SECOND LAW OF THERMODYNAMICS

THE 2ND LAW OF THERMODYNAMICS

• Can heat be completely converted into work in a
single process?

• Continuous conversion of heat in to work requires a

cyclic process ( a heat engine).

• All attempts to construct a heat engine that is 100%

efficient have failed.

• Two main statements contributed to the second low

of thermodynamics: Kelvin- Planck & Clausius.
 THE LAW STATES….
The Kelvin- Planck statement of the 2nd Law of
thermodynamics is a qualitative statement of the
impossibility of certain types of processes:
• It is impossible for an engine working in Hot Res. TH
a cycle to transform a given amount of
heat from a reservoir completely into Qhot Wout
work.
Engine
or Qcold
• Not all the thermal energy in a thermal
system is available to do work. Cold Res. TC
 THE SECOND LAW OF
THERMODYNAMICS

Hot Res. TH Hot Res. TH

400 J 100 J 400 J
400 J
Engine Engine

300 J
Cold Res. TC Cold Res. TC

• A possible engine. • An IMPOSSIBLE

engine.
 THE CLAUSIUS STATEMENT
No device has been observed for which W = 0 …..This
leads to a second way to state the second Law of
Thermodynamics:
Hot Res. TH
• Itis impossible to make a Qhot W
cyclic engine whose only in

effect is to transfer thermal Engine

energy from a colder body
to a hotter body Qcold
Cold Res. TC
The violation of the Kelvin–Planck statement leads to the
violation of the Clausius statement and vise versa .
CLAUSIUS INEQUALITY PROOF
 CLAUSIUS INEQUALITY PROOF

The system produces work δWsys as a result of this heat

transfer. Applying the energy balance to the combined
system identified by dashed lines yields:

 δWc = δQr – dEc

Where δWc is the total work of the combined system (δWrev

+ δWsys) and dEc is the change in the total energy of the
combined system. The cyclic device is a reversible one.
 CLAUSIUS INEQUALITY PROOF
 From Carnot principle:

 Applying δQr in the first low equation:

 Since the cycle is reversible, dEc = 0.

 Integrating over a cycle:

 CLAUSIUS INEQUALITY PROOF
It thus appears that the combined system is exchanging
heat with a single thermal energy reservoir while involving
(producing or consuming) work Wc during a cycle.
The Kelvin-Planck statement of the second law states that
no system can produce a net amount of work while
operating in a cycle and exchanging heat with a single
thermal energy reservoir
Hence, we reason that Wc cannot be
a work output, and thus it cannot be
a positive quantity.
 CLAUSIUS INEQUALITY PROOF
In the reversed cycle cases, all the quantities will have the
same magnitude but the opposite sign.

Therefore, the work Wc which could not be a positive

quantity in the regular case, cannot be a negative quantity
in the reversed case.

Then it follows that WC int rev =0 since

it cannot be positive or negative
quantity and therefore Thus we
conclude that the equality in the Clausius inequality holds for totally
or just internally reversible cycles and the inequality for the
irreversible ones.
 REVERSIBLE & IRREVERSIBLE PROCESS

 Reversible processes-ones that can be reversed

without leaving a trace on the surroundings. Both
system and surroundings must revert to initial
state at end of process.
 Implies net heat and net work exchange between
system and surroundings for combined process
(original and reverse) is zero.
 Such a process is an idealization- does not exist!
 REVERSIBLE & IRREVERSIBLE PROCESS

 Causes: friction, unconstrained expansion, mixing, heat transfer

under finite temperature differences, electrical resistance…etc.
 Internally reversible: no irreversibilities within system (the
system go back to its original state after a complete cycle, but
the surrounding does not).
 Externally reversible: no irreversibilities outside system
boundaries (surrounding is not affected by the completed
cycle).
 Totally reversible or simply reversible, if both have no
irreversibilities (the system/surrounding go back to its original
state after a complete cycle, but the does not).
EFFICIENCY
The efficiency of a heat engine is defined as
the ratio of the work done to the input heat:

W
e
QH
If there are no other losses, then

QH  W  QC

W  QH  QC

QH  QC QC
e  1
QH QH
Example: An Automobile Engine

An automobile engine has an efficiency of 22.0% and produces

2510 J of work. How much heat is rejected by the engine?

QH  W  QC W
e W
QH QH 
e
QC  QH  W

W 1 
QC   W  W   1
e e 

 1 
QC   2510 J    1  8900 J
 0.220 
An automobile engine that burns gasoline has been engineered to
have a relatively high efficiency of 22 %. While a car is being
driven along a road on a long trip, 14 gallons of gasoline are
consumed by the engine. Of the 14 gallons, how much gasoline
was used in doing the work of propelling the car?

a) 14 gallons

b) about 11 gallons

c) about 8 gallons

d) about 3 gallons

e) about 1 gallon
CARNOT PRINCIPLE

A reversible process is one in which both the system and the

environment can be returned to exactly the states they were in
before the process occurred.

CARNOT’S PRINCIPLE: AN ALTERNATIVE STATEMENT OF THE SECOND

LAW OF THERMODYNAMICS

No irreversible engine operating between two reservoirs at constant temperatures

can have a greater efficiency than a reversible engine operating between the same
temperatures. Furthermore, all reversible engines operating between the same
temperatures have the same efficiency.

Same can be stated for the Carnot refrigeration and heat pump cycles.
CARNOT ENGINE
 The Carnot engine is useful as an
idealized model.
 All of the heat input originates from a
single temperature, and all the rejected
heat goes into a cold reservoir at a single
temperature.
 Since the efficiency can only depend on
the reservoir temperatures, the ratio of
heats can only depend on those
temperatures
QC T
 C
QH TH

QC TC TC
e  1  1 ec  1 
QH TH TH
CARNOT ENGINE
Example : A Tropical Ocean as a Heat Engine

Water near the surface of a tropical ocean has a temperature of 298.2 K, whereas
the water 700 meters beneath the surface has a temperature of 280.2 K. It has
been proposed that the warm water be used as the hot reservoir and the cool water
as the cold reservoir of a heat engine. Find the maximum possible efficiency for
such and engine.

TC 280.2 K
ec  1   1  0.060
TH 298.2 K
 CARNOT REFRIGERATION & HEAT PUMP
 It is the idealized model for refrigeration and heat pump
cycles.
 The cycle takes the reversed direction of the Carnot engine
cycle (it will go anti-clock wise) and work is negative (input
work).
 In Heat pump: useful heat is utilized at the hot reservoir for
space heating purpose.
 In Refrigerator: useful heat is pulled-out from the cold
reservoir for space cooling purpose.
 Since the efficiency can only depend on the reservoir
temperatures, the ratio of heats can only depend on those
temperatures
QC QC QH QH
COP( Rfr.)   COP( HP)  
W QH  QC W QH  QC
QC TC

QH TH

TC TH
COP( Rfr.) c  COP( HP) c 
TH  TC TH  TC
Sheet 1: on chapter 5 (second low of thermodynamics)
(5.23), (5.27), (5.39) & (5.45)

FUNDAMENTALS OF ENGINEERING
THERMODYNAMICS (MORAN J.)