ENGINEERING THERMODYNAMICS I

Prof. J F Kanyua

Module 2 (Part 4)

2nd Law of Thermodynamics

1) Recall 1st Law

1st Law of Thermodynamics deals with conservation of energy and introduces the
concepts of closed system, reversibility, cyclic process, properties of fluid (h, u).

∑ dQ = ∑ dW
The 1st Law is a natural Law.
2) 2nd Law of Thermodynamics.
Recall definition of “Thermodynamics”: Study of relationship between properties
of a fluid and heat and work transfer.
Recall the heat and work transfer devices introduced earlier.
3) Heat Engine
A heat engine is a system operating in a cycle and producing a quantity of work
from a supply of heat.
A heat engine converts heat energy to mechanical energy (work). The source of
heat energy may be a fossil fuel, nuclear fuel, geothermal energy, solar energy
etc. which provide heat at high (relatively) temperatures.
Since the purpose of the heat engine is to convert heat energy to mechanical
energy, the greater the % of heat energy converted to work energy, the better is
the heat engine.
This introduces the concept of cycle efficiency of a heat engine which is defined
as:
η = Work Done / Heat Supplied
The 1st Law does not in any way imply that some of the heat supplied in the cycle
must be rejected i.e. the 1st Law does not say that cycle efficiency cannot be equal
to unity (100%).
4) Perpetual Motion Machine of First Kind
This is a machine in which a net work output is produced without some heat
being supplied.
The 1st Law says that the perpetual motion machine of the first kind is not
possible.
5) 2nd Law of Thermodynamics

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 Recall definitions of heat sink and heat source.

Statement of 2nd Law:

 It is impossible to construct a system which operates in a cycle, extracting heat
from a heat reservoir, and doing an equivalent amount of work on the
surroundings.
 It is impossible for a heat engine to produce net work in a complete cycle if it
exchanges heat only with bodies at a single fixed temperature (implies single
heat reservoir)

HEAT SOURCE

Q1

W
HE

Q2

HEAT SINK
HEAT ENGINE

From 1st Law:

∑ dQ = ∑ dW (Net Work)

Or Q1 – Q2 = W

η = W/Q 1 = (Q 1 – Q 2 ) /Q 1

If Q 2 = 0 i.e. system exchanges heat with only one heat reservoir, then η = 1
which is contrary to 2nd Law of Thermodynamics.

If W < Q 1 (i.e. η < 1.0) then some heat must be rejected and Q 2 must have a
finite value, and a heat sink must be available.

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Note:

1st Law and 2nd Law apply simultaneously.

6) Reversibility and Irreversibility

The reversible process was introduced with respect to non-flow processes, and
stated that as a system changes from the initial state to the final state, the system
passes through a series of equilibrium states. This will happen only if heat and
work cross the boundary in a particular way i.e.
a) Heat transfer must occur by virtue of an infinitesimally small temperature
difference, and
b) Work must only be done when the force exerted by the surroundings on the
moving boundary is infinitesimally different from the force due to the pressure of
the fluid in the system.

When the above conditions are fulfilled, only an infinitesimal change in temperature
of the heat reservoir, or force applied to the boundary by surroundings is necessary
to reverse the process and make the system to return to its original state through a
series of equilibrium states.

In this way, any work done by the system on the surroundings is returned to the
system, and any heat supplied by the surroundings to the system is returned to the
surroundings (reservoir).

In this way, there is no effect left in the system and the surroundings of either the
original process or the reversed process because any changes required to reverse the
process are infinitesimal.

We have now shown how the idea/concept of reversibility can be applied to both
non-flow and steady-flow processes.

7) Criterion for Reversibility

When a working fluid (system) undergoes a reversible process, both the fluid and
the surroundings can always be restored/returned to their original states.

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 This criterion allows us to treat a steady-flow process as a reversible process
provided that the fore-mentioned conditions are met.

Heat transfer across an infinitesimal temperature difference implies a reversible

heat transfer process is isothermal.

In real life, a steady-flow process cannot be said to undergo a process at all,

because the properties of the fluid within it are constant everywhere with respect
to time, and fluid is clearly never in a state of equilibrium.

8) Effect of Friction
Whenever one part of a fluid moves relative to another or relative to a solid
boundary with finite velocity, friction will always be present.
This is due to the viscous nature of fluids.

Friction acts in such a way as to convert some of the KE of the fluid into random
molecular energy (heat).

Reversal of a process converts more KE into random molecular energy and is

therefore not a “reversal” process.
 Friction in Non-Flow Processes
 Friction in Steady-Flow Processes

9) Reversible and Irreversible Cycles

9.1) Reversible Cycle

In a reversible cycle, all the processes are reversible. When the cycle is reversed,
all the quantities of heat and work crossing the boundary are reversed in
magnitude and direction.

A reversible cycle may consist of:

 Reversible non-flow processes, or

 Open or closed cycle made up of more than one reversible steady-flow
processes.

Sadi Carnot (1824) gave the original concept of a reversible cycle – in the form of the
Carnot Cycle described hereinafter.

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9.2) Series of Hot and Cold Reservoirs

The foregoing shows that for a process to be reversible, the processes during
heat addition or rejection must be isothermal processes.

This restriction may be overcome by the following arrangement:

a) The “heat source” is arranged to be a series of heat reservoirs (Series A) in

which small differences in temperature are allowed in the series.
b) The “heat sink” is arranged as a series of heat reservoirs (Series B) in which
small differences in temperature are allowed to exist.

Heat Sources Heat Sinks

W
A1 B1

A2 B2
Increasing Temp.
Increasing Temp

A3 B3

A4 B4

A5 B5

A6 B6

c) At any time during the heat transfer to the system, a heat source exchanges
heat with the part of the system whose temperature is infinitesimally lower than
that of the heat source.

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 d) At any instant, during the heat transfer process from the system to the heat
sink, the heat transfer is between the part of the system whose temperature is
infinitesimally higher than that of the heat sink.

The total heat transferred from the heat sources is the sum of the heat transfers from
each heat source (say Q 1 ). Similarly, the total heat transferred to the heat sinks is the
sum of the heat transfers to each heat sink. (say Q 2 )

Note:

1) If any of the processes in a cycle is irreversible, the whole cycle is irreversible.

2) If any of the processes in a cycle is irreversible, then the efficiency of such a cycle
is less than that of a cycle in which all processes are reversible.
3) The 1st Law is satisfied even when the cycle is irreversible but the cycle efficiency
is reduced.
4) In real life, there are no reversible processes.
5) A cycle efficiency calculated on the assumption of all processes being reversible
is the highest efficiency that such a plant can attain (See Carnot Cycle
afterwards).

10) Clausius Statement of 2nd Law

10.1) General Introduction

Also referred to as Corollary No. 1 of the 2nd Law.

Recall from earlier statement of 2nd Law that reference was to a heat engine i.e. a
cycle in which heat is supplied from a reservoir, and work done by the system.

Clausius Statement of 2nd Law introduces the concept of a heat pump in which heat
taken from the heat reservoir at the lower temperature is transferred to the heat
reservoir at the higher temperature. i. e. heat is being “pumped”.

10.2) Clausius Statement

 It is impossible to construct a system which will operate in a cycle and transfer

heat from a cooler reservoir to a hotter reservoir without work being done on the
system by the surroundings.

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OR

 It is impossible to construct a device (system) that, operating in cycle, will

produce no effect other than the transfer of heat from a cooler to a hotter body.

10.3) Proof of Clausius Statement

Recall definition of reductio ad absurdum.

Assume the converse to the Clausius Statement to be true.

Hotter Reservoir

Q2

W=0

Q1

Colder Reservoir

i.e for this heat pump, W = 0 as the system takes Q 1 units of heat from the Colder
Reservoir and delivers Q 2 units of heat to the Hotter Reservoir.

As far as the 1st Law is concerned, Q 1 = Q 2

Suppose we now operate a heat engine between the two reservoirs:

Hotter Reservoir

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HP HE
 Q2 Q3

W =0 W

Q1 Q4

Colder Reservoir

The 1st Law for the heat engine gives:

Q 3 – Q 4 = W or Q 3 = Q 4 + W

i.e. HE must be supplied with Q 3 = Q 4 + W units of heat energy for the Hotter
Reservoir.

If we make Q 1 = Q 4 , then the combined plant does not need the Colder Reservoir
because heat rejected by the Heat Engine can be directly transferred to the Heat
Pump.

This situation is impossible (i.e. operating with only one heat reservoir) according to
the 2nd Law of Thermodynamics and therefore the converse proposition cannot be
true and the original statement (Clausius statement of 2nd Law = Corollary I) is true.

10.4) Importance of Clausius Statement

Introduces the concept of a Heat Pump which is the basis of refrigeration cycle.

Note that Carnot proposed the Carnot Cycle and Reversed Carnot Cycle before the
Laws of Thermodynamics had been developed.

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