The Second law of thermodynamics

Chapter 7
 The Second law of thermodynamics
Cont

 The first law of thermodynamics states that during any

cycle that a system undergoes, the cyclic integral of
the heat is equal to the cyclic integral of the work.

 However, we know from our experience that because

a proposed cycle does not violate the first law does not
ensure that the cycle will actually occur.

 It is this kind of experimental evidence that led to the

formulation of the second law of thermodynamics.
 The Second law of thermodynamics
Cont

 In its broader significance the second law acknowledges

that processes proceed in a certain direction but not in
the opposite direction.

 A hot cup of coffee cools by virtue of heat transfer to the

surroundings, but heat will not flow from the cooler
surroundings to the hotter cup of coffee.

 Gasoline is used as a car drives up a hill, but the fuel

level in the gasoline tank cannot be restored to its
original level when the car coasts down the hill.
 Motivating the 2nd Law of thermodynamics

 The 1st law of thermodynamics alone does not predict

the direction of a process, e.g.
o Can a hot object naturally cool down to a temp
below its surrounding?
o Can a hot mass return to its initial position by losing its
internal energy?
 The first law does not distinguish between reversible
and irreversible processes
 The 2nd law can be used in conjunction with the 1st law
to determine the capability of a process.
 Uses of the 2nd Law

 Predict process direction

 Establish equilibrium conditions
 Determine theoretical best performance of cycles,
engines, and other devices.
 Evaluating quantitatively the factors that preclude the
attainment of the best theoretical performance level.
 Define a temp scale independent of properties of any
thermometric substance.
 Develop means for property evaluation for derived
properties, such as h and u in terms of properties that are
more readily obtained experimentally.
 Second Law of Thermodynamics
Kelvin-Planck Form
 1824 – 1907
 Physicist and mathematician
 Proposed the use of absolute
temp scale
 Work in thermodynamics led to
idea that energy cannot
spontaneously pass from colder
to hotter objects.
o Kelvin-Plank statement is “more
useful” in practice, since it deals
with thermodynamic cycles.
 Second Law of Thermodynamics
Kelvin-Planck Form
 "It is impossible for any device that operates on a cycle
to receive heat from a single reservoir and produce a net
amount of work ".

This statement talks about the heat engine.

 Kelvin-Planck statement
"It is impossible for any system to operate in a
thermodynamic cycle and deliver a net amount of energy by
work to its surroundings while receiving energy from a single
thermal reservoir".
 Second Law of Thermodynamics
Kelvin-Planck Form

The Kelvin-Planck statement of the 2nd law of

thermodynamics states that no heat engine can produce a
net amount of work while exchanging heat with a single
reservoir only. In other words, the maximum possible
efficiency is less than 100%.

 th < 100%
 Second Law of Thermodynamics
Clausius Form

o Rudolf .Clausius,(1822-1888)
o A German professor (1850-
1851)
o Second law of thermodynamics;
“entropy”;
o Temperature scale;
 Second Law of Thermodynamics
Clausius Form
 " It is impossible to construct a device that operates in a
cycle and produces no effect other than the transfer of heat
from a lower-temp body to a higher-temp body ".
 Clausius Statement
" It is impossible for any system to operate in such a way
that the sole result would be an energy transfer by heat from
a cooler to a hotter body "

There is no such a heat pump that transfers heat from a low

temp reservoir to a high temp reservoir without consuming
external work.
 Second Law of Thermodynamics
Clausius Form, cont

 This statement is related to the refrigerator or heat pump.

In other words, heat cannot flow itself from a cold body to a
hot body without the help of an external agency (i.e. without
the expenditure of mechanical work). This also implies that
the coefficient of performance is always less than infinity.

i.e COP  
 Heat Engine

 A heat engine may be defined as 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 temp body to a low temp body.
 Heat Engine
Considered a heat engine (Fig.)
in which water (steam) is the working
fluid. An amount of heat, QH, is
transferred from the furnace to the
water in the boiler to form steam which
then works on the turbine rotor to
produce work WT, the steam is
condensed to water in the condenser
in which an amount of heat QL is
rejected from the system, and finally
work WP is done on the system to
pump it to the boiler. The system
repeats the cycle.
Heat Engine, cont
 Heat Engine, cont

 The working substance

absorbs energy by heat from a
high temp energy reservoir Qh.

 Work is done by the engine

Weng.

 Energy is expelled by heat to

a lower temp reservoir Qc.
 Heat Engine, cont

Thermal efficiency is defined as

th = Net work output of the cycle / Total heat input to the
cycle.

= Wnet / QH .................................................………… (1)

From First Law of Thermodynamics

∫ W = ∫ Q

or, WT  WP = Q H  QL
 Heat Engine, cont

From Eqn (1) & (2) we get

th = QH  QL/QH
= 1 QL/ QH

Examples:
 Diesel cycle ( Diesel Engine).
 Otto cycle (Gasoline Engine).
 Stirling Engine.
 Carnot cycle (idealized heat engine).
Refrigerator

Fig.7.2 A simple Refrigeration cycle

 Refrigerator

The efficiency of a refrigerator is expressed in terms of the

coefficient of performance which we designated with the
simple . For a refrigerator the objective, that is the energy
sought, is QL, the heat transferred from the refrigerator
space. The energy that costs is the work W. Thus the
coefficient of performance  is
Refrigerator
 Heat Pump

 Device that transfer heat

from a low-temp medium to a
high temp-medium
 Energy is extracted from
the cold reservoir, QC

 Energy is transferred to the

hot reservoir, Qh

 Work must be done on the

engine, W
 Three Observations should be made
about these two statements

 First Observation. Both are negative statements. It is

of course impossible to " prove “ these negative statements.
However, we can say that the 2nd law of thermodynamics
rests on experiment evidence. Every relevant experiment
that has been conducted either directly or indirectly verifies
the 2nd law, and no experiment has ever been conducted
that contradicts the 2nd law. The basis of the 2nd law is
therefore experimental evidence.
 Observations

 Second Observation. These two statements of the

second law are equivalent, if the violation of each statement
implies the violation of the others. That is a violation of the
Clausius statement implies a violation of the Kelvin-Planck
statement.

 The third observation. Frequently the 2nd law of

thermodynamics has been stated as the impossibility of
constructing a perpetual-motion machine of the second kind.
 A perpetual-motion machine of the first kind would
create work from nothing.
 Violation of the Clausius statement implies
a violation of the Kelvin-Planck statement.

Fig. Demonstration of the equivalence of the two statements of the

second law.

The device at the left is refrigerator that requires no work and

thus violates the Clusius statement.
 Violation of the Clausius statement implies
a violation of the Kelvin-Planck statement.

 Let an amount of heat QL be

transferred from the low temp
reservoir to this refrigerator, and let
the same amount of heat QL be
transferred to the high temp
reservoir. Let an amount of heat
QH that is greater than QL be
transferred from the high temp
reservoir to the heat engine, and
let the engine reject the amount of
heat QL as it does an amount of
work W, which equal QH - QL.
 Violation of the Clausius statement implies
a violation of the Kelvin-Planck statement.

 Because there is no net

heat transfer to the low-temp
reservoir, the low-temp
reservoir, along the heat
engine and the refrigerator,
can be considered together
as a device that operates in a
cycle and produces no effect
other than the raising of a
weight (work) and the
exchange of heat with a
single reservoir.
 Violation of the Clausius statement implies
a violation of the Kelvin-Planck statement.

 Thus, a Violation of the Clausius statement implies a

violation of the Kelvin-Planck statement. The complete
equivalence of these two statements is established when it
is also shown that a violation of the Kelvin-Planck statement
implies a violation of the Clausius statement .
 A Perpetual-motion Machine of the 2nd kind

Fig.7.11 A Perpetual-motion Machine of the 2nd kind

 A Perpetual-motion Machine of the 2nd kind

 Consider Fig 7.11 which

might be a power plant of a ship.
An amount of heat QL is
transferred from the ocean to a
high- temp body by means of a
heat pump. The work required is
WI, and the heat transferred to
the high temp body is QH. Let the
same amount of heat be
transferred to a heat engine that
violates the Kelvin-Planck
statement of the second law and
does an amount of work W = Q .
 A Perpetual-motion Machine of the 2nd kind

Of this work an amount

QHQL is required to drive the
the heat pump, leaving the net
work (Wnet = QL) available for
driving the ship. Thus, we
have a perpetual machine in
the sense that work is done by
utilizing freely available
sources of energy such as the
ocean or atmosphere.
Equivalence of the two statements

(source)

=0

(sink)