Laws of Thermodynamics
Laws of Thermodynamics
Law of Thermodynamics
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LAWS OF THERMODYNAMICS A FOCUSSED APPROACH
Laws of Thermodynamics
THERMODYNAMIC SYSTEM & SURROUNDINGS
A thermodynamic system may be considered as a quantity of working substance with which
heat and work interactions are studied. The envelope enclosing the system, which may be real
or hypothetical is known as boundary of the system. The region outside the system is known
as surroundings. The transfer of mass and energy take place between the system and
surroundings.
Thermodynamic system are classified as
(a) closed (b) open (c) isolated
Closed systems
No mass can flow in or out, only heat or work or both may flow into and out of the closed
system. If heat is supplied to the cylinder from external source, the volume of the gas
increases and the piston moves up. Work transfer occurs due to the movement of the
boundary of the system.
The system turbine, gas turbine and rotary compressor are good examples of open system.
An isolated system
V
If there is any change in the requirement of work and heat to bring back the system from state
B to A, the process becomes irreversible. The processes used in practice are mostly
irreversible due to friction, heat transfer and mixing, but in many cases idealization is used
for analysis.
PRESSURE
The standard atmospheric pressure is defined as the pressure produced by a column of
mercury 769 mm high. The standard atmospheric pressure is 1.0332 kgf/cm2 and is denoted
by atm. In S.I. units, it is expressed in N/m2 or Pascal abbreviated as Pa. Various pressure
units are
1 Pa = 1 N/m2
1 bar = 105 Pa = 100 kPa = 0.1 MPa
1 atm = 101.325 kPa = 1.01325 bar
1 metre mercury head = 1.3366 bar
Consider a closed system of a piston and cylinder as shown in Fig. given above. The net
pressure of the gas in the system causes the piston to move in the forward direction. The force
acting on the piston is p.A, where A is the area of the piston, if the piston moves through a
small distance dx, the work done by the gas on the piston = p.A dx = p.dv as A.dx is the
change in the volume of the gas. If the gas expands from state 1 to 2 as shown in the figure,
the work done is given by,
v2
W p.dv
v1
HEAT
Heat is defined as the energy transferred without transfer of mass across the boundary or a
system due to a temperature difference between the system and surroundings.
The direction of heat transfer is taken from the high temperature system to the low
temperature system. Heat flow into a system is taken to be positive, and heat flow out of a
system is taken as negative.
The amount of heat transferred during a process or work done by the system during the same
process is dependent on the path followed during the process. Though the end conditions are
same. as shown in figure below.
The heat exchange and work don during the processes will be different for the two different
paths. Thus heat and work are said to be path functions and not point functions (or
properties).
INTERNAL ENERGY
Matter is composed of molecules which move continuously and randomly. In gases,
movement of the molecules is more pronounced than in solids and liquids. Matter possesses
internal kinetic energy due to the motion of its molecules. In addition to this internal K.E.,
matter has internal potential energy due to relative position of their molecules. The sum of
these two energies is known as specific internal energy (or simply internal energy) and it is
denoted by u, the unit commonly used being J/kg or kJ/kg. If the temperature of a gas is
increases by adding heat, the molecular activity increases. Therefore the internal energy of a
gas is a function of its temperature and its value can be increased or decreased by adding or
removing heat from the gases which are commonly used as working fluids.
Total internal energy is denoted by U, its unit is J or kJ.
ENTHALPY
Enthalpy (H) of a substance at any point is quantification of energy content in it, which could
be given by summation of internal energy and flow energy. Enthalpy is very useful
thermodynamic property for the analysis of engineering systems.
Mathematically, it is given as,
H U PV
On unit mass basis, the specific enthalpy could be given as,
h u pv
State the zeroth law of thermodynamics. Prove that this law is the basis for all temperature
measurements. How the mercury in the thermometer able to find the temperature of a body
using zeroth law of thermodynamics. How does the Seebeck effect make use of temperature
measurement by a thermocouple?
Zeroth law of thermodynamics states that if the bodies A and B are in thermal equilibrium
with a third body C separately then the two bodies A and B shall also be in thermal
equilibrium with each other. This is the principle of temperature measurement. Block
diagram shown in Fig. a and b show the zeroth law of thermodynamics and its application for
temperature measurement respectively.
(a)
(b)
Mercury thermometer. The major significance or use of zeroth law of thermodynamics is
in mercury thermometer.
When a thermometer is inserted in to the fluid, the fluid (say A) and the glass wall (say B)
will attain thermal equilibrium (they are at same temperature). The glass wall (B) and
mercury (say C) are at thermal equilibrium.
So A and B ; B and C are in thermal equilibrium.
This states that body A and C are in thermal equilibrium. Thus the temperature read by
mercury fluid in the bulb is the temperature of the measuring fluid.
Seebeck effect. Thermo electric thermometer works on the principle of Seebeck effect.
Seebeck effect says that a current flows or e.m.f. is produced in a circuit of two dissimilar
metals having one junction as hot while other as cold junction. Current produced in this way
is called thermo electric current while the e.m.f. produced is called thermo e.m.f.
Measurement of temperature is being done by knowing the e.m.f. produced which is the
thermometric property.
Q 2 Q3 Q1 E (W2 W3 W1 W4 )
Applying the energy balance at the two sections, it can be given as,
Energy added to the system + Stored energy of the fluid at inlet
= Stored energy of the fluid at outlet
Quantifying the various energies;
Energy of fluid at inlet shall comprise of stored energy and flow energy as given here.
= m1(e1 + p1v1)
Similarly, energy of fluid at outlet shall comprise of stored energy and flow energy,
= Stored energy + Flow energy
= m2 (e2 + p2v2)
The energy added to the system shall be the net energy interaction due to heat and work
interactions.
=Q–W
Writing energy balance, mathematically;
Q – W + m1 (e1 + p1v1) = m2 (e2 + p2v2)
or Q + m1(e1 + p1v1) = W + m2(e2 + p2v2)
If the mass flow rates at inlet and exit are same, then
Q + m(e1 + p1v1) = W + m(e2 + p2v2)
On unit mass basis
For path A Q A E A WA
For path B Q B E B WB
W cycle
Q cycle
or WA WB Q A Q B
i.e. Q A WA WB Q B
i.e. E A E B
Similarly, had the system returned from state 2 to state 1 by path C instead of path B, then
E A E C
Also E B E C
Therefore, it is seen that the change in energy between two states of a system is the same,
whatever path the system may follow in undergoing that change of state. Further, energy has
a definite value for every state of the system.
C12 C2
h1 Q h2 2 W
2 2
The sign of Q is negative because heat is rejected (or comes out of the boundary). The sign of
W is positive because work is done by the system (or work comes out of the boundary).
Steam Nozzle
In case of a nozzle as the enthalpy of the fluid decreases and pressure drops simultaneously
the flow of fluid is accelerated. This is generally used to convert the part of the energy of
steam into kinetic energy of steam supplied to the turbine.
C2 C12 2(h1 h2 )
Example
In a nozzle air at 627°C and twice atmospheric pressure enters with negligible velocity and
leaves at a temperature of 27°C. Determine velocity of air at exit, assuming no heat loss and
nozzle being horizontal. Take Cp = 1.005 kJ/kg.K for air.
Solution
Applying steady flow energy equation with inlet and exit states as 1, 2 with no heat and work
interaction and no change in potential energy.
C12 C2
h1 h2 2
2 2
Given that, C1 ≈ 0, negligible inlet velocity
C2 2(h1 h2 )
In a gas turbine unit, the gases flow through the turbine is 15 kg/s and the power developed
by the turbine is 12000 kW. The enthalpies of gases at the inlet and outlet are 1260 kJ/kg and
Solution
C2 2 1102
Kinetic energy at outlet = 6.05 kJ / kg
2 2 x1000
Substituting these values in eqn. (1), we get
1260 + 1.25 + Q = 400 + 6.05 + 800
∴ Q = – 55.2 kJ/kg
i.e., Heat rejected = + 55.2 kJ/kg = 55.2 × 15 kJ/s = 828 kW.
(ii) Inlet area, A
Using the relation,
CA
m
v
vm 0.45 x15
A 0.135 m 2
C 50
Solution
Show that a change in internal energy of a system is independent of the path followed by the
system.
Solution
Consider a system which changes its state from state 1 to state 2 by following path, and
returns from state 2 to state 1 by following the path B as shown in following figure.
QA = EA + WA (1)
and path B
QB = EB + WB (2)
The processes A and B together constitute a cycle, for which
Wcycle Qcycle
or WA + WB = QA + QB
or QA – W A = W B – Q B (3)
From eq (1, 2, 3)
EA = -EB
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Similarly had the system returned from state 2 to state 1 following the path C, instead of path
B, then
EA = -EC
Therefore EB = EC
which means the change in internal energy is independent of the path followed and
therefore internal energy is a thermodynamic property.
Show that the first law of thermodynamics implies that a Perpetual Motion Machine of the
First Kind (PMMFK) is impossible
Solution
We know that the macroscopic modes of energy can be convened from one form to the other
and work can be obtained. However, the microscopic modes of energy cannot be readily
converted into macroscopic modes of energy. An important application of thermodynamics is
to devise means of converting the microscopic modes of energy into the macroscopic modes
of energy. For this purpose heat engines which work cyclically arc devised. The first law of
thermodynamics when applied to a cyclic process gives
(dQ dW ) 0
or dQ dW
or Q W
where Q is the net heat interaction and W is the net work delivered.
An imaginary device which would deliver work continuously without absorbing energy as
heat is called a Perpetual Motion Machine of the First Kind (PMMFK). A perpetual motion
machine of the first kind has to operate on a cycle to deliver work continuously. If the device
does not absorb any energy as heat in a cycle, then dQ Q 0 . Then the first law of
thermodynamics tells that for such a device dW W 0 . Thus, the first law of
thermodynamics implies that it is impossible to devise a PMMFK. A PMMFK violates the
first law of thermodynamics.
State the limitations of the first law of thermodynamics with the help of examples involving
heat and work interactions.
We know that kinetic energy and potential energy are interconvertible and the macroscopic
modes of energy (KE and PE) can be readily converted into work. The conversion of
microscopic modes of energy (that is energy associated with the random molecular motion of
the matter) or internal energy into work requires a device called heat engine. Is it possible for
the complete conversion of internal energy into work in a heat engine? Or is it possible to
devise a heat engine, the efficiency (defined as the ratio of the net work done to the energy
absorbed) of which is equal to one? Is it possible to transfer energy as heat spontaneously
from a body at a lower temperature to a body at a higher temperature? All the above
questions which deal with work and heat interactions cannot be answered by the application
of the first law of thermodynamics and hence they reflect the limitations of the first law
thermodynamics.
Example
A stationary mass of gas is compressed without friction from an initial state of 0.3 m3 and
0.105 MPa to a final state of 0.15 m3 and 0.105 MPa, the pressure remaining constant during
the process. There is a transfer of 37.6 kJ of heat from the gas during the process. How much
does the internal energy of the gas change?
Solution
W1 2 pdV p V2 V1
V2
(1)
V1
Example
In a closed system
(a) 17 kJ of heat is added to the system whilst 8 kN-m of work is performed by the system,
determine the change in internal energy of the system.
Solution
We can apply the energy equation as obtained from the first law of thermodynamics applied
to a closed system, i.e.
Q W U
Heat Q should be taken positive if it is supplied to the system, and negative if rejected by the
system. Work W should be taken positive if it is developed by the system and negative if
supplied to the system.
(a) Q W U
17000 = 8000 + U (J = 1 N-m/J)
17000 8000
U 9 kJ (increase)
1000
(b) Q W U
0 16000 U U 16 kJ (decrease)
(b) Q W U
(d) Q W U U
W
21 = +0 W = 21 kN-m (work developed by the system)
J
Example
When a system is taken from state a to state b, in figure, along path acb, 84 kJ of heat flow
into the system, and the system does 32 kJ of work. (a) How much will the heat that flows into
the system along path adb be, if the work done is 10.5 kJ? When the system is returned from b
to a along the curved path, the work done on the system is 21 kJ. Does the system absorb or
liberate heat, and how much of the heat is absorbed or liberated? (c) If Ua = 0 and Ud = 42
kJ, find the heat absorbed in the processes ad and db.
Solution
Qacb = 84 kJ
Wacb = 32 kJ
We have
Qacb = Ub - Ua + Wacb
Ub - Ua = 84 - 32 = 52 kJ Ans.
(a) Qadb = Ub - Ua + Wadb
= 52 + 10.5
= 62.5 kJ Ans.
(b) Qb-a = Ua - Ub + Wb-a
= -52 -21
= - 73 kJ Ans.
The system liberates 73 kJ of heat.
(c) Wadb = Wad + Wdb = Wad = 10.5 kJ
Qad = Ud - Ua + Wad
42 - 0 + 10.5 = 52.5 kJ
Now Qadb = 62.5 kJ = Qad + Qdb
Qdb = 62.5 - 52.5 = 10 kJ Ans.
Example
A piston an cylinder machine contains a fluid system which passes through a complete cycle
of four processes. During a cycle, the sum of all heat transfers is -170 kJ. The system
completes 100 cycles per min. Completer the following table showing the method for each
item, and compute the net rate of work output in kW.
Process Q (kJ/min) W (kJ/min) E(kJ/min)
a-b 0 0 -
b-c 21,000 - -
c-d - 2,100 - - 36,600
d-a - - -
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Solution
Process a - b:
Q = E + W
0 = E + 2170
E = - 2170 kJ/min
Process b - c:
Q = E + W
21,000 = E + 0
E = - 21,000 kJ/min
Process c - d:
Q = E + W
- 2100 = - 36,600 +W
W = 34,500 kJ/min
Process d - a:
Q 170kJ
cycle
Problem
A mass of 8 kg gas expands within a flexible container so that the p-v relationship is of the
form pv1.2 = const. The initial pressure is 1000 kPa and the initial volume is 1 m3. The final
pressure is 5 kPa. If specific internal energy of the gas decreases by 40 kJ/kg, find the heat
transfer in magnitude and direction.
Answer: +2615 kJ
Problem
A mixture of gases expands at constant pressure from 1 MPa, 0.03 m3 to 0.06 m3 with 84 kJ
positive heat transfer. There is no work other than that done on a piston. Find E for the
gaseous mixture.
Answer: 54 kJ
A centrifugal pump delivers 50 kg of water per sec. The inlet and outlet pressures are 1 bar
and 4.2 bar, respectively. The suction is 2.2 m below the centre of the pump and delivery is
8.5 m above the centre of the pump. The suction and delivery pipe diameters are 20 cm and
10 cm, respectively. Determine the capacity of electric motor to run the pump.
Solution
Given data
C2 C2
mw u1 p1v1 1 Z1 g Q mw u2 p2 v2 2 Z 2 g W (1)
2 2
Considering the datum from suction 1, as shown
Z1 = 0, Z2 = 8.5 + 2.2 = 10.7 m
u2 – u1 = 0 ; Q = 0
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Thus eqn. (i) reduces to
C 2 C2 2
W mw ( p1v1 p2 v2 ) ( Z1 Z 2 ) g 1 (2)
2
As water is incompressible fluid
v2 = v1 = v = 1/ = 1/1000
The mass flow through inlet and exit pipe is given by
mw d12C1 d 2 2 C2
4 4
50 (0.2) 2 C1 x1000
4
C1 = 1.59 m/s
Similarly C2 = 6.37 m/s
Substituting the values in (2)
1 1 1.592 6.37 2
W 50 1x105 x 4.2 x105 x (0 10.7) x 9.81
1000 1000 2
= 22.2 kW
SPECIFIC HEAT
Specific heat of a substance is the amount of heat that must be added to unit mass of the
substance to raise the temperature through 1oC. The symbol “c” will be used for specific
heat.
Q
c(or C) J / kgK
m.t
Gases have two specific heats, namely, specific heat at constant volume and specific heat at
constant pressure.
Specific heat at constant volume (Cv): The amount heat required in kJ to raise the
temperature of 1 kg of the gas through 1 K at constant volume is known as specific heat at
constant volume. There is no work of expansion as the gas volume remains constant, and ,
therefore, all the heat supplied is used to increase its internal energy.
Specific heat at constant pressure (Cp): The amount of heat required in kJ to raise the
temperature of 1 kg of the gas through 1 K at constant pressure is known as specific heat at
constant pressure.
When the gas is heated at constant pressure, it gets expanded and moves the piston through a
distance L., therefore in addition to the heat required to increase the kinetic energy of the
molecule, further heat must be added to perform the work of moving the piston through a
Example
The specific heat of a gas at constant volume is 3.15 kJ/kg-oC and the ratio of specific heats
= 1.66 for the same gas. If 1.5 kg of this gas is heated from 50oC to 350oC at constant
pressure, determine heat supplied to the gas in kJ.
SOLUTION
We know that
Cp
Cv
Practically Wnet < Q1. Hence an engine can not be 100% efficient.
If Q2 > 0, there will always be heat rejection.
If Q2 = 0, then = 1 (100%), then we get perpetual motion machine (PMM). PMM is
impossible. Figure (a) shows a PMM.
(a) (b)
A heat engine has, therefore, to exchange heat with two thermal energy reservoirs at two
different temperatures to produce net work in a complete cycle (figure b). Motive power can
be produced till there is no difference of temperature.
Clausius’ Statement
It is impossible to construct a device working in cyclic process whose sole effect is transfer of
heat from a body at a lower temperature to a body of higher temperature.
Heat cannot flow of itself from a body at a lower temperature to a body at a higher
temperature. Some work must be expended to achieve this.
A schematic of the device which is impossible to devise according to the Clausius statement
of the second law of thermodynamics is shown in figure.
State the second law of thermodynamics as stated by Kelvin-Plank and Clausius. Show the
equivalence of the above two statements.
Solution
Equivalence of the Two statements: The equivalence is established by showing that any
device that violates Clausius statement leads to violation of Kelvin Planck statement and vice
versa.
Violation of the Kelvin-Planck statement leads to violation of Clausius statement of the second law of
thermodynamics.
To prove that violation of Kelvin-Planck statement implies the violation of the Clausius
statement, let us suppose that the Kelvin-Planck statement of the second law of
thermodynamics is incorrect. that is, it is possible to devise a cyclically operating device A
which absorbs energy Q as heat from a thermal reservoir at high temperature T1 and delivers
an equivalent amount of work W (W = Q) in a cycle as shown in figure.
Now let us consider another cyclically operating device B which absorbs energy Q2 as heat
from a low temperature reservoir at T2 (T2 <T1) and rejects energy Q1 as heat to a high
temperature reservoir at T1 when work W is done on the device in one cycle as shown in
figure (a). The device B is aided and hence it is not in violation of the Clausius statement.
The work done on the device B is given by W = Q1 - Q2. Let us consider the combination of
the devices A and B as shown in figure (b).The work delivered by the device A is used to
operate the device B and part of the energy Q rejected by device B is absorbed by device A.
W Q
or Q Q1 Q2
or Q1 Q Q2
The combination of the devices A and B is shown in figure (b). The combined device absorbs
energy Q2 as heat from a low temperature reservoir at T2 and rejects energy Q2 (Q2 = Q1 - Q)
as heat to the high temperature reservoir at T1 while it is unaided by any external agency.
That is, it is possible to devise a self acting cyclically operating device which transfers energy
as heat from a low temperature body to a high temperature body. This is in violation of the
Clausius statement of the second Law of thermodynamics. Thus, violation of the Kelvin-
Planck statement leads to violation of the Clausius statement.
Violation of Clausius statement leads to violation of the Kelvin-Planck statement of the
second law of thermodynamics.
To prove that violation of Clausius statement leads to violation of Kelvin-Planck statement,
let us assume that the Clausius statement of the second law of thermodynamics, is incorrect.
That is, it is possible to devise a self acting (or externally unaided) cyclically operating device
A which transfers energy Q as heat from a low temperature reservoir at T2 to a high
temperature reservoir at T1 (T1 > T2) as shown in figure (a). Now. let us consider another
device B which absorbs energy Q1 as heat from a high temperature reservoir at T1, does
work. W on the surroundings and rejects energy Q as heat to the low temperature reservoir at
T2, as shown in figure (a). The device B does not violate the Kelvin-Planck statement of the
second law of thermodynamics. The work delivered by device B is given by
W Q1 Q
Now, let us combine the devices A and B such that the energy Q rejected as heat at
temperature T2, by device B is directly fed to the device A and the energy Q rejected as heat
at temperature T1 by device A is directly absorbed by device B. The difference in the energy
(Q1 - Q) is absorbed by device B from the high temperature reservoir at T1 and the work
delivered by device B is W(W = Q1 - Q) as shown in figure (b).
Carnot Cycle
The second law of thermodynamics states that only a part of the heat supplied to the heat
engine can be converted into work. Naturally the next step is to examine the practical means
for doing so and analyse their effectiveness. Carnot postulated that the most efficient engine
is a reversible engine and be devised such an engine working on a cycle known as Carnot
cycle. All the constituent processes of the cycle are reversible processes as shown in figure
given below on p-v and T-s diagram.
Carnot cycle
1. The process 1-2 represents isothermal expansion of the working fluid in the cylinder.
2. The process 2-3 represents isentropic expansion of the working fluid.
3. The process 3-4 represents isothermal compression, and
4. The process 4-1 represents isentropic compression till the fluid reaches its original
condition completing the cycle.
The efficiency of the cycle is given by
Wnet T1 T2
Q1 T1
Carnot efficiency is the highest possible efficiency of a heat engine. The efficiency is also
independent of the type of the fluid used. Therefore it is considered as a standard of
comparison for heat engine performance.
Carnot Theorem
It states that of all heat engines operating between a given constant temperature source and a
given constant temperature sink, none has a higher efficiency than a reversible engine.
Let EA be any heat engine and EB be any reversible heat engine. We have to prove that the
efficiency of EB is more than that of EA. Let us assume that this is not true and A > B. Let
the rates of working of the engines be such that
Q1A Q1B Q1
Since A B
WA WB
Q1A Q1B
WA WB
Now, let EB be reversed. Since EB is a reversible heat engine, the magnitudes of heat and
work transfer quantities will remain the same, but their directions will be reversed, as shown
in figure (b).
Since WA > WB, some part of WA (equal to WB) may be fed to drive the reversed heat engine
B .
Since Q1A = Q1B = Q1, the heat discharged by B may be supplied to EA. The source may,
therefore, be eliminated (figure c). The net result is that EA and B together constitute a heat
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engine which, operating in a cycle, produces net work WA - WB, while exchanging heat with
a single reservoir at t2. This violates the Kelvin-Planck statement of the second law. Hence
the assumption that A > B is wrong.
Therefore B A
Q T
rev max 1 2 1 2
Q1 rev T1
T1 T2
or rev
T1
The COP (Coeff. of Performance) of a refrigerator is given by
Q2 1
(COP) refr
Q1 Q 2 (Q1 / Q 2 ) 1
For a reversible refrigerator, using
Q1 T1
Q 2 T2
T2
[COPrefr ]rev
T1 T2
Similarly, for a reversible heat pump
T1
[COPH.P. ]rev
T1 T2
CLAPEYRON’S THEOREM
It is derived from Carnot theorem.
Carnot efficiency is given by (T1 – T2)/T1 and for a small pressure drop dp, and the
corresponding temperature drop dT, the Carnot efficiency is given by dTs/Ts. Here Ts is
saturation temperature. In evaporation the heat supplied is latent heat.
dp h fg
or
dTs Ts (vg v f )
This is Clapeyron’s theorem.
The efficiency of a Carnot engine can be increased either by decreasing the sink temperature
while keeping the source temperature constant or by increasing the source temperature while
keeping the sink temperature constant. Which one of the above two possibilities is more
effective?
Solution
c 1
T2 T1 T1
c 2 T2
and T2 (T1 )
T1 T2 T12
c
T2 T1 1 T12 T1
.
c T1 T2 T2
T1 T 2
Distinguish between reversible and irreversible processes and give some examples of
irreversible processes.
Solution
A process is said to be reversible if both the system and its surroundings can be restored to
their respective initial states by reversing the direction of the process. If a process does not
satisfy the above criterion, it is an irreversible process.
Examples of irreversible processes are :
Expansion or compression with finite pressure difference.
Energy transfer as heat with finite temperature difference.
Free expansion of a gas.
Mixing of non identical gases.
Mixing of matter at different states.
Motion with friction.
Viscous fluid flow.
Spontaneous chemical reactions.
Example
Solution
Solution
Since the second law of thermodynamics distinguishes between reversible and irreversible
processes, one can use the following criterion to identify a reversible process. If a process can
proceed in either direction without violating the second law of thermodynamics, then it is a
reversible process. Suppose a process is proceeding in one direction and the assumption of
reversibility of the process leads to a violation of the second law of thermodynamics, then the
process can be called irreversible.
Solution
A heat engine is an energy conversion device. It is a cyclically operating device and its
primary objective is to convert the energy received as heat into work. It employs a working
fluid which undergoes cyclic change. The working fluid absorbs energy as heat from a source
and rejects energy as heat to a sink. The characteristics of a heat engine are :
It is a cyclically operating device.
Its primary purpose is to convert energy absorbed as heat into work.
It absorbs energy as heat from a high temperature source.
It rejects energy as heat to a low temperature sink.
It delivers some net work.
A heat engine can be represented as shown in figure.
Explain (i) heat pump (ii) refrigerator. How is COP of a heat pump related to the COP of a
refrigerator?
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Solution
Heat Pump
Heat pump refers to a device used for extracting heat from a low temperature surroundings
and sending it to high temperature body, while operating in a cycle. In other words heat pump
maintains a body or system at temperature higher than temperature of surroundings, while
operating in cycle. Block diagram representation for a heat pump is given below:
As heat pump transfers heat from low temperature to high temperature, which is non
spontaneous process, so external work is required for realizing such heat transfer. Heat pump
shown picks up heat Q2 at temperature T2 and rejects heat Q1 for maintaining high
temperature body at temperature T1.
For causing this heat transfer heat pump is supplied with work W as shown.
As heat pump is not a work producing machine and also its objective is to maintain a body at
higher temperature, so its performance can’t be defined using efficiency as in case of heat
engine. Performance of heat pump is quantified through a parameter called coefficient of
performance (C.O.P). Coefficient of performance is defined by the ratio of desired effect and
net work done for getting the desired effect.
COP = desired effect/Net work done
For heat pump :
Net work = W
Desired effect = heat transferred Q1 to high temperature body at temperature, T1.
Q1 Q1
COP
W Q1 Q2
Refrigerator
Refrigerator is a device similar to heat pump but with reverse objective. It maintains a body
at temperature lower than that of surroundings while operating in a cycle. Block diagram
representation of refrigerator is shown in given figure.
Refrigerator also performs a non spontaneous process of extracting heat from low
temperature body for maintaining it cool, therefore external work W is to be done for
realizing it.
Block diagram shows how refrigerator extracts heat Q2 for maintaining body at low
temperature T2 at the expense of work W and rejects heat to high temperature surroundings.
Performance of refrigerator is also quantified by coefficient of performance, which could be
defined as:
desired effect Q2 Q2
COPref
net work W Q1 Q2
Example
A reversible engine receives heat from a reservoir at 700oC and rejects the heat at
temperature T2. A second reversible engine receive heat reject by the first engine and reject
to the sink at 37oC. Determine the temperature T2 if (a) both the engines give same thermal
efficiency (b) both the engines develop same power.
Solution
973 T2 T2 310
973 T2
Example
An inventor claims that his petrol engine operating between temperatures of 2000oC and
600oC will produce 1 H.P.hr., consuming 120 gm of petrol having 46025 kJ/kg calorific
value. Check the validity of his claim.
Solution
As the efficiency claimed is less than the maximum possible, his claim is valid.
An inventor claims to have designed a heat engine which absorbs 1 kJ of energy as heat at
7270C and delivers 0.6 kJ of work when the ambient temperature is 270C. Would you agree
with this claim?
Solution
The maximum possible efficiency of a heat engine operating between two thermal reservoirs
is given by
W T 300
1 2 1 0.7
Q1 T1 1000
The claimed efficiency (0.6) is less than the maximum possible efficiency (0.7) and hence it
is feasible to devise such an engine.
Example
An inventor claims that his engine absorbs 300 kJ of energy from a thermal reservoir at 325
K and delivers 75 kJ of work. The inventor also states that his engine has two heat rejections:
125 kJ to a reservoir at 300 K and 100 kJ to a reservoir at 275 K. Check the validity of his
claim.
Solution
The validity of the proposed engine is checked on the basis whether it satisfies or not the first
and second laws of thermodynamics. The engine is theoretically feasible if both the laws are
satisfied. The device becomes impossible if any of the two laws is violated.
Q Q
The Clausius theorem requires that
T 0 and as the proposed engine gives T
0,
Which is the more effective way to increase the efficiency of a Carnot engine to increase T1,
keeping T2 constant; or to decrease T2, keeping T1 constant?
Solution
T2 T T
Then 1 2 2
T1 T T1
Since T1 T2
(1 2 ) 0
The more efficient way to increase the cycle efficiency is to decrease T2.
Example
A cyclic heat engine operates between a source temperature of 8000C and a sink temperature
of 300C. What is the least rate of heat rejection per kW net output of the engine?
Solution
Wnet
Now max 0.718
Q1
1
Q1 1.392kW
0.718
Now Q 2 Q1 Wnet 1.392 1 0.392kW
Example
A domestic food freezer maintains a temperature of -150C. The ambient air temperature is
300C. If heat leaks into the freezer at the continuous rate of 1.75 kJ/s what is the least power
necessary to pump this heat out continuously?
Solution
Freezer temperature
T2 15 273 258K
Example
A reversible heat engine operates between two reservoirs at temperatures of 6000C and 400.
The engine drives a reversible refrigerator which operates between reservoirs at
temperatures of 400C and - 200. The heat transfer to the heat engine is 2000 kJ and the net
work output of the combined engine refrigerator plant is 360 kJ.
(a) Evaluate the heat transfer to the refrigerant and the net heat transfer to the reservoir at
400C.
(b) Reconsider (a) given that the efficiency of the heat engine and the COP of the refrigerator
are each 40% of their maximum possible values.
Solution
(a) Maximum efficiency of the heat engine cycle (see figure) is given by
W1
Again 0.642
Q1
Q4
Also COP 4.22
W2
Since W1 - W2 = W = 360 kJ
W2 = W2 - W = 1284 -360 = 924 kJ
Q4 = 4.22 x 924 = 3899 kJ
Q3 = Q4 + W2 = 924 + 3899 = 4823 kJ
Q2 = Q1 + W1 = 2000 - 1284 = 716 kJ
Heat rejection to the 400C reservoir
= Q2 + Q3 = 716 + 4823 = 5539 kJ Ans. (a)
(b) Efficiency of the actual heat engine cycle
= 0.4 max = 0.4 x 0.642
W1 = 0.4 x 0.642 x 2000 = 513.6 kJ
W2 = 513.6 - 360 = 153.6 kJ
COP of the actual refrigerator cycle
Q4
COP 0.4x4.22 1.69
W2
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Therefore
Q4 = 153.6 x 1.69 = 259.6 kJ Ans. (b)
Q3 = 259.6 + 153.6 = 413.2 kJ
Q2 = Q1 - W1 = 2000 - 513.6 = 1486.4 kJ
Heat rejected to the 400C reservoir
= Q2 + Q3 = 413.2 + 1486.4 = 1899.6 kJ Ans. (b)
Example
A reversible engine is used for only driving a reversible refrigerator. Engine is supplied 2000
kJ/s heat from a source at 1500 K and rejects some energy to a low temperature sink.
Refrigerator is desired to maintain the temperature of 15ºC while rejecting heat to the same
low temperature sink. Determine the temperature of sink if total 3000 kJ/s heat is received by
the sink.
Solution
2000 Qsin k , HE 4
Also for engine Qsin k , hE Tsin k
1500 Tsin k 3
QR Qsin k ,R 1000
For refrigerator Qsin k ,R Tsin k
288 Tsin k 288
Substituting Qsink,HE and Qsink,R values.
4 1000Tsin k
Tsin k 3000
3 288
Tsin k 624.28 K
Temperature of sink = 351.28 ºC
A house requires 2 × 105 kJ/h for heating in winter. Heat pump is used to absorb heat from
cold air outside in winter and send heat to the house. Work required to operate the heat pump
is 3 × 104 kJ/h. Determine :
(i) Heat abstracted from outside ;
(ii) Co-efficient of performance.
Solution
Thus the same device has two values of C.O.P. depending upon the objective.
Problem
In a winter season when outside temperature is –1ºC, the inside of house is to be maintained
at 25ºC. Estimate the minimum power required to run the heat pump of maintaining the
temperature. Assume heating load as 125 MJ/h.
Answer: 3.02 kW
Problem
A heat pump working on the Carnot cycle takes in heat from a reservoir at 50C and delivers
heat to a reservoir at 600C. The heat pump is driven by a reversible heat engine which takes
in heat from a reservoir at 8400C and rejects heat to a reservoir at 600C. The reversible heat
engine also drives a machine that absorbs 30 kW. If the heat pump extracts 17 kJ/s from the
50C reservoir, determine (a) the rate of heat supply from 8400C source (b) the rate of heat
rejection to the 600C sink.
Answer: (a) 47.61 kW (b) 34.61 kW
Problem
Two reversible heat engines A and B are arranged in series. A rejecting heat directly to B.
Engine A receives 200 kJ at a temperature of 4210C from a hot source, while engine B is in
communication with a cold sink at a temperature of 4.40C. If the work output of A is twice
that of B, find (a) the intermediate temperature between A and B (b) the efficiency of each
engine, and (c) the heat rejected to the cold sink.
Example
Two Carnot engines I and II operate in series between a high temperature reservoir at
10270C and a low temperature reservoir al 270C. The engine I absorbs energy from the high
temperature reservoir and rejects energy to a reservoir at temperature T, The engine II
receives energy from the reservoir at T and rejects energy to the low temperature reservoir
The amount of energy absorbed by engine II from the reservoir at T is the same as that
rejected by engine I to the reservoir at T, If engines I and II are found to have the same
efficiency, determine the temperature T. If engine I receiver 100 kJ energy as heat from the
high temperature reservoir, calculate the work delivered by engine I and engine II.
Solution
Q2 T
Q1 T1
T 624.5
Q2 Q1 x100 48.038 kJ
T1 1300
A reversible engine works between three thermal reservoirs A, B and C. The engine absorbs
an equal amount of heat from the thermal reservoirs A and B kept at temperatures TA and TB,
respectively, and rejects heat to the thermal reservoir C kept at temperature TC. The
efficiency of the engine is times the efficiency of the reversible engine, which works
between the two reservoirs A and C. Prove that
TA T
(2 1) 2(1 ) A
TB TC
Solution
Since Q units of heat is supplied from reservoir A, the work output will be
T T
Q A C
TA
Likewise when the operation is between reservoir B and C, the work output will be
T T
Q B C
TB
For the given engine
Total heat output = 2Q
Total work output
T T TB TC
= Q A C Q
TA TB
Thermal efficiency
T T TB TC
Q A C Q
= TB
TA
2Q
1 TC TC
= 1 1
2 TA TB
1 TC TC
= 2
2 TA TB
1 TC TC TA TC TC
2 1
2 TA TB TA TA
TA
Multiplying both sides by 2 , we get
TC
TA T T
or (2 1) 2 A 2 A
TB TC TC
TA
= (2 1) 2 (1 )
TC
TA
= 2(1 ) (2 1)
TC
Example
Three Carnot engines E1, E2 and E3 operate between temperatures of 1000 K and 300 K.
Make calculations for the intermediate temperatures if the work produced by the engines are
in the ratio of 4:3:2.
Solution
See following figure for schematic arrangement of three Carnot engines in series.
For Engine E1
W1 T1 T2 1000 T2
1
Q1 T1 1000
Q W1 Q2
W 1000 T2
W1 Q2 1000
T2
Q2 W1
1000 T2
For Engine E2
W T2 T3
2
Q2 T2
W2 1000 T2 T2 T3
2
W1 T2 T2
W2 3
Since
W1 4
4
i.e. T2 (750 T3 ) (1)
7
Also Q2 Q3 W2
W T T
2 3
Q3 W2 T2
T3
i.e. Q3 W2
T2 T3
For Engine 3
W3 T3 300
3
Q3 T3
W3 T2 T3 T3 300
W2 T3 T3
W3 2
Since
W2 3
2
we get (T2 T3 ) T3 300 (2)
3
Solving (2) and (3)
T2 = 689 K and T3 = 455.80 K
Problem
Three Carnot heat engines are arranged in series. The first engine takes 4000 kJ of heat from
a source at 2000 K and delivers 1800 kJ of work; the second and third engines deliver 1200
kJ and 500 kJ of work respectively. Make calculations for the exhaust temperature of the
second and third Carnot engine.
Answer: 250 K, 500 K
ASSIGNMENT
Q.1. (AMIE W10, 6 marks): Explain the concept of macroscopic and microscopic viewpoint as applied to
study of thermodynamics.
Q.2. (AMIE S06, 5 marks): Explain the following terms in the context of thermodynamics: (i) System, (ii)
Surrounding, (iii) Universe, (iv) State, (v) Properties.
Q.3. (AMIE W08, 11, 10, S17, 18, 6 marks): What is a thermodynamic system? Differentiate between open
system, closed system and isolated system.
Q.4. (AMIE W05, S15, 4 marks): Define properly and mention its main characteristic in relation to a cyclic
process.
Q.5. (AMIE S12, 3 marks): Under what conditions is the work done equal to pdv ?
Q.6. (AMIE W09, S12, 6 marks): Show that energy is a property of a system. What are the modes in which
energy is stored in a system? What is the difference between the standard symbols of E and U?
Q.7. (AMIE S13, 6 marks): Explain the difference between energy in transit and energy in storage. What is
the energy per unit mass for a (i) non-flow system, and (ii) flow system?
Hint: Non flow means closed system.
Q.8. (AMIE W05, 4 marks): In what respects are the heat and work interactions (i) similar and (ii) dissimilar?
Q.9. (AMIE S07, 16, 5 marks): Define heat and work. Which are the characteristics common to both work
and heat?
Q.10. (AMIE S06, 2 marks): The two modes of energy transfer are work and heat. Does the mode of energy
transfer depend upon the choice of a system? Support your answer with the help of an example.
Q.11. (AMIE W09, 2 marks) Does heat transfer inevitably cause a temperature rise?
Q.12. (AMIE S10, 2 marks): Distinguish between thermodynamic work and heat transfer.
Q.13. (AMIE S06, 08, 5 marks): State and explain the conditions to be satisfied for thermodynamic
equilibrium.
Q.14. (AMIE W07, 2 marks): Distinguish between steady slate and equilibrium.
Q.15. (AMIE W05, 4 marks): Define property and mention its main characteristic in relation to a cyclic
process.
Q.16. (AMIE W06, S15, 4 marks): Distinguish clearly between the following, giving examples wherever
necessary:
(i) Closed system and open system;
(ii) Heat and work;
(iii) Point functions and path functions;
(iv) Enthalpy and internal energy.
Q.17. (AMIE W12, 2 marks): Differentiate between heat and internal energy.
Q.18. (AMIE W12, 2 marks): Explain system approach and control volume approach in the analysis of a flow
process.
Q.19. (AMIE W06, 4 marks): Define the first law of thermodynamics for a closed system. Explain the
limitations of the first law.
Q.20. (AMIE W10, 6 marks): Derive an expression for the first law of thermodynamics of an open system.
Q.21. (AMIE S10, W12, 6 marks): Explain the first law of thermodynamics for a change of state and prove
that energy is a property.
Q.22. (AMIE S15, 4 marks): Explain the first law of thermodynamics as referred to a closed systems
undergoing a cyclic change.
Q.23. (AMIE W16, 17, 8 marks): State the first law of thermodynamics for a closed system undergoing a
cycle. Apply the first law for a steady flow process by taking a real life example. How does Bernoulli's equation
compare with steady flow energy equation?
Q.69. (AMIE S11, 8 marks): It is proposed to compress air (ideal gas) reversibly from an initial state of 100
kPa and 27 °C to a final state of 500 kPa and 27 °C. Compare the work required for the following processes: (i)
Heating at constant volume followed by cooling at constant pressure, (ii) isothermal compression, (iii) adiabatic
compression followed by cooling at constant volume. For air, Cv = 20.93 J/molK and Cp = 29.302 J/molK.
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