MEE204 Engineering Thermodynamics

UNIT 2
LIMITATIONS OF THE FIRST LAW OF THERMODYNAMICS

A cup of hot coffee

does not get hotter
in a cooler room.

Transferring
heat to a
paddle
wheel will
not cause it
to rotate.

These processes

Transferring cannot occur even
heat to a though they are not in
wire will not violation of the first
generate
electricity. law.
 Processes occur in a certain direction,
and not in the reverse direction.

A process must satisfy both

the first and second laws of
thermodynamics to proceed.
MAJOR USES OF THE SECOND LAW
1. The second law may be used to identify the direction of processes.

2. The second law also asserts that energy has quality as well as
quantity. The first law is concerned with the quantity of energy and the
transformations of energy from one form to another with no regard to its
quality. The second law provides the necessary means to determine the
quality as well as the degree of degradation of energy during a process.
3. The second law of thermodynamics is also used in determining the
theoretical limits for the performance of commonly used engineering
systems, such as heat engines and refrigerators, as well as
predicting the degree of completion of chemical reactions.
 THERMAL ENERGY RESERVOIRS

A source supplies
Bodies with relatively large thermal energy in the form of
masses can be modeled as heat, and a sink
thermal energy reservoirs. absorbs it.

Temperature constant
 HEAT ENGINES
The devices that convert heat to
work.
1. They receive heat from a high-
temperature source (solar energy,
oil furnace, nuclear reactor, etc.).
2. They convert part of this heat to
work (usually in the form of a
Work can always rotating shaft.)
be converted to 3. They reject the remaining waste
heat directly and heat to a low-temperature sink
completely, but the (the atmosphere, rivers, etc.).
reverse is not true.
4. They operate on a cycle.
Heat engines and other cyclic
Part of the heat devices usually involve a fluid to
received by a heat and from which heat is
engine is transferred while undergoing a
converted to work, cycle. This fluid is called the
while the rest is working fluid.
rejected to a sink.
A steam power plant

A portion of the work output

of a heat engine is consumed
internally to maintain
continuous operation.
STEAM POWER PLANT I.C ENGINES
THERMAL EFFICIENCY

Schematic of
a heat engine.

Some heat engines perform better

Even the most
than others (convert more of the
efficient heat
heat they receive to work).
engines reject
almost one-half
of the energy
they receive as
waste heat.
CAN WE SAVE QOUT? In a steam power plant,
the condenser is the
device where large
quantities of waste
heat is rejected to
rivers, lakes, or the
atmosphere.
Can we not just take the
condenser out of the
plant and save all that
waste energy?
The answer is,
A heat-engine cycle cannot be completed without unfortunately, a firm
rejecting some heat to a low-temperature sink. no for the simple
reason that without a
Every heat engine must waste heat rejection process
some energy by transferring it to a in a condenser, the
cycle cannot be
low-temperature reservoir in order
completed.
to complete the cycle, even under
idealized conditions.
The Second Law of
Thermodynamics:
Kelvin–Planck Statement

It is impossible for any

device that operates on
a cycle to receive heat
from a single reservoir
and produce a net
amount of work.
A heat engine that violates the
Kelvin–Planck statement of the

No heat engine can have a
second law.
thermal efficiency of 100 percent,
or as for a power plant to
operate, the working fluid must
exchange heat with the
environment as well as the
furnace.
REFRIGERATORS AND HEAT PUMPS

The transfer of heat from a low-
temperature medium to a high-
temperature one requires special
devices called refrigerators.

Refrigerators, like heat engines,
are cyclic devices.

The working fluid used in the
refrigeration cycle is called a
refrigerant.

The most frequently used
refrigeration cycle is the vapor-
compression refrigeration cycle.

In a household refrigerator, the freezer compartment

Basic components of a where heat is absorbed by the refrigerant serves as
refrigeration system and the evaporator, and the coils usually behind the
typical operating conditions. refrigerator where heat is dissipated to the kitchen
air serve as the condenser.
 COEFFICIENT OF PERFORMANCE

The efficiency of a refrigerator is expressed

in terms of the coefficient of performance
(COP).
The objective of a refrigerator is to remove
heat (QL) from the refrigerated space.

The objective of a refrigerator is to Can the value of COPR be

remove QL from the cooled space. greater than unity?
 HEAT PUMPS
The objective
of a heat
pump is to
supply heat
QH into the
warmer
space. The work
supplied to a
heat pump is
used to extract
energy from the
cold outdoors
and carry it into
the warm
indoors.

Can the value of COPHP

be lower than unity?
What does COPHP=1
for fixed values of QL and QH represent?

Most heat pumps in operation today have a
seasonally averaged COP of 2 to 3.

Most existing heat pumps use the cold outside air
as the heat source in winter (air-source HP).

In cold climates their efficiency drops considerably
when temperatures are below the freezing point.

In such cases, geothermal (ground-source) HP
that use the ground as the heat source can be
used.

Such heat pumps are more expensive to install,
but they are also more efficient.

Air conditioners are basically refrigerators whose
refrigerated space is a room or a building instead
of the food compartment.
When installed backward,
The COP of a refrigerator decreases with
an air conditioner decreasing refrigeration temperature.
functions as a heat pump.
Therefore, it is not economical to refrigerate to a
lower temperature than needed.
 The Second Law of Thermodynamics:
Clasius Statement

It is impossible to construct a device

that operates in a cycle and produces
no effect other than the transfer of
heat from a lower-temperature body
to a higher-temperature body.
It states that a refrigerator cannot operate unless
its compressor is driven by an external power
source, such as an electric motor.
This way, the net effect on the surroundings
involves the consumption of some energy in the
form of work, in addition to the transfer of heat
from a colder body to a warmer one. A refrigerator that
To date, no experiment has been conducted that violates the Clausius
contradicts the second law, and this should be statement of the second
taken as sufficient proof of its validity. law.
EQUIVALENCE OF THE TWO STATEMENTS

Proof that the

violation of the
Kelvin–Planck
statement leads
to the violation
of the Clausius
statement.

Any device that violates the Kelvin–Planck statement also violates

the Clausius statement, and vice versa.
PERPETUAL-MOTION MACHINES

A perpetual-motion machine that

violates the second law of
A perpetual-motion machine that
thermodynamics (PMM2).
violates the first law (PMM1).

Perpetual-motion machine: Any device that violates the first or the
second law.

A device that violates the first law (by creating energy) is called a PMM1.

A device that violates the second law is called a PMM2.

Despite numerous attempts, no perpetual-motion machine is known to
have worked.
ANIMATIONS

Carnot cycle 1
Carnot cycle 2
Carnot cycle 3
A domestic food refrigerator maintains a
temperature of – 12°C. The ambient air
temperature is 35°C. If heat leaks into the
freezer at the continuous rate of 2 kJ/s
determine the least power necessary to pump
this heat out continuously. 0.36 kW

A cyclic heat engine operates between a

source temperature of 1000°C and a sink
temperature of 40°C. Find the least rate of
heat rejection per kW net output of the
engine ? 0.326 kW
A heat engine is joined to another heat engine in series.
The heat rejection of the first heat engine is supplied to the
second heat engine. Prove that the total thermal efficiency
is equal to the sum of the individual efficiencies minus its
product.
A reversible engine operates between temperatures T1
and T2. The heat rejected by this heat engine is received
by a second reversible heat engine at temperature T2
and rejected to a reservoir at temperature T3. If the
efficiencies of the engines are same then find the
relationship between T1, T2 and T3.
Two Carnot engines work in series between the source and
sink temperatures T1 and T3. If both engines develop equal
power, determine the intermediate temperature.
An ice plant working on a reversed Carnot cycle heat
pump produces 15 tonnes of ice per day. The ice is
formed from water at 0°C and the formed ice is
maintained at 0°C. The heat is rejected to the
atmosphere at 25°C. The heat pump used to run the
ice plant is coupled to a Carnot engine which absorbs
heat from a source which is maintained at 220°C by
burning liquid fuel of 44500 kJ/kg calorific value and
rejects the heat to the atmosphere.
Determine :
(i) Power developed by the engine ;
(ii) Fuel consumed per hour.
Take enthalpy of fusion of ice = 334.5 kJ/kg.
5.3 kW, 1.082 kg/h.
Two reversible heat engines A and B are
arranged in series. A rejects heat directly to B.
Engine A receives 200 kJ at a temperature of
421°C from the hot source while engine B is
in communication with a cold sink at a
temperature of 5°C. If the work output of A is
twice that of B, find (i) intermediate temperature
between A and B (ii) efficiency of each engine
(iii) heat rejected to the sink
A Carnot heat engine draws heat from a reservoir at
temperature T1 and rejects heat to another reservoir at
temperature T3. This Carnot engine drives a Carnot
refrigerator which absorbs heat from reservoir at
temperature T2 and rejects heat to a reservoir at
temperature T3. If the high temperature T1 = 600 K
and low temperature T2 = 300 K,
Determine :
(i) The temperature T3 such that heat supplied to
engine Q1 is equal to the heat absorbed by refrigerator
Q2.
(ii) The efficiency of Carnot engine and C.O.P. of
Carnot refrigerator. 400 K 33.33% 3
A reversible heat engine absorbs 2500
kJ/cycle of heat from a constant temperature
heat source at 2000 K and rejects some
energy as waste heat to a reservoir X. The
work output from the engine is used to drive a
reversible refrigerator and its source
temperature being 300 K. The heat outflow
from the refrigerator is also taken to the
reservoir X. If the total heat flow into the
reservoir is 3000 kJ/cycle, make calculations
for the temperature of reservoir X. 1028.5 K
Determine whether the following cases
represents the reversible, possible or impossible
heat engines.
a. 900 kW heat is rejected
b. 560 kW heat is rejected
c. 108 kW heat is rejected
In each case the engine is supplied with
1120 kJ/s of heat. The source and sink
temperature are maintained at 560 K and 280 K
respectively.
A Carnot refrigerator operates between
temperature -10°C and 30°C. Determine the
coefficient of performance. Subsequently it is
desired to change the temperatures so as to
make the coefficient of performance exactly
equal to 7.0. The amount of increase in the
higher temperature is equal to amount of
decrease in the lower temperature. Workout
the new temperatures. T1=301.867 K
T2=264.133 K
A heat engine operating between two reservoirs
1000K and 300K is used to drive heat pump which
extracts heat from the reservoir at 300 K at a rate
twice that at which engine rejects heat to it. If the
efficiency of the engine is 40% of the maximum
possible and the coefficient of performance of the
heat pump is 50% of the maximum possible, make
calculations for the temperature of the reservoir to
which the heat pump rejects heat. Also workout the
rate of heat rejection from the heat pump if the rate of
supply of heat to the engine is 50 kW.
322.5K 86kW
A reversible heat pump is driven by a
reversible heat engine. The engine receives Q1
amount of heat from a source at T1 and rejects
Q2 amount of heat to a sink at T2. The heat
pump extracts Q4 amount of heat from the sink
at T4 and discharges Q3 amount of heat to the
surroundings at T3. Derive an expression for
Q4/Q1 in terms of four reservoir temperatures.
Q4/Q1 = T4(T1-T2)/T1(T3-T4)
Two Carnot engines work in series between
the source and sink temperatures of 550 K
and 350 K. If both engines develop equal
power determine the intermediate
temperature.
A Carnot heat engine operates between 825 K and
550 K constant temperature thermal reservoirs. Half
of the work output from this engine drives a
generator and the other half is used to run a
reversed Carnot engine that abstracts heat from the
550 K temperature reservoir and rejects that to a
thermal reservoir at 715 K. Determine the heat
rejected to the reservoir by the reversed engine as a
percentage of heat supplied from the 825 K reservoir
to the heat engine. Proceed to calculate the heat
rejected per hour if the generator output is 400 kW.
Assume ƞgen = 90% 72.15% 3733.61 kW
A heat engine drives a heat pump. The heat
delivered by the heat engine as well as by the
pump is used to heat the water circulating
through the heat radiators of a building. The
efficiency of the heat engine is 27% and the
coefficient of performance of the heat pump is
4. Calculate ratio of heat transferred to the
circulating water to the heat taken by the heat
engine. 1.81
A reversible engine operates between a source at 700°C
and a sink at 50°C. The power developed by the engine
is used to drive a reversible refrigerator operating
between 50°C and -25°C. Engine receives 2500 kJ of
heat from the source and the combined engine
refrigerator produces a net work output of 400 kJ.
Determine the following.
1. The heat absorbed by the refrigerator from the
evaporator
2. Net heat transfer to the reservoir at 50°C
3. Calculate the above i) and ii) if the efficiency of the
engine and COP of the refrigerator are 45% of their
maximum. 4 198.6 kJ 6298.84 kJ 518.5 kJ 2618.5
kJ
 CARNOT THEOREM

The efficiency of an irreversible heat engine is
always less than the efficiency of a reversible heat
engine if they operating between the same two
reservoirs

The efficiencies of all reversible heat engines

operating between the same two reservoirs are
the same

• They are also known as the Carnot

principles
It is impossible for a heat engine to produce net work in a
complete cycle if it exchanges heat only with bodies at a
single fixed temperature.
 THE THERMODYNAMIC TEMPERATURE SCALE
A temperature scale that is independent of the properties
of the substances that are used to measure temperature is
called a thermodynamic temperature scale.
CLAUSIUS INEQUALITY
Figure shows a system that undergoes a
reversible cycle during which it exchanges heat
with three thermal reservoirs. Show that
A reversible heat engine is supplied 900 kJ of
heat from a heat source at 500 K. The engine
develops 300 kJ of net work and rejects heat to
two heat sinks at 400 K and 300 K. Determine
the engine thermal efficiency and magnitude of
heat interaction with each of the sink. 33.3 %
240 kJ 360 kJ
WHAT IS ENTROPY?
Boltzmann
relation

A pure crystalline substance at absolute zero

temperature is in perfect order, and its entropy is
zero (the third law of thermodynamics).

The level of molecular

disorder (entropy) of a
substance increases as
it melts or evaporates. Disorganized energy does not create much
useful effect, no matter how large it is.
43
 The paddle-wheel work done on a gas increases the
level of disorder (entropy) of the gas, and thus energy
is degraded during this process.

In the absence of During a heat

friction, raising a transfer process, the
weight by a rotating net entropy
shaft does not increases. (The
create any disorder increase in the
(entropy), and thus entropy of the cold
energy is not body more than
degraded during this offsets the decrease
process. in the entropy of
the hot body.) 44
 Some Remarks about Entropy
1. Processes can occur in a certain direction
only, not in any direction. A process must
proceed in the direction that complies with
the increase of entropy principle, that is,
Sgen ≥ 0. A process that violates this
principle is impossible.
2. Entropy is a nonconserved property, and
there is no such thing as the conservation of
entropy principle. Entropy is conserved
during the idealized reversible processes
only and increases during all actual
processes.
3. The performance of engineering systems is
degraded by the presence of irreversibilities,
The entropy change of a and entropy generation is a measure of the
system can be negative, magnitudes of the irreversibilities during that
but the entropy generation process. It is also used to establish criteria
cannot. for the performance of engineering devices.

45
 CHANGE IN ENTROPY OF THE UNIVERSE

(dS)isolated ≥ 0
(dS)universe ≥ 0
(dS)universe = (dS)system + (dS)surroundings
Boltzmann relation

Boltzmann constant

P thermodynamic probability

A pure crystalline substance at absolute zero

temperature is in perfect order, and its entropy is
zero (the third law of thermodynamics).
Nernst law
An iron cube at a temperature of 400°C is
dropped into an insulated bath containing 10
kg water at 25°C. The water and cube finally
reaches a temperature of 50°C at steady
state. Given that the specific heat of water is
equal to 4186 J/kg K. Find the entropy
changes for the iron cube and the water. Is
the process reversible ? If so why ?
– 2195 J/K 3372.24 J/K 1177.24 J/K
2.2 kg of ice at – 5°C is exposed to the atmosphere
which is at 20°C. The ice melts and comes into thermal
equilibrium with the atmosphere.
(i) Determine the entropy increase of the universe.
(ii) What is the minimum amount of work necessary to
convert the water back into ice at – 5°C ?

Cp of ice is 2.093 kJ/kg °C and the latent heat of fusion

of ice is 333.3 kJ/kg.
(i)0.20878 kJ/K (increase) (ii) 62.7 kJ
A closed system contains air at a pressure 1 bar,
temperature 300 K and volume 0.018 m3. This system
undergoes a thermodynamic cycle consisting of the
following three processes in series : (i) Constant volume
heat addition till pressure becomes 5 bar, (ii) Constant
pressure cooling, and (iii) Isothermal heating to initial
state.
Represent the cycle on T-S and evaluate the change in
entropy for each process and net entropy change
Take Cp = 0.718 kJ/kg K and R = 0.287 kJ/kg K.
0.0241 kJ/K. – 0.0338 kJ/K 0.00965 kJ/K.
Air at 20°C and 105 kPa bar occupies 0.025 m3.
The air is heated at constant volume until the
pressure is 450 kPa bar, and then cooled at
constant pressure back to original temperature.
Calculate :
(i) The net heat flow from the air.
(ii) The net entropy change.
Sketch the process on T-s diagram.
21.56 kJ. – 30.18 kJ – 8.62 kJ
0.0456 kJ/K 0.0326 kJ/K 0.013 kJ/K.
The specific heats of a gas vary linearly with absolute
temperature according to the following relations :
Cp = (0.85 + 0.00025 T) kg/kg K, and
Cv = (0.56 + 0.00025 T) kJ/kg K
If the entropy of the gas at 1 bar pressure and 273 K is
zero, find the entropy of the gas at 25 bar and 750 K
temperature 0.0448 kJ/kg K.
An insulated vessel of 0.5 m3 capacity is divided by a rigid
conducting diaphragm into two chambers A and B, each
having a capacity of 0.25 m3. Chamber A contains air at
1.4 bar pressure and 290 K temperature and the
corresponding parameters for air in chamber B are 4.2
bar and 440 K. Calculate :
(i) Final equilibrium temperature,
(ii) Final pressure on each side of the diaphragm, and
(iii) Entropy change of system.
Tf = 389.6 K. 1.88 bar 3.72 bar 0.0165 kJ/K.
 AVAILABILITY AND IRREVERSIBILITY
Energy has two parts
— Available part.
— Unavailable part.
Availability
The theoretical maximum amount of work which can be obtained from a
system at any state p1 and T1 when operating with a reservoir at the
constant pressure and temperature p0 and T0

Unavailable energy is
the portion of energy
that cannot be
converted to work by
even a reversible heat
engine.
A system that is in
equilibrium with its
environment is said to be at
the dead state.
AVAILABLE ENERGY IN A CYCLE
DECREASE IN AVAILABLE ENERGY WHEN HEAT IS TRANSFERRED THROUGH A
FINITE TEMPERATURE DIFFERENCE
AVAILABILITY IN NON-FLOW SYSTEMS
AVAILABILITY IN STEADY FLOW SYSTEMS
HELMHOLTZ AND GIBBS FUNCTIONS
 IRREVERSIBILITY

non-flow process

steady flow-process
 EFFECTIVENESS

One kg of air is compressed polytropically from 1 bar pressure

and temperature of 300 K to a pressure of 6.8 bar and
temperature of 370 K. Determine the irreversibility if the sink
temperature is 293 K. Assume R = 0.287 kJ/kg K, cp = 1.004 kJ/kg
K and cv = 0.716 kJ/kg K. 13.8 kJ/kg
SECOND-LAW EFFICIENCY, ƞII
Second-law efficiency of all reversible devices is _____
The second-law efficiency of naturally occurring
processes is _________
A heat engine that rejects waste heat to a sink at
530 K has a thermal efficiency of 36 % and a second-
law efficiency of 60 %. Determine the temperature
of the source that supplies heat to this engine.
1325 K

COP of a heat pump for residential buildings has a

value of 1.2. Assuming an indoor temperature of
21°C and outdoor temperature of 10°C, determine
the second-law efficiency of the heat pump. 4.49 %