Second Law of Thermodynamics

Leads Up To Second Law Of

Thermodynamics
It is now clear that we can’t construct a heat engine with just
one
+ve heat interaction.

The above engine is not possible.

 Second Law Of Thermodynamics
(contd…)
Is it possible to construct a heat engine with only one -
ve heat interaction?
Is the following engine possible?

The answer is yes, because

This is what happens in a
stirrer
 Second Law Of Thermodynamics
(contd…)
Perpetual motion machine of the second kind is not possible.

Perpetual motion machine of

the first kind violates I LAW W
(It produces work without
receiving heat)
 Common sense tells us that

1Heat flows from a body at higher A hot cup of coffee left in a room
temperature to a body at lower becomes cold. We have to expend
temperature energy to rise it back to original
temperature

Possible Not possible

(you can’t make room heat up your coffee!!)
 Common sense tells us that

2.Fluid flows from a point of Water from a tank can flow down To
higher pressure or potential. get it back to the tank you have to
to a lower one use a pump i.e, you spend energy

Possible
 Definitions of Reversible Process
 A process is reversible if after it, means can be found
to restore the system and surroundings to their initial
states.
Some reversible processes:
 Constant volume and constant pressure heating and
cooling - the heat given to change the state can be
rejected back to regain the state.
 Reversible Process (contd…)

 Isothermal and adiabatic processes -the work derived

can be used to compress it back to the original state
 Evaporation and condensation
 Elastic expansion/compression (springs, rubber bands)
 Lending money to a friend (who returns it promptly)
 Some Irreversible Process
spontaneous
motion with chemical reaction
friction

unrestrained
heat transfer expansion

T1 > P1 >
T2 P2

Q
 Reversible Cycle

 A cycle consisting of all reversible processes is a

reversible cycle. Even one of the processes is irreversible,
the cycle ceases to be reversible.

Otto, Carnot and Brayton cycles are all reversible.

A reversible cycle with clockwise processes produces work
with a given heat input. The same while operating with
counter clockwise processes will reject the same heat with
the same work as input.
 Other reversible cycles:

Diesel cycle Ericsson cycle Stirling cycle

 Clausius Statement of II Law of
Thermodynamics

It is impossible to construct a device which operates in a cycle and

produces no effect other than the transfer of heat from a cooler
body to a hotter body.
 Yes, you can transfer heat from a cooler body to a hotter body by
expending some energy.
 Clausius Statement (contd…)

 Note : It is not obligatory to expend work, even

thermal energy can achieve it.

 Just as there is maximum +ve work output you can derive

out of a heat engine, there is a minimum work you have to
supply (-ve) to a device achieve transfer of thermal energy
from a cooler to a hotter body.
 Carnot Cycle for a
Refrigerator/heat Pump

Heat sink
T1

Q1

T1>T2
T2 Q2
TH=T1
Heat source
TC=T2
 Heat pump

 A device which transfers heat from a cooler to a warmer body

(by receiving energy) is called a heat pump. A refrigerator is a
special case of heat pump.
Just as efficiency was defined for a heat engine, for a heat pump the
coefficient of performance (COP) is a measure of how well it is
doing the job.
 Heat Pump (contd…)

 A heat pump
• Invoke the definition: what we have achieved ¸ what
we spent for it
• COPHP = heat given out ¸ work done = ½Q1/W½
• Note : The entity of interest is how much heat could
be realised. Work is only a penalty.
 Heat Pump (contd…)

Reverse cycle air conditioners used for winter heating do the

above. Heat from the ambient is taken out on a cold day and
put into the room.

The heat rejected at the sink is of interest in a heat pump , ie.,

Q1.

In a refrigerator the entity of interest id Q 2 .

In this case COP R =  Q2/W 

NOTE:  ,COPHP COP R are all positive numbers  but COPs
can be > or < 1
 Heat Pump (contd…)
Relation between  and COPHP

It is not difficult to see that  COPHP =1

Apply I law to Carnot cycle as a heat pump/refrigerator:

-Q1+Q2 = -W or Q1=Q2+W
Divide both sides with W Q1/ W = Q2 / W + 1

or COPHP = COPR+1

The highest COPHP obtainable therefore will be T1/(T1-T2)

and highest COPR obtainable therefore will be T2/(T1-T2)

 Summation of 3 Laws
You can’t get something for nothing
To get work output you must
give some thermal energy
You can’t get something for very little
To get some work output there
is a minimum amount of
thermal energy that needs to
be given
You can’t get every thing
However much work you are
willing to give 0 K can’t be
reached.
Violation of all 3 laws: try to get everything for nothing
 Equivalence of Kelvin-Planck
and Clausius statements

II Law basically a negative statement (like most laws in

society). The two statements look distinct. We shall prove
that violation of one makes the other statement violation too.

Let us suspect the Clausius statement-it may be possible to

transfer heat from a body at colder to a body at hotter
temperature without supply of work
Equivalence of Kelvin-Planck
and Clausius statements

Let us have a heat engine

operating between T1 as source
and T2 as a sink. Let this heat
engine reject exactly the same Q2
(as the pseudo-Clausius device)
to the reservoir at T2. To do this
an amount of Q1 needs to be
drawn from the reservoir at T1.
There will also be a W =Q1-Q2
 Equivalence of Kelvin-Planck
and Clausius statements
Combine the two. The reservoir at T2 has not undergone
any change (Q2 was taken out and by pseudo-Clausius
device and put back by the engine). Reservoir 1 has given
out a net Q1-Q2. We got work output of W. Q1-Q2 is
converted to W with no net heat rejection. This is violation
of Kelvin-Planck statement.
 Equivalence of Kelvin-Planck
and Clausius statements
• Let us assume that Clausius statement is true and
suspect Kelvin-Planck statement
Pseudo Kelvin Planck engine
requires only Q1-Q2 as
the heat interaction to give
out W (because it does not
reject any heat) which drives
the Clausius heat pump
May be possible? Combining the two yields:
 The reservoir at T1 receives Q1
but gives out Q1-Q2 implying a net
delivery of Q2 to it.
Q2 has been transferred from T2
to T1 without the supply of any
work!!
 A violation of Clausius statement
 Equivalence of Kelvin-Planck
and Clausius statements
Moral: If an engine/refrigerator violates one version of
II Law,
it violates the other one too.
All reversible engine operating between the same two
fixed temperatures will have the same  and COPs.
If there exists a reversible engine/ or a refrigerator
which can do better than that, it will violate the Clausius
statement.
 Equivalence of Kelvin-Planck
and Clausius statements
Let us presume that the HP is super
efficient!!
For the same work given out by the engine
E, it can pick up an extra DQ from the low
temperature source and deliver over to
reservoir at T1. The net effect is this extra
DQ has been transferred from T2 to T1
with no external work expenditure.
Clearly, a violation of Clausius
statement!!
 Equivalence of Kelvin-Planck
and Clausius statements (contd…)

SUM UP

 Heat supplied = Q1; Source temperature = T1 ;Sink

temperature= T2
 Maximum possible efficiency = W/Q1= (T1-T2)/T1
 Work done = W= Q1(T1-T2)/T1
 Equivalence of Kelvin-Planck
and Clausius statements (contd…)

Applying I Law
Sum of heat interactions = sum of work interactions
Q1+ Q2=W= Q1 (T1-T2)/T1
Q1 is +ve heat interaction; Q2 is -ve heat interaction
 Equivalence of Kelvin-Planck
and Clausius statements
 Heat rejected = -ve heat interaction = -Q2= (Q1-W)=
Q1T2/T1
 For a reversible heat engine operating in a cycle Q1/T1+Q2 /
T2= 0
 or S(Q/T) = 0

Ideal engine
10,000/600 +(-5000/300)=0

Not so efficient engine

10,000/600+ (-7000/300) < 0