Second Law of Thermodynamics: Motivation ME 201

Spring 09

Gas

First Law: For a cycle Q W

Thought Experiment:
1. Weight is lowered, turning the paddle 
Shaft work is done on the gas.
2. Then heat is transferred from the system to
} Both Q and W are negative.
the surroundings completing the cycle.

Question : With the given surroundings, (i.e. container, paddle wheel and
weight) is the reverse cycle possible?

Second Law: Cycles 1

Second Law of Thermodynamics: Motivation ME 201
Spring 09

High Temperature

Q Q

Low Temperature

Heat can be transferred from high temperature body to low temperature body.

Question :
1. Is the reverse possible?
2. How can we make it possible? Can you think of an example?

Second Law: Cycles 2

Heat Engine ME 201
Spring 09

Gas
Gas
Gas Gas

TH TC

Heat Engine: A device that operates in a thermodynamic cycle and does a

certain amount of net positive work through the transfer of heat from a high
temperature body and to a low temperature body.

Second Law: Cycles 3

 Heat Engine: Practical Example ME 201
Spring 09

W (energy sought )
thermal
QH ( Energy that cos ts)
QH QL QL
1
QH QH

Second Law: Cycles 4

Heat Pump: Practical Example ME 201
Spring 09

Heat Pump: A device that operates in a cycle, that requires work, and that
accomplishes the objective of transferring heat from a low temperature body to a
high temperature body.
Efficiency of a refrigerator is expressed
QH as Coefficient of performance or COP:
Condenser W QL ( Energy sought )
W ( Energy that cos ts)
Expansion Compressor
QL 1
Valve QH QL QH 1
QL
Evaporator

QL Refrigeration Cycle

Second Law: Cycles 5

The Kelvin-Planck Statement ME 201
Spring 09

It is impossible to construct a device that will operate in a cycle and produce no

effect other than the raising of a weight and the exchange of heat with a single
reservoir.

Thermal Reservoir:
High Temperature A body to which and from
which can be transferred
QH indefinitely without change in
the temperature of the
reservoir.
W
Note: Thermal reservoir
always remains at a constant
temperature.
Example: Ocean, atmosphere
IMPOSSIBLE

Second Law: Cycles 6

The Clausius Statement ME 201
Spring 09

It is impossible to construct a device that will operate in a cycle and produce no

effect other than the transfer of heat from a cooler body to a hotter body.

High Temperature In effect it is impossible to

construct a refrigerator that
QH operates without an input of work.

QL
Low Temperature

IMPOSSIBLE

Second Law: Cycles 7

Four Observations about the 2nd Law statements ME 201
Spring 09

1. Both statements of the second law are negative statements. Consequently

they can not be directly „proved‟. However every relevant experiment
validates and non contradict the second law.
2. The two statements are equivalent. That is, truth of one implies truth of the
other, or violation of one implies violation of the other.
3. Second Law implies the impossibility of constructing a perpetual motion
machine (PMM) of the second kind.

Note:
PMM I would create work or energy out of nothing thus violating the First Law

PMM II would extract heat from a source and then convert the heat completely
into other forms of energy, thus violating the Second Law.

PMM III would have no friction, and thus run indefinitely. But produce no work.

4. It is impossible to have a heat engine of 100% efficiency.

Second Law: Cycles 8

Next Question ME 201
Spring 09

If 100% efficiency is impossible, what is the maximum efficiency

possible?

To answer we need to talk about :

Reversible and Irreversible Processes

A reversible process is one such that the system and all parts of the
surroundings can be restored to their initial state.

The effects of a reversible process can be undone such that there is no evidence
of the process ever having occurred. Reversing a reversible process leaves no
trace in either the system or the surroundings.

Second Law: Cycles 9

Factors that render processes irreversible ME 201
Spring 09

1. Friction

-Q

Incline Incline Incline

2. Unrestrained Expansion

Gas Vacuum Gas

3. Heat Transfer through a finite temperature difference

Second Law: Cycles 10

Factors that render processes irreversible ME 201
Spring 09

4. Mixing of Two Different Substances

O2 N2 O2+N2

5. Hysteresis effects and the i2R losses encountered in electrical circuits

6. Ordinary combustion

Second Law: Cycles 11

 The Carnot Cycle ME 201
Spring 09

If 100% efficiency is impossible, what is

High Temperature (TH) the maximum efficiency possible for a
QH thermodynamic cycle?
1. A reversible isothermal process in
Boiler
which heat is transferred from the high
temperature reservoir.
W 2. A reversible adiabatic process in
Pump turbine
which the temperature of the working
fluid decreases from high to low
temperature.
Condenser 3. A reversible isothermal process in
which heat is transferred to the low
QL Carnot Cycle temperature reservoir.
4. A reversible adiabatic process in
Low Temperature (TL) which the temperature of the working
fluid increases from low to high
temperature.
Second Law: Cycles 12
Two Propositions regarding efficiency of a Carnot Cycle ME 201
Spring 09

First Proposition:
It is impossible to construct an engine that operates between two given reservoirs
and is more efficient than a reversible engine operating between the same two
reservoirs.
Second Proposition:
All engines that operate on the Carnot Cycle between two given constant
temperature reservoirs have the same efficiency.

Second Law: Cycles 13

The Thermodynamic Temperature Scale ME 201
Spring 09

The efficiency of a Carnot cycle is only dependent on the temperatures of the

hot and cold reservoirs, hence
QL
thermal 1 (TL , TH )
QH QL TL
Lord Kelvin proposed thermal 1 1
QH TH
If we run the Carnot Cycle between the steam point and ice point (even though
practically impossible), the thermal efficiency would be
Tice point
thermal 1 0.2680 (1)
Tsteam point
If we wish to have the magnitude of the degree on the absolute scale to match
the magnitude of the Celsius degree, we can write
Tsteam point Tice point 100 (2)
Solving (1) and (2), Tsteam point 373.15 K and Tice point 273.15 K
It follows that T (C ) 273.15 T ( K )
Second Law: Cycles 14
Example 1 ME 201
Spring 09

A heat pump heats a house in the winter. The interior temperature should be 20 0C.
Heat transfer through the walls and ceiling are estimated to be 2400 kJ per hour
per degree temperature difference between the inside and outside.
a) If the winter outside temperature is 0 0C, what is the minimum power required
to drive the heat pump?

QH 2400 (293.15 273.15) TH=TROOM=293.15

48000 kJ / hour QH
QL TAMB TAMB W QH QL
QL QH
QH TROOM TROOM
44725 kJ / hour QL
W QH QL 48000 44725 kJ / hour TL=TAMB=273.15
3275 kJ / hour 0.91 kW
Second Law: Cycles 15
 Example 2 ME 201
Spring 09

A Carnot heat engine receives heat from a high temperature TA=800 K

reservoir at 527˚ C. the heat rejected from this engine is supplied to
a second Carnot engine. This second engine rejects heat to a low
QA
temperature reservoir at 17˚ C. the first engine reject 400 kJ to the
second engine. If both engines have the same efficiency, determine WA
the following: HE 1
• The temperature of the high temperature reservoir for the second
engine QB = 400 kJ
• The energy received by the first engine from the 527˚ C source
• The work done by each engine TB
• The efficiency of each engine
QB = 400 kJ
a. Both engine have same efficiency, so
T 290 HE 2
1 1 T 481 .6 K WB
800 T
b. QA = QB (TA/TB) = 400 (800/481.6) = 664.45 kJ Q0
c. WA = QA-QB = 264.45 kJ
WB = QB (1-T0/TB) = 159.136 kJ T0=290 K
d. Efficiency = 1- 290/T = 0.3978
Second Law: Cycles 16
 Summary ME 201
Spring 09
1. Motivation: 2nd Law gives direction in which processes and cycles can occur
2. Defined Heat Engine and Heat Pump/Refrigerator:
since 2nd Law is stated in terms of them
W QL QH 1 QL 1
1 HP REF
HE
QH QH
W 1 QL W QH 1
QH QL
3. Stated the Kelvin Planck and Clausius forms of the 2nd Law
1. Proved that both these statements are equivalent.
2. It is impossible to have a heat engine of 100% efficiency.
4. Asked ourselves then what is the maximum possible efficiency?
1. Defined reversible and irreversible processes
2. Described one particular reversible cycle – the Carnot Cycle.
3. Proved that a reversible cycle has the maximum efficiency, and all such
reversible cycles have the same efficiency.
4. Argued that since the efficiencies of all reversible cycles are equal, the only
parameter it depends on are TH and TL, i.e.
QL TL
thermal 1 (TL , TH ) 1
QH TH
 2nd Law for Processes: Inequality of Clausius ME 201
Spring 09

Q
0
High Temperature (TH) T
QH Proof:
1. Consider a reversible Carnot cycle:
Boiler
Q QH QL
0
Wrev T TH TL
Pump turbine 2. Consider an irreversible cyclic heat
engine
Wirr Wrev
Condenser QH QL ,irr QH QL ,rev
QL QL,irr QL,rev
Carnot Cycle
Q QH QL ,irr
Low Temperature (TL) 0
T TH TL
Second Law: Processes 18
Entropy: A property of a system ME 201
Spring 09

Let a system undergo a reversible process from

P 2 state 1 to state 2 along a path A, and let the cycle
A be completed along path B.
Since cycle is reversible,
B 2 1
C Q Q Q
1 0
T 1
T A 2
T B
v
Now consider another reversible cycle, which proceeds first along path C, and
then completed along path B. For this cycle,
2 1
Q Q Q
0
T 1
T C 2
T B
Subtracting one from the other,
2 2
Q Q
1
T A 1
T C

Second Law: Processes 19

Entropy: A property of a system ME 201
Spring 09

Q
Since is the same for all reversible paths between state 1 and 2, conclusion
T
is that this quantity is independent of the path, and only depend on the end states, in
other words, it‟s a property. This property is called ENTROPY
Q
dS
T rev
2
Q
S 2 S1
1
T rev

NOTE: Since entropy is a property, S 2 S1 is the same for all processes, both
reversible and irreversible, between these two states. The above equation only
enables us to find the change in entropy along a reversible path. However, once the
change has been evaluated, this value is the magnitude of the entropy change for all
processes between these two states.

Second Law: Processes 20

 Entropy of a pure substance ME 201
Spring 09

Values of specific entropy are given in thermodynamic tables in the same manner as
specific volume and specific enthalpy.
The corresponding unit is kJ/kg.K

In the saturation region,

the entropy may be
calculated using the
„quality‟.

s (1 x) s f x sg

Second Law: Processes 21

 Entropy change in a Reversible Process ME 201
Spring 09

TH Let us consider a reversible Carnot Cycle

QH
1. A reversible isothermal process in which heat is transferred
1 Boiler 2 from the high temperature reservoir.
2 2
Q 1 1 Q2
turbine
W S 2 S1 Q
Pump
1
T rev TH 1 TH
2. A reversible adiabatic process in which the temperature of
Condenser the working fluid decreases from high to low temperature.
3
4 3 Q
QL S3 S 2 0
2
T rev
TL 3. A reversible isothermal process in which heat is transferred
to the low temperature reservoir.
4 4
Q 1 Q
T S 4 S3 Q 3 4
1 2 3
T rev TL 3 TL
W 4. A reversible adiabatic process in which the temperature of
4 3 the working fluid increases from low to high temperature.
QH 1
Q
QL S1 S 4 0
4
T rev

S Second Law: Processes 22

The Thermodynamic Property Relations ME 201
Spring 09

Q dU W
Q TdS and W PdV TdS dU PdV
H U PV
dH dU PdV VdP
dH TdS VdP TdS dH VdP

For a unit mass Tds du Pdv

Tds dh vdP
On a mole basis Td s du Pd v
Tds dh v dP
Second Law: Processes 23
 Entropy change in an Irreversible Process ME 201
Spring 09

2 1
P 2 A B Q Q Q
For 1 2 1, 0
T 1
T A 2
T B

2 1
C B Q Q Q
For 1 2 1, 0
1 T 1
T C 2
T B

v 2
Q
2
Q
Subtracting 2nd equation from 1st, T T
1 A 1 C
2 2 2
Since path A is reversible, and since entropy is a property, Q
dS A dSC
2 2 1
T A 1 1
Q
Therefore, dSC
1 1
T C
Equality for a reversible
Q process
As path C was arbitrary, in general, dS
T Inequality for an irreversible
Second Law: Processes process 24
Increase in entropy principle ME 201
Spring 09
Q
In general, dS
T
For an isolated system, Q 0 dSisolated dS sys dS surr 0
sys
Example 2:
Suppose that 1 kg of saturated water vapor at 100 0C is condensed to a saturated
liquid a 100 0C in a constant-pressure process by heat transfer to the surrounding
air, which is at 25 0C. What is the net increase in entropy of the water plus
surroundings?
For the control mass (water) from the steam tables,
S c . m. ms fg 1 6.0480 6.0480 kJ / K
Concerning the surroundings, we have
Qto surroundings mhfg 1 2257.0 2257.0 kJ / K
Q 2257
S surr 7.5700 kJ / K
T0 298.15
Snet Sc.m. Ssurr 6.0480 7.5700 1.5220 kJ / K
Second Law: Processes 25
Lost work ME 201
Spring 09

Q
For irreversible processes dS
T
Q
dS S gen provided, S gen 0
T irr
Qirr TdS T S gen
dU Wirr
Again TdS dU PdV
Combining Wirr PdV T S gen
This shows that the work is reduced by an amount proportional to the entropy
generation. For this reason, the term T S gen is often called “lost work”, although
it is not a real work or energy quantity lost, but a lost opportunity to extract work.

Second Law: Processes 26

Summary ME 201
Spring 09

1. Second Law of Thermodynamics

Q
0
2. Inequality of Clausius T
a) ‘Equality’ holds for reversible processes
b) ‘Inequality’ holds for irreversible processes.

Q
dS
3. The property ENTROPY T
a) ‘Equality’ holds for reversible processes
b) ‘Inequality’ holds for irreversible processes.

4. Thermodynamic Property Relations: 5. Increase in Entropy dS isolated 0

sys
Tds du Pdv 6. Lost Work
Tds dh vdP Wirr PdV T S gen

Second Law: Processes 27

Entropy change for an ideal gas ME 201
Spring 09

Tds du Pdv Tds dh v dP

For an ideal gas, du cv0 dT For an ideal gas, dh c p0 dT
and P R and v Ru
T v T P
Therefore Therefore
dT dv dT dP
ds cv0 R ds c p0 Ru
T v T P
2 2
dT v2 dT P2
s2 s1 cv 0 R ln s2 s1 c p0 Ru ln
1
T v1 1
T P1
T
0
c p0
In ideal gas tables sT dT is listed.
T0
T 0 0 P2
s2 s1 sT2 sT1 Ru ln
P1
Second Law: Processes 28
Example 3 ME 201
Spring 09
Oxygen is heated from 300 to 1500 K. Assume that during this process the pressure
dropped from 200 to 150 kPa. Calculate the change in entropy per kg.
Use ideal gas tables and compare with result obtained by assuming constant specific
heat value of c p 0 1.0714 kJ / kg K

From ideal gas table, s2 s1 sT02 sT01 Ru ln P2

P1
150
s2 s1 (258.068 205.329) 8.3145 ln
200
s2 s1 55.131 kJ / kmol K
55.131
s2 s1 1.7228 kJ / kg K
32
Using c p 0 1.0714 kJ / kg K ,
2
dT P2 1500 8.3145 150
s2 s1 c p0 R ln 1.0714 ln ln
1
T P1 300 32 200
1.7991 kJ / kg K
Second Law: Processes 29
 Isentropic Efficiency ME 201
Spring 09

For all the steady-flow devices we consider (such as turbines, compressors, pumps,
and nozzles) the reversible adiabatic (isentropic) process is the standard to which
real processes can be compared. Wact
The isentropic efficiency is thus defined as isen
Wisen
Example 4 (Text Book Ex 7.7)
Consider a steam turbine in which the
steam enters as superheated vapor at
800 K and 6 Mpa and exits at 0.1 Mpa.
The flow rate of the steam is 15 kg/s,
and the isentropic efficiency of the
turbine is 90%. Determine the outlet
state of the steam and the power
produced by the turbine.

Go through book solution

Second Law: Processes 30