SECOND LAW OF THERMODYNAMIC

CHAPTER 4

EKB 1043: CHEMICAL ENGINEERING THERMODYNAMIC PREPARED BY: ARASU UTTRAN

 Second law of thermodynamics
• Heat cannot spontaneously pass from a colder body to a warmer body
• All spontaneous process are irreversible
• There is general tendency in nature for energy to pass from higher
temperature region to a lower temperature
• The second law provides the necessary means to determine the quality as
well as the degree of degradation of energy during a process
• 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
 Basic concept of Heat engine, heat pump and
refrigerator
• Thermal reservoir: body with large capacity which can supply or
absorb a significant amount of thermal energy without undergoing
any change in temperature. For example, oceans, lakes and rivers.
• Working fluid: substance which in operations absorb the heat from
hot reservoir, release the heat to a cold reservoir.
• Source: reservoir that supplies heat as energy known as a heat
source
• Sink: a reservoir that absorbs heat as energy is known a as heat sink
Heat engine
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
rotating shaft.)
3. They reject the remaining waste heat
to a low-temperature sink (the
atmosphere, rivers, etc.).
4. They operate on a cycle.
Heat engines and other cyclic devices
usually involve a fluid to and from
which heat is transferred while
undergoing a cycle. This fluid is called
the working fluid.
 Characteristics of heat engine
• Absorb heat from high temperature source
• Releases heat into low temperature sink
• Heat engine operates on a cycle
• It delivers the net work

Application of Heat engine

• Steam turbine, Train using coal
A steam power plant

A portion of the work output of

a heat engine is consumed
internally to maintain
continuous operation.

6
Thermal efficiency
 Kelvin–Planck Statement
It is impossible for any device that No heat engine can have a thermal efficiency
operates on a cycle to receive heat from a of 100 percent, or as for a power plant to
single reservoir and produce a net amount operate, the working fluid must exchange heat
of work. with the environment as well as the furnace.
 Example 1 & 2
1. A heat engine has a total heat input of 1.3 kJ and a thermal efficiency of 35%. How much work
will it produce?

2. Solar energy stored in large bodies of water, called solar ponds, is being used to generate
electricity. If such a solar power plant has an efficiency of 4 percent and a net power output of
350 kW, determine the average value of the required solar energy collection rate, in kJ/h.
 Example 3
• A coal-burning steam power plant produces a net power of 300 MW with an overall thermal efficiency of 32
percent. The actual gravimetric air–fuel ratio in the furnace is calculated to be 12 kg air/kg fuel. The heating
value of the coal is 28,000 kJ/kg.
• Determine (a) the amount of coal consumed during a 24-hour period and (b) the rate of air flowing through the
furnace

(a) The rate and the amount of heat inputs to the power plant are:

MJ
The amount and rate of coal consumed during this period are:

(b) Noting that the air-fuel ratio is 12, the rate of air flowing
through the furnace is:
Refrigerators

• 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.
Refrigerators

In a household refrigerator, the freezer compartment

where heat is absorbed by the refrigerant serves as the
evaporator, and the coils usually behind the refrigerator
where heat is dissipated to the kitchen air serve as the
condenser.
 Coefficient of Performance
of a Refrigerator
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

remove QL from the cooled space.
Heat Pumps
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.

17
 Clausius Statement
It is impossible to construct a device that
It states that a refrigerator cannot operate
operates in a cycle and produces no effect
unless its compressor is driven by an external
other than the transfer of heat from a lower-
power source, such as an electric motor.
temperature body to a higher-temperature
body.
Equivalence of the Two Statements

Any device that violates the Kelvin–Planck statement also violates the Clausius statement, and vice versa.
 Example 4
A food freezer is to produce a 5 kW cooling effect and its COP is 1.3. How
many kW of power will this refrigerator require ?
 CARNOT cycle
Aim of this cycle:

• To estimate the work obtained from heat during its passage from a
higher to a lower temperature
• To obtain the maximum work in cyclic operation where every step is
to be carried in a reversible fashion

The heat engine operating on this cycle is known as Carnot engine.

 Carnot engine
Consist of four successive operational steps:
1. Reversible isothermal expansion
2. Reversible adiabatic expansion
3. Reversible isothermal compression
4. Reversible adiabatic compression
Carnot engine
Carnot engine
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.
Such a temperature scale offers great
conveniences in thermodynamic calculations.
 THE CARNOT HEAT ENGINE

The Carnot heat engine is the most efficient of

all heat engines operating between the same
high- and low-temperature reservoirs.

No heat engine can have a higher efficiency

than a reversible heat engine operating
between the same high- and low-temperature
reservoirs.

Any heat Carnot heat

engine engine

27
 Any refrigerator or heat pump
THE CARNOT REFRIGERATOR
AND HEAT PUMP

Carnot refrigerator or heat pump

No refrigerator can have a higher COP

than a reversible refrigerator operating
between the same temperature limits.
 THE CARNOT REFRIGERATOR
AND HEAT PUMP Any refrigerator or heat
pump

Carnot refrigerator or heat pump

How do you increase the

COP of a Carnot
No refrigerator can have a higher COP refrigerator or heat pump?
than a reversible refrigerator operating How about for actual ones?
between the same temperature limits.
29
 Second Law
Irreversibility,disorder:ENTROPY
 Qrev
dS =
T

• In a irreversible process, the entropy of the universe increases

• For any process, the entropy of the universe never decrease
• A spontaneous heat transfer (from hotter body to a colder one) implies an increment of entropy
(It is a irreversible process)

Entropy: a thermodynamic function of disorder

 Entropy
• Entropy S, is an intrinsic property of a system, functionally related to the measurable
coordinates which characterize the system.
• If a process is reversible and adiabatic, dQrev = 0, dSt = 0. The entropy of a system is
constant during a reversible adiabatic process and the process is isentropic.
• Since entropy is a state function, the entropy changes of the irreversible and
reversible processes are identical.
 Entropy changes of an ideal gas
• For one mole of fluid undergoing a mechanically reversible process in a
closed system:

dU = dQrev − PdV

dH = dU + PdV + VdP

dQrev = dH − VdP
dH = C Pig dT V = RT / P
dQrev dT dP
dS = = CPig −R
T T P

S T C
ig
P dT P
= − ln
R T0 R T P0
For an ideal gas with constant heat capacities undergoing a reversible
adiabatic process:
S T C
ig
dT P
= P − ln
R T0 R T P0
S = 0
C Pig T2 P
0= ln − ln 2
R T1 P1

R / C Pig
T2  P2 
=  
T1  P1 
ig
C
C =C +R  = P
ig ig
P V
CVig
( −1) / 
T2  P2 
=  
T1  P1 
• Let a quantity of heat |Q| be transferred from the hotter (TH) to the cooler (TC)
reservoir. The entropy changes of the two reservoirs are:

−|Q| |Q|
S = t
H S =
t
C
TH TC

 TH − TC 
Stotal = S + S =| Q | 
t
H
t
C

 TH TC 

• For the process of irreversible heat transfer, ΔStotal is always positive, approaching
zero as the process becomes reversible.
Stotal  0
A 40 kg steel casting (CP= 0.5 kJ/kgK) at a temperature of 450°C is quenched in 150 kg of oil
(CP= 2.5 kJ/kgK) at 25°C. If there are no heat losses, what is the change in entropy of (a) the
casting, (b) the oil, and (c) both considered together?
40 kg steel casting
T1= 450oC
Cp= 0.5 kJ/Kg.K

150 kg oil
T1= 25oC
Cp= 2.5 kJ/Kg.K
A 40 kg steel casting (CP= 0.5 kJ/kgK) at a temperature of 450°C is quenched in 150 kg of oil
(CP= 2.5 kJ/kgK) at 25°C. If there are no heat losses, what is the change in entropy of (a) the
casting, (b) the oil, and (c) both considered together?
Find final Temperature (40)(0.5)(T2 − 450) + (150)(2.5)(T2 − 25) = 0 T2 = 46.25 C
(a) the casting
dQ C P dT T2  46.52 + 273  kJ
S = 
t
= m = mCP ln = (40kg )(0.5kJ / Kg .K ) ln  = −16.33
T T T1  450 + 273  K

(b) the oil

dQ C dT T  46.52 + 273  kJ
S t =  = m P = mCP ln 2 = (150kg )(2.5kJ / Kg .K ) ln  = 26.15
T T T1  25 + 273  K

kJ
(c) total entropy change Stotal = S + S = (−16.33kJ / K ) + (26.15kJ / K ) = 9.82
t t
cast oil
K
 Entropy changes in MIXTURE of NON IDEAL
GASES
• This is an irreversible process and will yield a considerable entropy change.
• Suppose NA and NB are gram moles of two ideal gases A and B, mixed at constant
temperature T and constant pressure P. Then the total mole number of the
mixture:
N = N A + NB
NA
xA =
N
NB
xB =
N
 Step 1: Before mixing two gases
• Gases A and B are allowed to undergo an isothermal expansion from an initial pressure P to their
partial pressure pA and pB in the final mixture. In this step, the expression on their entropy
changes can be derived from the 1st law of thermodynamics

' 0
SA = N A (CP ln T − R ln P + S A )
S B' = N B (CP ln T − R ln P + S B0 )
 Step 2: After mixing
• The ideal gases are allowed to pass through a semi-permeable
membrane which permit the flow of any one of the two gases A and B
• The total pressure P remains constant, and it comprises partial
pressure pA and pB.
• Hence the partial pressure of gas A in mixture = pA/P=xA and of gas
B=pB/P=xB.
• The entropy changes associated with this step are:
 '' 0
SA = N A (CP ln T − R ln p A + S A )
S B'' = N B (CP ln T − R ln pB + S B0 )

Entropy change due to mixing is:

'' '' ' '

SM = S A + S B − S A − S B
After substitution:

SM = − NR( xA ln xA + xB ln xB )
N= number of moles
R= Universal gas constant
 Entropy changes in temperature (Liquids)
• Two fluids in a heat exchanger are at different temperatures.
• They would mix up and exchange the heat with each other.
• After certain period of time, both fluids will attain a final
temperature.
• This process would of course be accompanied by a change in entropy:
 For a isobaric process, the entropy change will be:
T
dQ 2

S = 
T T
dQP
2
dT2
T2
S P =  =  CP = CP ln
T T 1 T
T
1
T
T1
T1

dQ= heat change For a isochoric process, the entropy change will be:
T1 = Initial temperature
T2=Final temperature
T T
dQ 2
dT 2
T
SV =  V =  CV = CV ln 2
T T T1
T1
T1
For a given mass of fluid m, the preceding expression will be

For a isobaric process, the entropy change will be:

T2
dT T2
S P = m  CP = mCP ln
T T1
T1

For a isochoric process, the entropy change will be:

T
dT 2
T2
SV = m  CV = mCV ln
T T1
T 1
 Mathematical statement of second law of
thermodynamics
• Suppose a heat reservoir at a temperature TH is brought in contact with a second
reservoir at a lower TL. Let a quantity of heat Q be transferred from the high-
temperature to the low-temperature reservoir. So the net change in entropy

Q Q  TH − TL 
Stotal = − = Q 
TL TH  TH TL 
• If the process are IRREVERSIBLE heat transfer, total ENTROPY would
be POSITIVE, if Q=+VE, TH>TL
• If the process are REVERSIBLE, TH>TL, total ENTROPY approaches
ZERO.
Since no thermal transfer from system and surroundings, the entropy change:

Sisolated  0
The isolated system consist of a system and the surroundings. Therefore the entropy
change of an isolated system is the sum of the entropy chanegs of the system and the
surroundings, or
S system + S surroundings  0
Stotal  0
As for conclusion, the total change of entropy can be classify:

S  0( Irreversib le)
S = 0(Re versible )
 Entropy balance for open systems

Net rate of change Time rate of Time rate of Total rate

in entropy of change entropy change entropy of entropy
flowing streams in control in surroundings generation
volume
t
d (mS ) cv dSsurr
( Sm
 ) fs + + = SG  0
dt dt

d ( mS ) cv Q j
 ( Sm
 ) fs + − = SG  0
dt j T , j
In a steady-state flow process, 1 mol/s of air at 600 K and 1 atm is continuous-ly mixed with 2 mol/s of air at
450K and 1 atm. The product stream is at 400K and 1 atm. Determine the rate of heat transfer and the rate
of entropy generated for the process. Assume that air is an ideal gas with CP = (7/2)R, that the surroundings
are at 300K, and that kinetic- and potential-energy changes are negligible.
 Temperature of
surrounding

𝑄ሶ
𝑆𝐺ሶ = 𝑛𝑆
ሶ − 𝑛ሶ 𝐴 𝑆𝐴 − 𝑛ሶ 𝐵 𝑆𝐵 −
𝑇𝜎
𝑄ሶ
= 𝑛ሶ 𝐴 (𝑆 − 𝑆𝐴 ) + 𝑛ሶ 𝐵 (𝑆 − 𝑆𝐵 ) −
𝑇𝜎
𝑇 𝑇 𝑄ሶ
= 𝑛ሶ 𝐴 𝐶𝑃 ln + 𝑛ሶ 𝐵 𝐶𝑃 ln −
𝑇𝐴 𝑇𝐵 𝑇𝜎
7 400 400 8729.7
= ( )(8.314) (1) ln + (2) ln +
2 600 450 300
𝐽
= 10.446
𝐾𝑠

R=8.314 J/mol.K

Q = nH − n A H A − n B H B = n AC P (T − TA ) + n B C P (T − TB ) = −8729.7 J / s
 The third law of thermodynamics

• The absolute entropy is zero for all perfect crystalline substances at

absolute zero temperature.
• When the form is non-crystalline, e.g., amorphous or glassy, calculations show
that the entropy of the more random form is greater than that of the
crystalline form.
• The absolute entropy of a gas at temperature T, where Tf and Tv are
temperatures of fusion and vaporization:

Tf (CP ) S H f Tv (C ) H v T (C P ) g
S= dT + + P l
dT + + dT
0 T Tf T f T Tv Tv T
Perfect crystal at 0 K Crystal deforms at T > 0 K
 THIRD law of thermodynamics
• Definition: The absolute entropy of a pure crystalline substance is zero at
absolute zero temperature (T=0K).

T T
C dT
f
H f b
CPl dT H v
T
CPg dT
S =  Ps + + + +
T Tf T Tb T
0 T f
Tb

Tf : melting point
Tb: boiling point NOTE: This equation only to
CPS: specific heat of solid measure the heat capacity at
CPl: specific heat of liquid cryogenic temperature, and third
CPg: specific heat of the gas law is confined strictly to pure
ΔHf: latent heat of fusion crystalline substances
ΔHv: latent heat of vapourization
 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.
Exercise 1:
A heat engine is working between a source at 550oC and a sink at
27oC. Calculate the efficiency of the heat engine. (Ans: 63.5%).

Exercise 2:
A system received heat (50kJ) from temperature source region
(T=373K) to lower region (T=275K). Calculate
i) Efficiency (Ans: 0.262@26.2%)
ii) Minimum work required (13.1kJ)
iii) Amount of heat released (36.9kJ)
Exercise 3
Calculate the change in entropy when 5 mole of an ideal gas
expands from a volume 5L to 50L at 27oC. R=1.987 cal/mol.K.
(Ans=22.876 cal /K)

Exercise 4
Calculate the entropy of 1mol of air containing 21% oxygen,
79% nitrogen by volume. R= 8.314 J/mol.K (Ans= 4.273 J/K)
Exercise 5
Calculate the change in entropy with given mass of argon 80g,
heated from 300K to 500K (isochoric process). Cv=0.3122
kJ/kg.K (Ans=0.0128 kJ/K)