Lecture 5

Thermodynamics.
Chapter 4

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2nd Law of Thermodynamics

A heat engine is a system that operates
continuously and across whose boundaries
only heat and work flows.
High temperature
energy reservoir
Q1

Forward
Heat Engine

Q1 + ve
W - ve
Q2 - ve

Q - ve

Q2

1
Reverse
Heat Engine W + ve

Low temperature
energy reservoir

Q2 + ve

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Definition of second law of thermodynamics in

the context of forward heat engine;
It is impossible for a heat engine to produce a
net work output in a complete cycle if it
exchanges heat only with a single reservoir.
Q1 >
-W
Cycle efficiency, = - W / Q1
The second law implies that the cycle
efficiency must always be less than unity.

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Definition of second law in context of reversed heat engine;

It is impossible to construct a device that operating in a
cycle will produce no effect other than the transfer of heat
from a cooler to a hotter body.
W

>

The effectiveness of a reversed heat engine is defined in term

of a coefficient of performance, COP.
For refrigerator COPref
=
Q2 / W
For heat pump
COPhp
=
- Q1 / W
COP for both refrigerator and heat pump is always greater
than unity.

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Entropy
a thermodynamic quantity representing the unavailability of a system's thermal
energy for conversion into mechanical work, often interpreted as the degree of
disorder or randomness in the system.
Entropy follows the second law of thermodynamics.
Consider a reversible adiabatic process for any system on a Pv diagram shown by AB.
Then it undergoes a reversible isothermal process at temperature T1 from B to C.
Then it undergoes a Reversible adiabatic process from C to A.
Heat is only transferred from B to C during the isothermal process. It means that the
system draws heat from a reservoir at one fixed temperature. This is impossible
because it violates the second law. Therefore, it is concluded that it is not possible
to have two reversible adiabatic processes passing through the same state A.
One important characteristic of a thermodynamic property of a system is that its any
fixed value is represented by a unique line on a diagram of properties. The
uniqueness of the lines implies that two lines representing two different values of
the same property will never cross each other.
Keeping in view the above-mentioned characteristic of a thermodynamic property it is
concluded that there must be a property represented by a reversible adiabatic
process. This property is called entropy, s.

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There is no change of entropy in a reversible adiabatic process. Each

reversible adiabatic process represents a unique value of entropy.
ds
=
dQ / T for all working substances.
(1)
dQ is the heat added reversibly
Change in entropy
in kJ/kg K
Total entropy
S
=
m.s
Or, from eq (1)
dQ
=
T . ds
or
for any reversible process
A diagram can be plotted with Temperature and Specific entropy as the
axes. The area under the curve on such a diagram will represent
heat supplied in a reversible process.
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T s diagram
Reversible Processes on the T s diagram.
Reversible Isothermal Process.
Heat Supplied =
T ( s2 s1 )
For Perfect gas
From non-flow equation
dQ =
du + P dv
From Joules law

du

Cv dT

dQ =
Cv dT + P dv
For an isothermal process, dT = 0
Therefore, dQ =
P dv
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From characteristic gas equation, we have

P =
RT/v
Putting for P
dQ =
R T dv / v
Now, we have
s2 s1
=
dQ / T (from state 1 to 2)
=
R T dv / ( T v ) (from v1 to v2)
=
R dv / v (from v1 to v2)
s2 s1
Heat supplied, Q
= R T ln (P1 / P2)

R ln (v2 / v1) =

T (s2 s1)

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R ln (P1 / P2)
R T ln (v2 / v1)

Reversible adiabatic Process (Isentropic

Process)
It was stated earlier that no simple method was
available for fixing the end states of a vapor
undergoing an isentropic process. Now, using
the fact that the entropy remains constant,
the end states can be found easily from tables.
Isentropic process follows Pv = C, where is
called isentropic index.

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Enthalpy properties
The change H is positive in endothermic
reactions, and negative in heat-releasing
exothermic processes.

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Heat Engine Cycles

1. The Carnot Cycle.
Carnot showed that the most efficient possible heat engine cycle is one in
which all the heat is supplied at one fixed temperature and similarly all the
heat is rejected at a lower fixed temperature.
Process 1 to 2
isentropic expansion from T1 to T2
Process 2 to 3
isothermal heat rejection
Process 3 to 4
isentropic compression from T2 to T1
Process 4 to 1
isothermal heat supply
The cycle is completely independent of the working substance used.
The Cycle efficiency

Carnot

T1 T2 s B s A
T
1 2
T1 s B s A
T1
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2. The Constant Pressure Cycle.

This is ideal cycle for the closed cycle gas turbine unit. Air is
the working substance is this case.

Work input to compressor

T2 T1 )
Work output from turbine
T3 T4 )
Heat supplied in heater
T3 T2 )
Heat rejected in cooler
T4 T1 )

Efficiency=

( h2 h1 )

Cp (

( h3 h4 )

Cp (

( h3 h2 )

Cp (

( h4 h1 )

Cp (

1 - ( T4 T1 ) / ( T3 T2 )
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3.The Otto Cycle.

This is the ideal air standard cycle for the petrol
engine, the gas engine, and the high speed oil
engine.
Process 1 to 2
isentropic compression
Process 2 to 3
reversible constant volume
heating
Process 3 to 4
isentropic expansion
Process 4 to 1
reversible constant volume
cooling
=

-1

1 - (T4 T1) / (T4 T1) rv -1

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1 - 1 / rv

4. The Diesel Cycle

Process 1 to 2
Process 2 to 3
heating
Process 3 t 4
Process 4 to 1
cooling

isentropic compression
reversible constant pressure
isentropic expansion
reversible constant volume

Thermal efficiency, =
Q / Q1
=
1 - ( - 1 ) / * ( 1) rv-1 +
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