Chapter-2

First Law of Thermodynamics

• The fundamental implication of this law is that

“although energy assumes many forms, the
total quantity of energy is constant, and when
energy disappears in one form it appears
simultaneously in other forms.
• Joule’s experiments proved that heat is also a
form of energy and established a equivalence
between heat and work.
 Joules Experiment

• The experiment devised by Joule to demonstrate the

conservation of energy. When the constraint is removed,
potential energy in the form of a suspended weight is
converted into the kinetic energy of a moving paddle wheel
in a container of water sealed against other inflow or
outflow of energy.
• The moving paddle wheel heats the water by a precise
amount consistent with the falling weight.
Ex 2.2 Calculate ∆U and ∆H in kJ for 1 kmol
water as it is vaporized at the constant
temperature of 373 K and a constant
pressure of 101.3 kPa . The specific
volumes of the liquid and vapor at these
conditions are 1.04 x 10-3 and 1.675
m3/kmol respectively; 1030 kJ of heat is
added to water for this change.
• The expansion work done by the system
during vaporization is
• W = -P∆V = 101.3 X(1.675−0.00104)
= - 169.57 kJ
• Q = 1.03 x 103 kJ
• ∆U = Q + W = 1.03 x 103 + (−169.57) = 860.43 kJ
• ∆H = ∆U + ∆(PV)
• For a constant pressure process, this becomes
• ∆H = ∆U + ∆(PV)
• ∆H = ∆U + P∆(V) = 1.03 x 103 kJ
 Statements of the second law
• 1)Heat generally cannot flow from a material spontaneously at lower temperature
to a material at higher temperature.
• The natural tendency of the heat is to flow from high temperature reservoir to low
temperature reservoir. It was based on the findings of Sadi Carnot, who said that
the efficiency of the heat engine is not dependent on the type of working fluid but
on the maximum and minimum temperature within the cycle.
• 2) Kelvin-Planck statement
• Kelvin-Planck’s statement is based on the fact that the efficiency of the heat
engine cycle is never 100%. This means that in the heat engine cycle some heat is
always rejected to the low temperature reservoir Fig. The heat engine cycle always
operates between two heat reservoirs and produces work.
Hot
Reservoir
Reservoir
QS
Qs
Heat W =QS-QR
engine
Heat W =Qs
engine
QR

Cold
Impossible heat Reservoir
engine by II law
Possible heat engine
by II law
 Statements of the second law
• 3. Clausius statement:
• “It is impossible to construct a heat pump that, operating
continuously will produce no effect other than transfer of heat from
a low temperature body to high temperature one”. It implies that
energy in the form of work has to be supplied to the heat pump to
transfer heat from a cold body to a hot body.
• 4. Entropy:
• According to the second law, it is impossible for a self acting
machine, to transfer energy from a given state to a higher state of
availability. All spontaneous processes are irreversible to an extent
and are accompanied by degradation of energy.
• To make these statements quantitative, there is need for a function
that characterizes the degradation of energy. The function that is
fundamental in the development of the second law is entropy.
HEAT ENGINE

Source
Desired
Effect

Qin Heat
Engine
W
Required
Effect

Qout

Sink
From first law of thermodynamics

Q W

Qin  Qout Wnet

 coefficient of performance (COP)
• The performance index here is called
coefficient of performance (COP).
• In refrigerator (and heat pumps) the
performance is the ratio of two independent
parameters and hence the possibility of getting
the value more than unity is always there.
• But the term efficiency is restricted to a
maximum of unity.
• This can be much larger than unity.
From first law

Q W

Q1  Q2 W

Q2
COP 
Q1  Q2
 Refrigerator

Sink
[Atmosphere]
Require
d Effect Q1

Refrig
W erator
Desire
d Q2
Effect

Source
[conditioned Space]
 Heat Pump

Sink
Desire [Conditioned Space]
d
Effect Q1
Heat
W Pum
Requi p
red
Effect
Q2
Source
[Atmosphere]
 Carnot cycle
• This cycle was introduced by Sadi Carnot.
• The Carnot cycle consists of an alternate series of reversible isothermal
processes and two reversible adiabatic or isentropic process.
• The p-V diagram for Carnot cycle is as follows:
Process 1-2: Reversible adiabatic compression
Process 2-3: Reversible isothermal heat absorption
Process 3-4: Reversible adiabatic expansion
Process 4-1: Reversible isothermal heat rejection
During the process 2-3, heat Q1 is absorbed by the working fluid
reversibly and isothermally from the hot temperature reservoir at
temperature T1 and the system performs an amount of work
given by the area under the curve 2-3 of the p V diagram.
In process 3-4, the working fluid undergoes reversible adiabatic
expansion, the temperature decreases from T1 to T2. The area
under the curve 3-4 gives the net work obtained from this step.
During process 4-1, the system rejects heat Q 2 to a low
temperature reservoir at constant temperature T2. The area
under the curve 4-1 gives the net work done by the system.
In the final step 1-2, the system undergoes reversible adiabatic
compression during which the temperature rises from T 2 to T1.
The area under the curve 1-2 gives the net work done on the
system.
•
• The enclosed area 1-2-3-4 represents the net work delivered by the engine.
•
• Work done during the cycle, W = Q1-Q2
W Q1  Q 2
• Efficiency of the Carnot cycle, = 
Q1 Q1

• The Carnot cycle has maximum efficiency than any other cycle and depends only on the
two temperature levels. W Q Q T T
• η  1 2
 1 2
Q1 Q1 T1
Q 2 T2

Q1 T1

• Carnot said that the work produced by the engine is not due to consumption of heat;
rather it is due to transportation of heat from high temperature reservoir to the low
temperature reservoir.
• The efficiency of heat engine cycle increase as the value of the maximum temperature
within the cycle increases and the value of minimum temperature within the cycle reduces.
The more is the difference between the maximum and minimum value more is the
efficiency of the heat engine cycle.
A heat engine operates between a heat source
at 800 K and a heat sink at 300 K. What is the
maximum efficiency of the engine?

T1  T2 800  300
η 
T1 800

= 63 %
• An engineer claims to have invented a heat
engine to operate between 500 C and 100 C at
an efficiency of 95%. Comment on his claim.
• Solu: The theoretical efficiency possible is = 1-
T2/T1 = 1- (373/773) = 0.51
• The machine can deliver only a maximum of
51% efficiency. Hence the claim of the
engineer is wrong.
• A heat engine receives heat at the rate of
1500 kJ/min and gives an output of 8.2 kW.
Determine :
• (i) The thermal efficiency ; (ii) The rate of heat
rejection
Q1 = 1500 kJ/min

=1500/60

= 25 kJ/s

Work output, W = 8.2 kW = 8.2 kJ/s.

(i) Thermal efficiency, ηth=W/Q1

= 8 2/25
= 0.328
= 32.8%
Hence, thermal efficiency = 32.8%. (Ans.)

(ii) Rate of heat rejection,

Q2 = Q1 – W = 25 – 8.2
= 16.8 kJ/s
Hence, the rate of heat rejection = 16.8 kJ/s.
It is required to freeze 1 kg water at 273 K by means of a refrigeration
machine, which operates in the surroundings at 300 K. The latent heat of
fusion of ice at 273 K is 334.11 kJ/kg.
Determine:
(a) The minimum amount of work required
(b) The heat given up to the surroundings

Q2 T
COP   2
W T1  T2

Q 2 T1  T2 
W 334.11(300  273)/273
T2
 Entropy as a state function
• Suppose we have two heat reservoirs, which are systems
sufficiently large that their temperatures do not change when
energy flows into or out of them. A reversible cycle exchanges
heat with the two heat reservoirs:

• where
• Q1 is the amount of heat that the cycle absorbs from the first reservoir,
• T1 is the temperature of the first reservoir and
• Q2 is the amount of heat delivered to the second,
• T2 is the temperature of the second reservoir.
Calculations involving Entropy Changes

• Phase change:
• The entropy change in phase changes from one
phase to another involving like melting,
evaporation etc can be calculated from the
values of the latent heat of phase change and the
temperature at which the phase change is carried
out. The phase changes can be considered as a
reversible process occurring at constant
temperature.
• S 
V
H V
T
 Calculate the entropy of evaporation
of dry saturated steam at 500 kPa.
• Latent heat of vaporization = ∆HV = 2106 kJ/kg,
saturation temp = 425 K
• = 2106/425 = 4.96 kJ/kg K
 Processes involving ideal gases
• For a change in state of 1 mole of ideal gas, the change in
entropy is given by the following equations, assuming
constant specific heats.
T2 V2
ΔS C V ln  Rln
T1 V1
T2 P2
ΔS C P ln  Rln
T1 P1
T2
For a constant volume process, ΔS C V ln
T1
T2
For a constant pressure process , ΔS C P ln
T1
V2 P1
For an isothermal process, ΔS Rln Rln
V1 P2
Determine the change in entropy when 2
kg of a gas at 277 K is heated at constant
volume to a temperature of 360 K. The
specific heat at constant volume = 1.42
kJ/kg K
T2
ΔS mC V ln
• Solu: T1
= 2x1.42ln(360/277) = 0.744
kJ/K
 Adiabatic Mixing Process

• When two substances at two different

temperatures are mixed adiabatically, both
will attain an intermediate temperature T and
the total entropy change will be the sum of
the entropy change for each substance given
by dQ R T dT
S   C P
T T1 T

• where T1 denotes the initial temperature

Ten kilograms water at 375 K is mixed adiabatically
with 30 kg water at 275 K. What is the change in
entropy? The specific heat of water is 4.2 kJ/kg K and is
independent of temperature.
• Let T be the final temperature attained by the system, Then the heat balance
gives
• 10x4.2(375-T) = 30x4.2(T-275)
• T= 300 K
• ∆S1 = change in entropy of hot water
• ∆S2 = change in entropy of cold water

 300 
ΔS1 10x4.2ln   9.37kJ/K
 375 
 300 
ΔS2 30 x4.2ln   10.96kJ/K
 275 

• Total entropy change is ∆S=∆S1 + ∆S2 = 1.59 kJ/K

 Mathematical statement of the second law
• Entropy is a property of the system that determines the direction of change. All
spontaneous processes or naturally occurring processes are irreversible and is
accompanied by an increase in entropy.
• A spontaneous process occurring in a closed adiabatic system is accompanied by
an increase in entropy.
• For a reversible process occurring in a closed adiabatic system, the entropy change
must be zero, as there is no heat exchange.
• As the isolated system is a closed adiabatic system, , it can be concluded that the
entropy change of an isolated system in any process must be equal to or greater
than zero.
• or ΔS(isolated) 0
ΔSsystem  ΔSsurroundings 0
ΔStotal 0
As the universe is a perfect example of an isolated system, combining the first and second
laws of thermodynamics, it can be stated that the energy of the universe is conserved while
the entropy is increasing.
 Third law of Thermodynamics
• Entropy is the measure of the randomness of
molecular arrangement of a system. An
orderly configuration results in low entropy.
Based on experimental observations, the
Third law has been postulated as “The
absolute entropy is zero for a perfect
crystalline substance at absolute zero
temperature”
 LIQUEFACTION PROCESSES
• Liquefaction processes make the task of storage, handling,
and transportation of gases simple.
• For example,
• Liquid propane in cylinders serves as a domestic fuel,
• Liquid oxygen is carried in rockets,
• Natural gas is liquefied for ocean transportation, and liquid
nitrogen provides low-temperature refrigeration.
• Gas mixtures are liquefied for separation into their
component species by distillation.
 LIQUEFACTION PROCESSES
• Liquefaction results when a gas is cooled to a temperature in
the two-phase region.
• This may be accomplished in several ways:
• 1. by heat exchange at constant pressure.
• 2. by an expansion process from which work is obtained.
• 3. by a throttling process.
 Analyze the expansion processes
Expansion Processes
The process brings about pressure decreases. Turbine, Nozzles
and Throttling are the devices used for this purposes.

• Turbines (Expanders)
• The expansion of a gas in a nozzle to produce a high-velocity stream is a
process that converts internal energy into kinetic energy. This kinetic
energy is in turn converted into shaft work when the stream impinges on
blades attached to a rotating shaft.
 Analyze the expansion processes
Nozzles
• A nozzle is a device which accelerates fluid. During this process, velocity
of fluid increases with decreasing pressure.
• Turbo machines like steam turbines, water turbines and gas turbines
produce power by utilising the kinetic energy of the jets produced by
passing high pressure steam, water and gas through the devices called
nozzles.
• These nozzles serve two purposes:
(1) To convert pressure energy and thermal energy into kinetic energy and
(2) To direct the fluid jet at the specific angle known as nozzle angle.
 Analyze the expansion processes

• Throttling devices
• A significant reduction in pressure can be achieved by
introducing a restriction into a line through which a gas or
liquid flows. This is commonly done by means of an
adjustable valve, a porous plug, or a capillary tube. They are
called throttling devices.
 Analyze the compression processes
• Compression Processes
• Compression process brings about pressure increases. Compressors, pumps, fans,
blowers and vacuum pumps are the devices used for this purposes.

• Compressors
• The compression of gases may be accomplished in equipment with rotating blades
(like a turbine operating in reverse) or in cylinders with reciprocating pistons.
Rotary equipment is used for high-volume flow where the discharge pressure is
not too high. For high pressures, reciprocating compressors are required. The
energy equations are independent of the type of equipment; indeed, they are the
same as for turbines or expanders, because here too potential- and kinetic-energy
changes are presumed negligible.
 Analyze the compression processes

• Pumps
• Liquids are usually transported by using pumps.
These are usually done by rotating equipment's.