Second Law of Thermodynamics

It is an observed fact that certain processes can only

proceed spontaneously in one direction (hot coffee gets
colder)

TH TC

Much Later
TH TC TE TE

The following does not occur

TE TE

TH TC

Another example, connecting high pressure tank with a

low pressure tank:

PH PL PE PE
Closed
valve

where PE is the final pressure

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The following does not occur:

PE PE PH PL

In both cases there is a possibility for doing work using an

engine.

Example 1:
TH
Such an engine can take heat
Engine E Work
from the hot body to form
steam and then direct the
steam through a turbine
TC

Example 2:
PH
Such an engine can direct the
E Work gas stream directly through a
turbine
PL

The question that arises is how much work can be done,

i.e., what is the maximum work produced by the engine?

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The evolution of the Second Law

The First Law of Thermodynamics is used to calculate

end states of a system as it evolves, it does not answer the
following questions:
1) In what direction does a spontaneous process go
2) What is the maximum possible work

The Second Law of Thermodynamics starts with a simple

principal concerning the direction of heat flow and
evolves into developing a new property called entropy
(S)

Clausius Statement
It is impossible for a system to operate in such a way that
the sole result is the transfer of heat from a cold to a hot
body

Kelvin Planck Statement

It is impossible for a system that operates in a cycle to
generate work while transferring heat with a single
reservoir

TR
NOT POSSIBLE
according to K-P
HEAT

System undergoing
E WORK
a cycle, e.g., engine

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Recall, a reservoir is a body that has so much thermal
capacity that its temperature doesn’t change when heat
transfer occurs

To illustrate the equivalence of the two statements

consider the following:

TH (hot)

Q1

TC (cold)

Connect two thermal reservoirs with high thermal

conductivity metal and assume Q1 heat flows from TC to
TH which according to Clausius is not possible

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Then place a heat engine between TH and TC that draws
Q1 heat from the TH reservoir and dumps Q2 heat to the TC
reservoir

TH
Q1
W W
Q1
E Q1 E
Q2 Q2
TC TC

This is quivalent to

E W=Q1-Q2

Q1-Q2
TC

This engine takes heat from one reservoir (Tc) to produce

work Æ this is not possible according to K-P statement
and thus demonstrating the equivalency of the two
statements

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Heat Engines

Work can easily be converted to heat and other forms of

energy, but converting heat into work is not so easy

W W=0

Q Q

Converting heat into work requires a heat engine

Earliest heat engine operated on steam:

Process I - add steam into the piston-cylinder to raise
the pressure above atmospheric pressure and thus push the
piston down
Process II - add water to condense the steam and
lower the pressure below atmospheric pressure so the
piston is “pulled” back up

Process I Process II
Steam
from boiler Water
from tank

Drain water

Patm Patm
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Thermal Efficiencies

Basic characteristics of heat engine are:

TH
1) Receive heat, QH, from a high
QH
temperature source
W

2) Convert part of this heat to work, W E

QC
3) Reject the remaining waste heat,
TC
QC, to a low temperature sink

4) Operate on a cycle

These devices involve a working fluid to and from which

heat is transferred

First Law applied to the heat engine cycle yields

∆E = Qnet − W
0 = (Qin − Qout ) − W
0 = (QH − QC ) − W ∴Wheat = QH − QC
engine

The efficiency of the cycle is defined as

work done W
η heat = =
engine maximum work WMAX
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Maximum possible work corresponds to

QC = 0 Æ WMAX= QH therefore,

W
η heat =
engine QH

Thermal efficiency is the ratio of the work done and the

heat input, substituting for W

QH − QC QC
η heat = = 1−
engine QH QH

For an internal combustion (IC) engine heat is supplied by

combustion QH and heat rejected through the exhaust QC,
typically the thermal efficiency of combustion is around
30%

Other engine mechanical inefficiencies translate into an

even lower overall efficiency

ηoveral = ηcombustionη mechanical

ICengine

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Can we have a 100% thermally efficient engine?
Consider the following simple heat engine designed to lift
a weight of mass M

Engine consists of a frictionless, adiabatic

piston-cylinder device with two sets of
M
stops and weight placed on the piston.
30oC Initial temperature of the gas is 30oC

Add 100 kJ of heat Q to the gas from a

M source at 100oC
- gas heats up
- gas expands raising the piston
Qin= 100 kJ
100oC

Q = W + ∆U
M - heat goes into work done, W, to raise
the piston Æ this results in a PE
90oC increase of the mass (say 30 kJ)
- the remaining 70 kJ goes into
increasing the temperature of the gas
30 kJ
Load is removed and gas temperature is
M 90oC
* Even under ideal conditions (frictionless
90oC and adiabatic) more heat added than work
done

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To complete the cycle, cool the gas back to 30oC

For 100% efficiency the 70 kJ excess

energy added to the gas must be returned
to the 100oC source for later use
30oC Æ results in heat flow from cold to hot,
Qout= 70 kJ Clausius statement says not possible
100oC

Must transfer heat to colder reservoir, say

20oC, to drop temperature back to 30oC
70 kJ excess energy rejected
30oC
This energy cannot be re-used in the cycle
Qout= 70 kJ because the lowest working fluid
20oC
temperature is 30oC Æ waste energy

We can conclude that every heat engine must waste some

energy by transferring it to a low-temperature reservoir in
order to complete the cycle, even under idealized
conditions

This is consistent with the Kelvin Planck statement

109
Refrigerators

A refrigerator takes heat from a hot reservoir (hot room)

and dumps it into a cooler reservoir (cooler outdoors).
TH
The refrigeration cycle is the
opposite of the heat engine QH
requiring work input
W E
QC
TC

Note: this is not inconsistent with Clausius’ statement

because the heat transfer from the cold to the hot reservoir
is not spontaneous.

Applying First Law to the refrigeration cycle

∆E = Qnet − W
0 = (Qin − Qout ) − (−W )
0 = (QC − QH ) + W ∴Wrefr = QH − QC

Coefficient of performance (COP) β defined as

heat removed QC QC
β= = =
work done Wrefr QH − QC
Typical values of β are 3-4
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Reversible and Irreversible Processes

Have shown that no engine can have 100% efficiency, the

question becomes what is the maximum efficiency a heat
engine can achieve?

The maximum efficiency will correspond to a cycle

consisting of a series of idealized reversible processes

A reversible process is one which the system and its

surroundings can be returned to their respective original
states at the end of the reverse process

If the system and surroundings cannot be returned to their

respective original states the process is termed
irreversible and the process is said to involve
irreversibilities.

A process is internally reversible if no irreversibilities

occur inside the system boundary, irreversibilities may
occur outside the system

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Demonstrating Irreversibilities via the 2nd Law

1) Consider quasi-equilibrium adiabatic compression

(system pressure PS is uniform and PSVk= const.)

WC ∆U C = Q − WC
PS
1 P2V2 − P1V1
WC = ∫12 PS dV = const ∫12 dV =
Vk 1− k
2 1

The reverse quasi-equilibrium adiabatic expansion

(system pressure PS is uniform and PSVk= const.)

WE ∆U E = Q − WE
PS
1 P1V1 − P2V2
WE = ∫21 PS dV = const ∫21 dV =
2 1
Vk 1− k

WC = −WE ⇒ ∆U C = − ∆U E

When the piston is returned to the initial position:

1) the system IE is recovered, ∆U1-2+∆U2-1= 0
2) the energy from the surroundings used to compress the
gas is returned by the work done by the gas during
expansion

Quasi-equilibrium compression and expansion processes

are reversible

112
Consider rapid adiabatic compression (system pressure
not uniform and thus PVk = const does not apply)
P(x) WC

Pressure is higher at the piston face.

Wrapid = ∫12 Ppiston dV > Wrev = ∫12 PS dV
compr face

∆U C = Q − Wrapid
compr

∆U C > (∆U C ) rev

The reverse rapid adiabatic expansion

P(x)

Pressure is lower at the piston face

Wrapid = ∫21 Ppiston dV < Wrev = ∫21 PS dV

exp an face

∆U E = Q − Wrapid
exp an

∆U E < (∆U E ) rev

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More work done by the surrounding during rapid
compression compared to the work done by the gas
during rapid expansion

The increase in the gas IE during compression is greater

than the gas IE decrease during expansion, ∆U1-2 > ∆U2-1

The excess IE is equal to the work deficit of the

surroundings

In order to return the system and the surroundings to their

original states, 100% of the excess IE of the gas must be
transferred to the surroundings in the form of work via a
heat engine Æ impossible according to K-P

Rapid compression and expansion processes are

irreversible

114
2) Consider a block sliding down an inclined plane

ZiÆ Zf

Zi
UiÆ Uf
M
Zf

System includes the block and the inclined plane

Neglect heat transfer to surroundings, Apply First Law

(U f − U i ) + Mg ( Z f − Z i ) + ( KE f − KEi ) = Q − W
U f − U i = Mg ( Z i − Z f )

Friction between the block and the plane converts the PE

of the block into internal energy of the system

Since there is no interaction between the system and the

surroundings (i.e., Q= 0, W= 0) the state of the
surroundings remain unchanged

To show reversibility return the system to its initial state

Lets consider a cycle consisting of three processes:

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Process I: Reverse process of the original, assume it is
possible to drag the block back to the initial height Zi and
recover initial internal energy Ui for the system
M
ZfÆ Zi

Zi
UfÆ Ui
Zf

Process II: Lower the block to Zf by a frictionless pulley

generating work W equal to the drop in PE of the mass
Mg(Zi – Zf)

ZiÆ Zf

Ui M
Zf

Process III: Add heat Q of the amount equal to Uf – Ui by

contacting the inclined plane with a hot reservoir

Q
TH
U iÆ Uf M
Zf

116
At the conclusion of the cycle consisting of processes I,
II, and III
- the block is returned to the initial height Zf
- the system (block and incline) returned to Uf

The net result of the cycle is to draw heat from a single

reservoir and produce an equal amount of work, this is
impossible according to K-P statement Æ Process I
(assumed) is not possible

Since we can’t return the system to the original state via

Process I (reverse of the original process), the original
process, from state i to state f, is irreversible

Any process involving friction is irreversible

117
3) Consider the heating of a soda can in a warm room

Ta= 20oC
Q
5oC Æ 20oC

To restore the can to its original state of 5oC one needs to

refrigerate the can, the refrigerator needs work input

Refrigerator
TC= 2oC W TC= 20oC
Q
Q QH
20oC Æ 5oC

Energy balance of the refrigerator yields QH= Q +W

The net heat returned to the surroundings QH is the heat

from the can Q plus the work input to the refrigerator W
thus the final IE of the surroundings is higher than the
original IE by an amount equal to W

The only way to return the surrounding to the original IE

is to use a heat engine to convert 100% of the excess IE
into work used by the refrigerator

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This is impossible according to K-P statement and thus
the original process is irreversible

The source of the irreversibility in this case is the heat

transfer across a finite temperature difference

Irreversibilities include:
- dry and fluid friction
- heat transfer through a finite temperature difference
- rapid compression and expansion of a fluid
- unrestrained expansion of a fluid
- spontaneous mixing of different gases

* All real processes include some irreversibility

119