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CHAPTER – I - BASIC CONCEPTS OF THERMODYNAMICS
Introduction – macroscopic and microscopic approach – system – control volume
– properties – processes and cycles – homogeneous and heterogeneous system
– thermodynamic equilibrium – quasi static process.
REFERENCES:
1. Y.A. CENGEL, M.A. BOLE, - THERMODYNAMICS – AN ENGINEERING
APPROACH.
2. ROGERS & MAYTHEW – ENGINEERING THERMODYNAMICS –
Longman Publishers.
3. EASTOP & MEEONKEY – APPLIED THERMODYNAMICS FOR
ENGINEERING TECHNOLOGISTS
4. R. JOEL – ENGINEERING THERMODYNAMICS - Longman Publishers.
5. P.K. NAG – ENGINEERING THERMODYNAMICS - Tata McGraw –Hill
Publishing Company Limited, New Delhi.
MARK DISTRIBUTION:
ATTENDANCE : 5 MARKS
MID TERM EXAM : 30 MARKS
ASSIGNMENT : 5 MARKS
FINAL EXAM : 60 MARKS
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TOTAL MARKS : 100 MARKS
CHAPTER – I
BASIC CONCEPTS OF THERMODYNAMICS
1.1. Introduction:
Thermodynamics is the branch of science which deals with the transfer of energy
and its effect on physical properties of substances. It is based upon observations of
common experience which have been formulated into thermodynamics laws. These laws
govern the principles of energy conversion. Thermodynamics applications are found in
the fields of technology, notably internal combustion engines, steam turbines, steam and
nuclear power plants, air conditioning, refrigeration, jet propulsion compressor etc.
1.3. System:
A thermodynamic system is defined as a quantity of matter or a region in space
upon which attention is concentrated in the analysis of a problem. Everything external to
the system is called as surroundings or the environment. The system is separated from the
surrounding by the system boundary. The boundary may fixed or moving. A system and
its surroundings together comprise a universe.
1.4. Types of system:
1.4.1. Closed system:
It is a type of system of fixed mass. There is no mass transfer across the system
boundary. There may be energy transfer into or out of the system. Ex: a certain quantity
of fluid in a cylinder bounded by a piston constitutes a closed system.
System
No mass transfer
Energy in Surroundings
System
Surroundings
Energy in
Mass out
1.4.3. Isolated system:
Isolated system is one in which there is no interaction between the system and
surroundings. It is of fixed mass and energy, and there is no mass or energy transfer
across the system boundary.
V
Change of state and process: Any operation in which one or more of the properties of a
system changes is called a change of state. The succession of states passed through
during a change of state is called the path of the change of state. When the path is
completely specified, the change of state is called a process. Eg. Constant pressure
process.
Cycle: A thermodynamic cycle is defined as a series of state changes such that the final
state is identical with the initial state.
When the conditions for any one of the three types of equilibrium are not
satisfied, a system is said to be in a non equilibrium state.
Now if the single weight on the piston is made up of several very small pieces of
weights (figure.3) and these weights are removed one by one very slowly from the top of
the piston, at any instant of the upward travel of the piston, if the gas system is isolated,
the departure of the state of the system from the thermodynamic equilibrium state will be
infinitesimally small.
So every state passed through by the system will be an equilibrium state. Such a
process, which is but a locus of all the equilibrium points passed through by the system,
is known as a quasi – static process.
CHAPTER – II
TEMPERATURE SCALE AND ENERGY INTERACTIONS
2.1. Introduction:
The property which distinguishes thermodynamics from other sciences is
temperature. One might say that temperature bears as important a relation to
thermodynamics as force does to statistics or velocity does to dynamics. Temperature is
associated with the ability to distinguish hot from cold. When two bodies at temperatures
are brought into contact, after some time they attain a common temperature and are then
said to exist in thermal equilibrium.
2.3.3. Thermocouple:
which depends on the difference in temperature between the hot and cold junctions and
is, therefore, a thermodynamic property of the circuit. This e.m.f. can be measured by a
micro voltmeter to a high degree of accuracy. The choice of metals depends largely on
the temperature range to be investigated, and copper – constantan, chromel – alumel and
platinum – platinum – rhodium are typical combination in use.
A thermocouple is calibrated by measuring the thermal e.m.f. at various known
temperatures, the reference junction being kept at 00 c.
The results of such measurements on most thermocouples can usually be
represented by a cubic equation of the form.
ε = a + bt + ct2 + dt3
Where ‘ε’ the thermal e.m.f. The constants a, b, c and d are different for each
thermocouple.
The advantage of thermocouple is that it comes to thermal equilibrium with the
system whose temperature is to be measured quite rapidly, because its mass is small.
Gas system
p1, v1
Let the piston move out to a final position 2, which is also a thermodynamic
equilibrium state specified by pressure p2 and volume V2. At any intermediate point in the
travel of the piston, let the pressure be p and V. This must be an equilibrium state, since
macroscopic properties p and V are significant only for equilibrium states. When the
piston moves an infinitesimal distance dl, and if ‘a’ be the area of the piston, the force
F = p.a
And the infinitesimal amount of work done by the gas on the piston.
dW = F.dl = p.a.dl = p.dV
Where,
dV = a.dl = infinitesimal displacement volume.
The differential sign in dW is work in infinitesimal volume.
When the piston moves out from position 1 to position 2 with the volume
changing from V1 and V2, the amount of work W done by the system will be
W1-2 = integral of pdV
The magnitude of the work is given by the area under the path 1-2 as shown in
below figure. Since p is at all times a thermodynamic co-ordinate, all the states passed
through by the system as the volume changes from V1 to V2 must be equilibrium states,
and path 1-2 must be quasi – static. The piston moves infinitely slowly so that every state
passed through is an equilibrium state. The integration pdV can be performed only on a
quasi – static path.
p
p1 ----
p2 ------------------
v
v1 v2
Work transfer
1 2
p W1-2
v1 v2 v
b) Constant volume process:
It is also called as isochoric process.
W1-2 = pdV = 0.
p ------------ 1
------------ 2
V
p2 ------------------
V
v1 v2
-----------------------------
System
Weight
Flow area A1
The amount of work involved in each process is not the function of the end states of
the process. It depends on the path of the system follows.
System
Surroundings
Q (- ve)
Heat flow into the system is taken as positive, and heat flow out of the system is
taken as negative.
A process, in which no heat crosses the boundary of the system, is called an
adiabatic process. A wall which is impermeable to the flow of heat is an adiabatic wall,
where as a wall which permits the flow of heat is a diathermic wall. The unit of heat
transfer is Joule in SI unit and calorie in MKS unit.
One calorie is the energy required to raise the temperature of 1gram of water by
1degree Celsius. [1 cal = 4.187 J]
CHAPTER – III
FIRST LAW OF TD FOR CLOSED AND OPEN SYSTEM
3.1. Introduction:
According to conservation of energy, “Energy can be neither created nor
destroyed but it can be transferred from one form to other form”. The transfer of heat and
the performance of work may both cause the same effect in the system. Heat and work
are different forms of the same entity, called energy, which is conserved. Energy which
enters the system as heat may leave the system as work, or energy which enters the
system as work may leave as heat.
This is applied for a closed system undergoing a cycle and undergoing a change
of state.
Figure 1
The system was initially at temperature t1, the same as that of atmosphere, and
after work transfer let the temperature rise to t2. The pressure is always 1 atm. The
process 1-2 undergone by the system is shown in figure 2 in an generalized
thermodynamic coordinates X and Y. let the insulation now be removed. The system and
surroundings interact by heat transfer till the system returns to the original temperature t1,
attaining the condition of equilibrium with the atmosphere. The amount of eat transfer Q2-
1 from the system during the process, 2-1 as shown in figure.2.
1 Q1-2
Y Figure 2
W1-2 2
X
The system thus executes the cycle, which consists of a definite amount of work
input W1-2 to the system followed by the heat transfer of an amount of heat Q 2-1 from the
system.
If the cycle involves many more heat and work quantities, the same result will be
found. It is expressed algebraically,
(∆W) cycle = J (∆Q) cycle
Where ‘J’ - The joule’s equivalent. This is expressed in the form
∫dW = ∫dQ
Where the symbol ∫ denotes the cyclic integral for the closed path.
This is called first law for a closed system undergoing a cycle.
cycles, and the algebraic summation of all energy transfer across system boundaries are
zero.
But if a system undergoes a change of state during which both heat and work
transfer are involved, the net energy transfer will be stored or accumulated within the
system. If Q is the amount of heat transferred to the system and W is the amount of work
transferred from the system during the process as shown in figure, the net energy transfer
(Q-W) will be stored in the system. Energy in storage is neither heat nor work, and is
given the name internal energy of the system.
Q
System
Therefore
Q – W = ∆E
Where ‘∆E’ - increase in the energy of the system.
Or
Q = ∆E + W
Here Q, W and ∆E are all expressed in the same units (in Joules). Energy may be
stored by a system in different modes.
If there is more energy transfer quantities involved in the process as shown in
figure, the first law gives
Q2
Q3
W3
Q1
W1 System
W2 W4
3.7. Enthalpy:
The enthalpy of a substance h, is defined as
h = u + pv.
It is an intensive property of a system.
Total enthalpy
H = U + pV.
3.8. Specific heat at constant pressure:
The specific heat at constant pressure (cp) is defined as the rate of change of
enthalpy with respect to temperature when the pressure is held at constant.
Q Q
Engine Engine
W W
3.11. First law applied to Flow processes or First law applied to open system:
3.11.1. Steady flow processes:
As a fluid flows through a certain control volume, its thermodynamic properties
may vary along the space coordinates as well as with time. If the rates of flow of mass
and energy through the control surface change with time, the mass and energy with in the
control volume also would change with time.
At the steady state of a system, any thermodynamic property will have a fixed value at a
particular location, and will not alter with time. Thermodynamic properties vary along
with the space coordinates, not with the time. ‘Steady state’ means that the state is steady
or invariant with time.
3.11.2. Mass balance and energy balance in a simple steady flow process:
CHAPTER – IV
SECOND LAW OF THERMODYNAMICS
4.1. Introduction:
The first law of thermodynamics states that a certain energy balance will hold
when a system undergoes a change of state or a thermodynamic process. But it does not
give any information on whether that change of state or the process is at all feasible or
not. The first law cannot indicate whether a metallic bar of uniform temperature can
spontaneously become warmer at one end and cooler at the other. All that the law can
state is that if this process did occur, the energy gained by one end would be exactly
equal to that lost by the other. It is the second law of thermodynamics which provides the
criterion as to the probability of various processes.
Joule’s experiment amply demonstrates that energy, when supplied to a system in
the form of work, can be completely converted into heat. But the complete conversion of
heat into work in a cycle is not possible. So heat and work are not completely
interchangeable forms of energy. Work is said to be high grade energy and heat is low
grade energy. The complete conversion of low grade energy into high grade energy in a
cycle is impossible.
If Q2 = 0 (i.e. W = Q1, or eff. = 100 % ) the heat engine will produce net work in a
complete cycle by exchanging heat with only one reservoir, thus violating the Kelvin –
Planck statement. Such a heat engine is called a perpetual motion machine of the second
kind, abbreviated to PMM2. a PMM2 is impossible.
4.6. Refrigerator:
A refrigerator is a device which, operating in a cycle, maintain a body at a
temperature lower than the temperature of the surroundings. There is a performance
parameter in a refrigerator cycle, called the co efficient of performance, abbreviated to
COP, which is defined as the ratio of desired effect produced to the work input. The COP
value always less than one for refrigerator.
initial states, without producing any changes in the rest of the universe. Let the state of a
system be represented by A and let the system be taken to state B by following the path
A-B. If the system and also the surroundings are restored to their initial states and no
change in the universe is produced, then the process A-B will be a reversible process. In
the reverse process, the system has to be taken from state B to A by following the same
path B-A. A reversible process should not have any trace to show that the process had
ever occurred. A reversible process is an idealized hypothetical process, approached only
as a limit. It is said to be an asymptote to reality.
4.8.2. Irreversible or natural process:
Any natural process carried out with a finite gradient is an irreversible process.
All spontaneous processes are irreversible. The causes of irreversibility are mentioned
below:
1. Lack of equilibrium during the process
2. Involvement of dissipative effects
1. Lack of equilibrium during the process:
The lack of equilibrium (mechanical, thermal, chemical) between the system and
its surroundings or between two systems, or two parts of the same system, causes a
spontaneous change which is reversible. The following are specific examples in this
regard.
• Heat transfer through a finite temperature difference
• Lack of pressure equilibrium within the interior of the system or between the
system and the surroundings.
• Free expansion
2. Irreversibility due to dissipative effects:
The irreversibility of a process may due to the dissipative effects in which work is
done without producing an equivalent increase in the kinetic or potential energy of any
system. The transformation of work into molecular internal energy either of the system or
of the reservoir takes place through the agency of such phenomena as friction, viscosity,
inelasticity, electrical resistance, and magnetic hysteresis. These effects are known as
dissipative effects, and work is said to be dissipated.
4.11. Entropy:
When the first law of thermodynamics was applied for thermodynamic processes,
the existence of a property, the internal energy, was found. Similarly, the second law of
thermodynamics was applied for thermodynamic processes, it leads to the definition of a
new property, known as entropy. In fact, thermodynamics is the study of three E’s,
namely energy, equilibrium and entropy. It is a function of quantity of heat which
shows the possibility of conversion of heat into work.
It may be stated roughly that the entropy of a system is a measure of degree of
molecular disorder existing in the system.
4.12. Clausius’ theorem:
Let a system be taken from an equilibrium state i to another equilibrium state f by
following the reversible path i-f, as shown in figure. Let a reversible adiabatic i-a be
drawn through i and another reversible adiabatic b-f be drawn through f. then a reversible
isotherm a-b is drawn in such a way that the area under i-a-b-f is equal to the area under
i-f. Applying the first law for
Process i-f
Qi-f = Uf – Ui + Wif
Process i-a-b-f
Qiabf = Uf – Ui + Wiabf
Since
Wif = Wiabf
Therefore
Qi-f = Qiabf = Qia + Qab + Qbf
Since
Qia= 0 and Qbf = 0
Qif = Qab
Heat transferred in the process i-f is equal to the heat transferred in the isothermal
process a-b.
Thus any reversible path may be substituted by a reversible zigzag path, between
the same end states, consisting of a reversible adiabatic followed by a reversible isotherm
and then by a reversible adiabatic, such that the heat transferred during the isothermal
process is the same as that transferred during the original process.
Let a smooth closed curve representing a reversible cycle be considered (Refer
figure). Let the closed cycle be divided into a larger number of strips by means of
reversible adiabatics. Each strip may be closed at the top and bottom by reversible
isotherms. The original closed cycle is thus replaced by a zigzag closed path consisting of
alternate adiabatic and isothermal processes, such that the heat transferred during all the
isothermal processes is equal to the heat transferred in the original cycle. Thus the
original cycle is replaced by a number of Carnot cycles. If the adiabatics are close to one
another and the number of Carnot cycles is large, the saw-toothed zigzag line will
coincide with the original cycle.
For the elemental cycle abcd, dQ1 heat is absorbed reversibility at T1, and dQ2
heat is rejected reversibility at T2
1 R2
P R1
2
CHAPTER – VII
PSYCHROMETRY
7.1. Introduction:
The name ‘psychrometrics’ is given to the study of the properties of air – water
vapour mixtures. It also includes the study of behavior of dry air and water vapour
mixing under various sets of conditions. Atmospheric air is considered to be a mixture of
dry air and water vapour. The control of moisture content in the atmosphere is essential
for the satisfactory operation of many processes involving hygroscopic materials like
paper and textiles, and its important in comfort air conditioning.
Moist air: It is the mixture of dry air and water vapour. The amount of water vapour
present in the air depends upon the absolute pressure and temperature of the mixture.
Saturated air: It is the mixture of air and water vapour, when the air has diffused the
maximum amount of water vapour into it.
Humidity: The amount of water vapour present in the air is called as Humidity.
Specific humidity: It is defined as the mass of water vapour per unit mass of dry air in a
mixture of air and water vapour.
W=m/G
Specific humidity is the maximum, when air is saturated at temperature ‘T’
Wmax = ms / G
Finally,
W = 0.622 (pw / p - pw)
Ws = 0.622 (ps / p - ps)
Degree of saturation: It is the ratio of actual specific humidity and the saturated specific
humidity. It is denoted by the symbol ‘μ’.
μ = (pw /ps) (p - ps / p - pw)
Dry bulb temperature (DBT): It is the temperature measured with the help of an
ordinary thermometer. It is measured in degree Celsius.
Wet bulb temperature: It is the temperature measured with the help of thermometer,
when the bulb is enveloped by a cotton wick saturated with water.
Dew point temperature: It is the temperature at which the water vapour begins to
condense.
Wet bulb depression: It is the temperature difference between DBT and WBT.
Dalton’s law of partial pressures: It states, “The total pressure exerted by the mixture
of air and water vapour is equal to the sum of the pressures, which each constituent
would exert, if it occupied the same space by itself”.
P = Pa + Pw