(a) STEAM- POWER PLANTS:

Steam-power plants operate on a closed cycle. The working fluid undergoes a series of operations and returns to the
initial state.
The thermodynamic analysis of steam power plants is done by comparing the performance of the actual cycles with
certain idealized cycles.
The following shows ideal steam-power cycles with a view to suggest methods for the evaluation of their thermal
efficiencies and point out how the actual cycles deviate from these ideal cycles. Though the working fluid considered is water, the
discussion is applicable for vapour-power cycles in general.
1. Rankine cycle
The components of a Rankine cycle, also known as the standard vapour-power cycle are shown in diagram below.

Water at low temperature and pressure is compressed isentropically to the boiler pressure by the feed pump (1–2).
 In the boiler, heat is supplied to the water at constant pressure, whereby, its temperature rises to the saturation
temperature corresponding to the pressure in the boiler.
Further supply of heat results in the evaporation of water and in superheating the vapour, thus produced (2–3).
The superheated vapour at the elevated pressure is then allowed to expand isentropic ally in a turbine to the
condenser pressure (3–4).
In the condenser, the low-pressure exhaust steam from the turbine gives out its heat to the cooling water at constant
pressure (4–1).
The saturated liquid water leaving the condenser then enters the feed pump and the cycle is repeated.

The cycle is represented on a T-S diagram, as illustrated in the figure below. Let Q1 be the heat absorbed at constant
pressure in the boiler and Q2 be the heat rejected at constant pressure to the cooling water in the condenser, both correspond to unit
mass of the working fluid. Then,
Q 1=H 3−H 2 , Q2=H 4−H 1
Net work obtained per unit mass ¿ ( H 3−H 1 )−(H 4−H 1)
Wnet ( H 3−H 1 )−(H 4−H 1)
Efficiency of the ranking cycle, ŋ= =
Q1 H 3−H 2

In graph (b), is shown the T-S diagram of a Carnot engine operating between the same average temperature
levels.
A Carnot cycle consists of two reversible adiabatic operations and two reversible isothermal operations.
Comparing the preceding figures, it can be readily concluded that the efficiency of the Rankine cycle is less than that of a Carnot
cycle operating between the same thermal reservoirs.
(a) (b)

NB,
In a rankine cycle, the steam is superheated so that no liquid state exists inside the turbine.
Condensation in the turbine can cause corrosion and erosion of the turbine blades.
There are several modifications to the Rankine cycle leading to better practical designs.
In the reheat cycle there are two expanders working in series, where steam from the high pressure stage is heated again in
the boiler before it enters the low pressure expander.
This avoids moisture in the turbine and also increases the efficiency.
The regenerative cycle is another modification to increase the efficiency of the Rankine cycle.
In many Rankine cycle implementations, the water enters the boiler in the sub cooled state,
And also, the large difference in temperature between the one at which heat is supplied to the boiler and the fluid
temperature will give rise to irreversibilities which will cause the efficiency to drop.
In the regenerative cycle, the output of the condenser is heated by some steam tapped from the expander.
This causes the overall efficiency to increase, due to the reasons noted above.

2 The reheat cycle.

The efficiency of Rankine cycle can be improved by increasing the pressure in the boiler. However, this will lead to an
increase in the proportion of the liquid in the exhaust from the turbine. This problem is circumvented in a reheat cycle. The reheat
cycle uses high pressure during the absorption of heat, yet eliminates the presence of excessive moisture in the discharge from the
turbine. The cycle is presented in figure above.
 The superheated steam leaving the boiler is admitted to a high-pressure turbine, and after expansion is returned to the boiler for
reheating. It is heated to a high temperature in the boiler, and then sent to a low-pressure turbine where it is expanded to the
condenser pressure.

3 Regenerative cycle.
In the Rankine cycle, the feed water enters the boiler in a sub-cooled state corresponding to the pressure in the boiler and it is
heated to the saturation temperature before vaporization begins.
But the heating medium in the boiler is at a very high temperature. Because of this large difference between the temperature of the
heating medium and that of the feed water, the heat interaction in the boiler is a highly irreversible process. The process can be carried
out more or less reversibly, if the water from the condenser rather than being pumped directly to the boiler is first heated by steam
extracted from various stages of expansion in the turbine.
The heating process thus approaches a reversible isothermal heat interaction process. In this way, the thermal efficiency of
the Rankine cycle could be greatly improved. The Rankine cycle modified in this manner is known as the regenerative cycle.
 (b) INTERNAL COMBUSTION ENGINES
I nternal combustion engine differs from steam power plants such that the former operates on open cycles whereas
the latter on closed cycles.
In internal combustion engines, the working fluid which is a mixture of air and fuel is burned inside the engine
and after a series of processes which results in the production of mechanical work, the combustion products are discarded.
The working fluid does not undergo a cycle of changes in an internal combustion engine, as does the steam in a
steam power plant. However, the engine operates on a closed mechanical cycle. The internal combustion engines involve no
transfer of heat through surfaces, which restrict the temperature and pressure, as is the case with the boiler of the steam power
plants.
The high temperatures and the absence of heat transfer surfaces are the main advantages of internal combustion
engines over steam power generation systems.
The thermodynamic analysis of internal combustion engine is made possible by devising ideal closed cycles with air as the working
fluid and by comparing the performance of actual cycles with these ideal air-standard cycles. The assumptions involved in this
approach are:
1. The working fluid is a fixed mass of air and it undergoes no chemical change. Air is assumed to behave as an ideal gas.
2. The combustion process in the actual cycle is replaced by a heat transfer process in the ideal cycle. Heat is assumed to be
transferred from an external heat source.
3. The exhaust stroke in the actual engine is replaced by a heat rejection step in the ideal cycle.
Heat is assumed to be transferred to the surroundings.
4. The air is assumed to have constant specific heat and all the processes are internally reversible. The Otto cycle and the Diesel cycle
are the two important air-standard cycles used for the analysis internal combustion engines.
1 The Otto cycle

• This is the ideal situation for processes found in reciprocating internal combustion engines which are used by most automobiles.
• The working fluid is an ideal gas, as opposed to the air/fuel mixture in an engine.

The Otto cycle Step 1 - 2, heat is absorbed at constant volume:

Q1−2=C V ( T 2 −T 1 )
Step 2 - 3, the gas expands reversibly and adiabatically during
which work is done.
For adiabatic process:
γ−1 γ −1
⇒ T 2 V 2 =T 3 V 3

Step 3 - 4, heat is rejected at constant volume and

low temperature.
Q3−4 =−C V ( T 4 −T 3 )=C V ( T 3 −T 4 )
Step 4 – 1, the gas is compressed reversibly and adiabatically.
 γ −1 γ −1
⇒ T 4 V 4 =T 1 V 1 Thermal efficiency of Otto cycle:

• Considering the isothermal processes, the thermal efficiency for Otto cycle is:
( Q 1−2 ) −( Q3−4 )
η=
( Q1−2 )
Q3−4
⇒ η=1−
Q1−2

T 3−T 4
⇒ η=1−
T 2−T 1
• Considering the adiabatic processes, since V1 = V2 & V3 = V4:

( ) ( )
γ −1 γ −1
T V V T1
⇒ 2= 3 = 4 =
T3 V 2 V1 T4
T2 T1
⇒ =
T3 T 4
• And efficiency becomes:

⇒ η=1−
(
T 3 1−
T4
T3 )
(
T 2 1−
T1
T2 )
T3
⇒ η=1−
T2
2. The Diesel engine:
The Diesel engines differ from the Otto engines; insofar as in the former, the temperature at the end of compression
exceeds the fuel ignition temperature and the combustion of fuel occur spontaneously. The Diesel cycle consists of the following
processes:

1. Process 1 –2: Air assumed to behave as an ideal gas, is compressed isentropially to a high temperature and pressure. The
temperature of the gas increases from T1 to T2.
2. Process 2–3: Heat Q1 is supplied to the fluid at constant pressure. The temperature increases to T3. (In actual engines, this is
accomplished by injecting the fuel to the hot compressed air at the end of the compression stroke. The fuel ignites spontaneously
and the piston starts moving outward slowly.)
3. Process 3–4: The gas undergoes an isentropic expansion by which the pressure and temperature of the gas decrease. The
temperature attained after the expansion process is T4.
4. Process 4–1: Heat Q2 is rejected at constant volume thus decreasing the temperature and pressure of the gas further. (In actual
engines, during the corresponding stage, the discharge port opens and the combustion products are exhausted.)

Heat absorbed Q1 = mCP (T3 – T2)

Heat rejected Q2 = mCV (T4 – T1)
Thermal efficiency is obtained as
ŋ= =1− =1−
Q1 γ (T AND
Q 1 REFRIGERATION 3−T LIQUEFACTION:
2)

Refrigeration is the process of producing and maintaining a temperature below that of the surrounding
atmosphere. Refrigeration p r o c e s s e s f i n d w i d e
a p p l i c a t i o n s i n c h e m i c a l p r o c e s s industries.
The process is used in manufacturing synthetic rubber, textiles, chlorine, plastics, hydrogen fluoride, etc.
Refrigeration is used to remove heat of chemical reactions and to liquefy process gases for gas separation by distillation and
condensation.
Liquefaction processes for the production of pure gases such as oxygen and nitrogen from air and liquefaction and storage
of natural gases employ refrigeration principles.
Separation of volatile hydrocarbons in petroleum industries, separation of gasoline from natural gas, solvent recovery,
crystallization of salts from solutions, manufacture of ice, treatment, transport and preservation of food and beverages, etc., are some
other important applications o f r e f r i g e r a t i o n operation.
(a) Carnot Refrigerator:

A refrigerator is a heat pump that absorbs heat from a region at a temperature below that of the surroundings and and rejects
heat to the surroundings.it operates with the highest possible efficiency on a Carnot refrigeration cycle, the reverse of Carnot engine cycle
Coefficient of performance of a Carnot refrigerator:

The efficiency or coefficient of performance (COP) of a refrigerator is defined as the quantity of heat absorbed at the low
temperature per unit of work.

From Figure above, which represents schematically the refrigeration process, Let Q2 be the heat that is absorbed at a low
temperature T2 and Q1 be the heat rejected at high temperature T1.
By first law of thermodynamics, the external work required to bring about this transfer is
W = Q1 – Q 2
Q2 Q2
COP= =
W Q1−Q2

Refrigerator Capacity
The refrigerator capacity determines the rate of circulation of the refrigerant, which in turn, decides the design and size of the various
units such as condenser, compressor, evaporator, and the expansion devices.
The capacity is sometimes measured in ton of refrigeration.
One ton is defined as the heat absorption at the rate of 12000 BTU per hour
(One BTU is the amount of heat required to raise the temperature of one pound, i.e. 0.4536 kg of water by one degree Fahrenheit,
or (1/1.8) K. Thus, 1BTU = 1.055 kJ). This rate corresponds to the rate of heat removal that is required to freeze 1 ton of water in a
day originally at 273 K. One ton of refrigeration is equivalent to a refrigeration rate of12660 kJ/h in SI units.

Choice of
refrigerator
The important properties of a refrigerant are as follows.
1. Boiling temperature: It is necessary that the operating pressure be maintained above atmospheric to avoid air and moisture leaks
into the system. The normal boiling point of the refrigerant should, therefore, be lower than the desired temperature levels in the
refrigerator.
2. Freezing point: The freezing point of the refrigerant should be well below the minimum temperature at which the system is
operated.
3. Critical temperature and pressure: The critical temperature and pressure of the refrigerant should be above the operating system
temperature and pressure. If the operating temperature is above the critical temperature, it is impossible to condense the gas by
compressing it to high pressures.
4. Condenser and evaporator pressures: The condenser pressure should not be very high. If pressure is very high, the cost of equipment
and the cost of operation would be excessive. If the evaporator pressure is excessively low, the compression ratio would be
abnormally high. If the refrigerant has sub-atmospheric vapour pressures at the temperature in the refrigerator coils, the possibility of
contamination by leaks cannot be overruled.
5. Specific v o l u m e : Specific volume of the vapour determines the size of the compressor. Low suction volumes are desirable
for reciprocating compressors and high suction volumes for centrifugal compressors.
6. Latent heat: A high latent heat of vaporization of the refrigerant is desired, because it results in high refrigerating effect per unit
weight of the refrigerant and low rate of circulation of the refrigerant.
7. Specific heat of liquid: If the specific heat of the refrigerant liquid is unduly high, large quantity of heat would have to be removed to
cool the hot liquid entering the evaporator to bring its temperature down to the saturation value. Therefore, low specific heat of the
liquid refrigerant is preferred.
8. Molecular weight: Molecular weight of the refrigerant affects the compressor size because the specific volume of the vapour is
directly related to it. A high-molecular weight refrigerant gives high specific volumes for the vapour, which is preferred for
centrifugal compressors, whereas for reciprocating compressors a low molecular weight for the refrigerant is advantageous.
9. Safety a s p e c t s : Refrigerants are grouped according to toxicity and flammability. Halogenated hydrocarbons are relatively
non-flammable, non-toxic, and non-explosive. These belong to Group 1. Group 2 refrigerants are either toxic or flammable.
Examples are methyl chloride and sulphur dioxide. The highly flammable and explosive refrigerants like propane, propylene, ethane,
ethylene, methane, etc., fall into group 3.
1 0. Other desirable properties: Normally, a refrigerant would be in use for a very long period. Consequently, the chemical
stability of the refrigerant is another important criterion in the choice of a proper refrigerant. They should also be non-corrosive,
should have low viscosity and high thermal conductivity.
(b) Heat pump:
This is a thermodynamic system operating in a thermodynamic cycle that removes heat from a low temperature body
and delivers heat to a high temperature body.
The heat pump receives external energy in form of work or heat from the surroundings.
A heat pump is a refrigerator operating in reverse order. Here, work is done to pump heat from a cold reservoir such as a river
or the surrounding land into a hot sink such as the inside of a house.
Heat pumps are used to heat houses and commercial buildings during the winter and cool them during the summer. During winter,
the liquid refrigerant is allowed to evaporate in coils kept in the outside air.
Heat is absorbed from the low-temperature source and the liquid gets vaporized during this stage. The vapour is then compressed to
such a pressure that it can be condensed at a high temperature. In the condenser, the heat is transferred to cooling water or air
which is used for heating the houses. By reversing the flow of the refrigerant, the same unit can be used to absorb heat from the
rooms and reject it to the outside air during summer.

The coefficient of performance of a heat pump used for winter heating can be defined as the ratio of heat rejected to
the high-temperature sink to the work required for the transfer. COP is
Q1/W.
 (c) Liquefaction processes
. Liquefaction processes make the task of storage, handling, and transportation of gases simple.
In addition to the benefits such as the reduction of storage space and transportation costs achieved by liquefaction process
in general, gas liquefaction is widely used for separation of gaseous mixtures into their component parts.
Air liquefaction and separation are used to produce liquid oxygen and nitrogen widely used in missile and rocket
development and low-temperature refrigeration. The developments in the space research have led to a manifold increase in the use of
liquid helium. Liquid hydrogen finds application in nuclear weapons development and rocket propulsion.
There are three general methods of engineering importance for liquefaction of gases:
1. Vaporization of a liquid
2. Joule–Thomson expansion
3. Expansion of gas in an engine delivering external work.

1. Vaporization of Liquid
This method can be used to reach liquid–air temperatures by employing a series of liquids of different boiling points. The
liquid of the lowest boiling point absorbs heat from the system to be refrigerated, and delivers this heat to the next higher boiling liquid
in a condenser–boiler combination. Finally, the fluid of the highest boiling point is condensed by cooling (by air or water) thus
discharging the heat to the atmosphere.
This method has been used for liquefaction of air and natural gas.
The lowest temperature that can be attained by this method is 63 K, the triple point of nitrogen.
2. Free Expansion
F or liquefaction of the gas by this method, the initial pressure of the gas should be raised to such a high value that on
Joule–Thomson expansion, which is an isenthalpic operation, the constant enthalpy lines cut into the two-phase region as shown in
graph below. Otherwise, no liquefaction is possible by Joule–Thomson expansion. For example, the gas at an initial state such as
the one represented by a point A in the figure below, cannot be liquefied by throttling.

The Linde process for gas liquefaction works on the principle of Joule–Thomson expansion.
It can be used for liquefaction of gases that cool on Joule–Thomson expansion, that is, for gases that possess a positive Joule–
Thomson coefficient.
Most gases have a positive Joule–Thomson coefficient at ordinary conditions, hydrogen and helium being exceptions. Even
hydrogen and helium have positive coefficients below 100 K and 20 K respectively.
The Linde process for liquefaction of air is shown in diagram below
 The temperature of the air at the upstream side of the throttle valve is reduced to a sufficiently low value (e.g. 170 K at 100
bars) so that the constant enthalpy lines cut into the two-phase region.
The cooling of air is achieved by passing it counter-currently to the liquefied part of the air leaving the throttling valve. Fresh
air and the un liquefied air form the input to the compressor.
Air leaving the compressor is cooled by ambient air or by cooling water and subsequently by counter-current heat exchange
with the recycled air. In the throttling valve, a fraction of the gas is liquefied. By applying the first law, it can be shown that the
fraction x of the liquefied air is given by
HC = xHF + (1 – x)HA

Or

3. Isentropic Expansion
The Claude process for gas liquefaction utilizes isentropic expansion of a compressed gas.
The throttle valve, in figure above will be replaced by an expansion turbine. The process can be followed on the T-S diagram
as shown in figure below.

The v e r t i c a l l i n e DE represents the isentropic expansion. The fraction of gas liquefied can be determined as follows.
An energy balance around the heat exchanger, turbine, and the separator gives
xHC = (1 – x)HA + xHF + WS
Where WS is the work delivered by the turbine. If the turbine operates adiabatically, the shaft work
WS is equal to the decrease in enthalpy of the gas during expansion.
 WS = HD – HE

The fraction of the gas liquefied in an isentropic expansion is clearly greater than that in a free expansion.
However, since the turbine is to be operated with a two-phase mixture, the isentropic expansion process has certain practical
difficulties.
To overcome these, only a portion of the gas leaving the compressor may be expanded isentropically. The remaining portion
is cooled in a heat exchanger before it is expanded in a throttle valve.
The saturated gas leaving the turbine is used to cool the portion of the gas that is throttled. In this way, the inlet stream to the
valve can be cooled to a very low temperature, which will result in greater liquefaction.
The cost of power is an important consideration in the commercialization of a liquefaction process, and hence, it is essential
that the thermodynamic efficiency of the process is known. This is defined as the ratio of the minimum reversible work for the given
process to the actual work. This can be evaluated as the product of two other efficiencies, viz., the cycle efficiency and practical
efficiency.

The reversible work is the least possible amount of work that is necessary to effect a given change in the state of the system.
It is given by the second law of thermodynamics as
– W = DH – T0DS
Where T0 is the temperature of the heat sink to which heat may be rejected in large quantities.
The reversible work depends only on the initial and final states of the system and is independent of the cycle.

References;
1.Smith, J.M;VanNess,H.C;&Abott,M.C;”introduction to chemical Engineering Thermodynamics”,McGraw
Hill,7tEdition,2004
2.Narayanan,K.V; “A Text Book of Chemical Engineering Thermodynamics”,prentice Hall of india pvt.Ltd;2001