CHAPTER 3

THERMODYNAMICS

OUTLINE
Introduction
Zeroth law of thermodynamics
First law of thermodynamics
Application of first law
Second law of thermodynamics
Application of second law

INTRODUCTION
Thermodynamics is the study of the

conversion of heat energy into different

forms of energy (in particular, mechanical,
chemical, and electrical energy); different
energy conversions into heat energy; and
its relation to macroscopic variables such
as temperature, pressure, and volume.
Two most important properties to be used

is heat and temperature

PROPERTIES
Temperature :- defined as quantity

of heat energy contain in a system.

SI unit :- Kelvin
Heat :-Form of energy that is

transferred between object because

of temperature difference.
SI unit for heat is joule, (Kgm2s-2)

ZEROTH LAW OF
THERMODYNAMICS
states that if two systems are at the same

time in thermal equilibrium with a third

system, they are in thermal equilibrium with
each other.

If A and C are in thermal equilibrium with B,

then A is in thermal equilibrium with B.

Practically this means that all three are at the
same temperature, and it forms the basis for
comparison of temperatures.

FIRST LAW OF
THERMODYNAMICS
The first law of thermodynamics is the

application of the conservation of energy

principle to heat and thermodynamic
processes:

THE INTERNAL ENERGY (U)

total energy content of system.
Sum of the kinetic, potential, chemical,

electrical, nuclear and all other forms of

energy possessed by the atoms and
molecules of the system.

THE WORK DONE BY A SYSTEM

W(
)
Positive if the system loss energy to its

surrounding.
If the surrounding
W do work on the system so
V then
as to give it energy,
is a
negative quantity.
In a small expansion
, a fluid at constant
pressure p does work given by

W p V

ISOBARIC PROCESS
process carried out at constant pressure,

P 0

ISOVOLUMIC PROCESS
process carried out at constant volume,

V 0
when a gas undergoes such as process,

W pV 0
so the first law of thermodynamics becomes

Q U

ISOTHERMAL PROCESS
a constant temperature process
U 0
for ideal gas,
so the first law of thermodynamics becomes

Q W
if ideal gas changing from (p1,V1) to (p2,V2)

where
pV p V
1 1

2 2

V2
V2
Q W p1V1 ln( ) 2.30 p1V1 log( )
V1
V1

ADIABATIC PROCESS
no heat is transferred to or from the

system
Q 0

so the first law of thermodynamics becomes

0 U W
any work done by the system is done at the

expense of the internal energy. Any work done

on the system serves to increase the p
internal
1 , V1 , T1
energy.
p2 , V2 , T2
For an ideal gas changing from conditions (
) to (
) in adiabatic process,


1 1

2 2

PV P V

c p /c n

1
1 1

and T V

1
2 2

TV

SPECIFIC HEATS OF GASES

Gas heated at constant volume, heat

energy supplied goes to increase the internal

energy of the gas molecules.
Gas heated at constant pressure, heat
energy supplied goes to increase the internal
energy of the gas molecules and does
mechanical work in expanding the gas.

R
c p cv
(ideal gas)
M
R = 8314 J/kmol.K or 1.98 cal/mol. 0C -

universal gas constant,

M - kg/kmol or g/mol
Cp , CV J/kg.K = J/kg.0C or cal/g. 0C

SPECIFIC HEAT RATIO

cP / cV
For monoatomic gases (He, Ne, Ar),
1.67
For diatomic gases (O2, N
at
2),1.40

ordinary temperature.

EXAMPLE
Question:
In a certain process, 8000 cal of heat is

furnished to the system while the system does

6000 J of work. By how much does the internal
energy of the system change during the
process?

Answer:

Q (8000cal )(4.184 J / cal ) 33.5kJ

from the first law,Q U W
U Q W 33.5kJ 6kJ 27.5kJ

W 6kJ

P-V DIAGRAM
General Gas Equations

PV
P2V2
PV
1 1
c or

T
T1
T2
P = absolute pressure (Pa)
V = Volume (m3)
T = absolute temperature (K)
c = constant

Equation of State

PV mRT
m = mass of gas (kg)
P = absolute pressure (Pa)
V = Volume (m3)
T = absolute temperature (K)

Gas Constant

8314
R
, J / kgK
M
M = Relative Molecular Mass

EXAMPLE
Question 1:
A mass of gas has volume 4m3 when the

temperature is 1200C and the pressure is

25kPa(gauge). Determine the volume of this
mass of gas at normal atmospheric condition
(200C and 101.3kPa)

Answer 1:

P1 25 101.3 126.3kPa
P2 101.3kpa
PV
P2V2
1 1

T1
T2
126.3 293
3
V2

4 3.72m
101.3 393

Question 2:
A compressed air tank in a cylinder has a

volume 0.1767m3. After filling, a pressure

gauge fitted to tank reads 1MPa when atm
pressure is 101.3kPa and the temperature of
the air in tank is 200C. Calculate the mass of
air in tank.R for air = 287J/kgK

Answer 2:
Abs pressure :

P 1 10 101.3 10 1.1013 10 Pa
6

Abs temperature :

T 20 273 293K

PV mRT
m 2.314kg

A "p-V diagram" is a graph showing changes

in the pressure and volume of a sample of

gas.
1. Change of P (and T) at constant
volume; an isovolumetric change.
2. Change of V (and T) at constant
pressure; an isobaric change.
3. Change in P and V at constant
temperature; an isothermal change.
4. Change in P and V in an
insulated container (no heating of
the gas); an adiabatic change.

Polytropic Process pressure, volume and

temperature all change

An example of polytropic process is the
compression/expansion of gas under
conditions where some heat flow occurs. Most
actual compression/expansion processes on
gases follow the polytropic process

PV c
n

PV P2V2
n
1 1

Work,

T2
V1 n 1
or
( )
T1
V2
P2
T2
or
( )
P1
T1

PV
1 1 P2V2
W
n 1

n
n 1

Refer to the table given for the relation of P-V

formula.

EXAMPLE
Question
A mass of 0.2kg of nitrogen (relative
molecular mass, M = 28) of 100kPa(abs) and a
temperature of 300K is slowly compressed, so
the temperature remain constant, until the
pressure reaches 1MPa(abs).Calculate:
the initial volume
the final volume
the work transfer
the heat flow

Solution:

PV
1 1 mRT1
8314 8314
RN2

297 J / kgK
M
28
mRT1
3
V1
0.178m
P1

PV
1 1 P2V2
V2 0.0178m

V2
W PV
41kJ
1 1 ln
V1
Q 41kJ

EXAMPLE
Question:
A gas of mass 0.06kg is heated at constant
pressure of 200kPa(abs) from temperature
1000C and volume 3L to temperature 3000C
and volume 4.6L. The specific heat capacity at
constant volume of gas,CV = 700J/kgK.
(1m3=1000L)Determine:
a) internal energy
b) work done
c) heat supplied

Solution:
U=mC

(T2 T1 ) 0.06(700)(200) 8400 J

200 10 (4.6 3) 10

Q W

320 J

HEAT ENGINES
A heat engine typically uses energy provided

in the form of heat to do work and then

exhausts the heat which cannot be used to do
work.
Thermodynamics is the study of the
relationships between heat and work. The first
law and second law of thermodynamics
constrain the operation of a heat engine. The
first law is the application of conservation of
energy to the system, and the second sets
limits on the possible efficiency of the
machine and determines the direction of

Efficiency of Heat
Engine
Analysed by black- box system :
Under steady state conditions over a certain

time period :

Qs W QR
Or W Qs QR

work output of a heat

engine

Using a time
period of 1s:
& &

P QS QR

engine

,power output of the heat

The efficiency or coefficient of performance

(COP) is: W
QR
Q&R
P QS QR

1
1
QS Q&S
QS
QS
Q&S

, efficiency
of heat
engine.
:
QS quantity
of heat
suppliedWhere
(J)
QR quantity of heat rejected (J)
W work output (J)
Q& heat - supply rate (W)
S

Q&R heat - rejection rate (W)

P power output (W)

The following process constitute the

Carnot Cycle :
1 2

isothermal compression : heat

rejected to sink at constant temperature ;the
pressure
2 3 increase.
adiabatic compression; the
pressure and temperature both increase
without any heat flow taking place.

 3 4

isothermal expansion; heat

supplied from source at constant
temperature ; pressure decrease
4 1

adiabatic expansion; pressure and

temperature both decrease until they have
their same initial values; no heat flow occurs.

CARNOT CYCLE

Maximum efficiency of a heat engine the

limiting efficiency ( or maximum possible

efficiency ) of heat engine is known as the
CARNOT EFFICIENCY, given by the
equation :

TH TC
TC
C
1
TH
TH

Where,
TH = temperature in Kelvins of the working
substance when heat flows in from source
(Thot
temperature ).
C

= temperature in Kelvins of the working

substance when heat flows out to the sink
( cold temperature ).

Using these two expressions together:

Example
Question
Determine the maximum possible efficiency

of the an internal combustion engine using

the atmosphere (ambient) at 200C , the
temperature after combustion being 14500C

Answer:

TH 1723K , TC 293K
TC
293
C 1
1
0.83 83%
TH
1723

STIRLING CYCLE
An external heat, closed two stroke cycle,

uses a gas as the working substance.

STIRLING CYCLE EFFICIENCY, given by the
equation :

TH TC
TC

1
TH
TH

EXAMPLE
Question:
In a stirling- cycle engine, the working substance
achieves a maximum temperature of 600 0C and a
minimum temperature of 1000C. The heat supply
rate is 50kW and the actual efficiency is 25%.
Determine:
the ideal efficiency;
the ideal power output;
the actual power output;
the actual heat rejection rate

Solution:

ideal
Pideal

TC
373
1
1
0.573
TH
873
Q& 0.573 50 28.6kW
ideal

Pactual actual Q& 0.25 50 12.5kW

Q& Q& P 50 12.5 37.5kW
R

OTTO CYCLE
Positive displacement, four stroke, internal

combustion, spark ignition, open cycle.

Theoritical work and efficiency ; compression
and expansion are adiabatic, so heat flow
occurs only during the constant volume;
Heat supplied, QS

mCV (T3 T2 )

Heat rejected, QR
(positive)

mCV (T4 T1 )

Work,

W QS QR
Cycle efficiency,

work
W

heat supplied QS

SECOND LAW OF
THERMODYNAMICS
Second Law of Thermodynamics can be
stated in three equivalent ways:
1. Heat flows spontaneously from a hotter to

colder object, but not vice versa.

2. No heat engine that cycles continuously can
change all its heat in to useful work-out.
3. If system undergoes spontaneous change, it
will change in such way that its entropy will
increase or, at best, remain constant.

REFRIGERATOR
In a continuous refrigeration process, heat

absorbed at low temperature is continuously

rejected to the surroundings at higher temperature.
Basically, refrigeration cycle is reversed heat
engine cycle.
Heat is transferred from a low temperature level to
higher second law, this requires an external source
of energy.
Ideal refrigerator, like the ideal heat engine
operates on a carnot cycle, consisting 2 isothermal
steps and 2 adiabatic steps.

REFRIGERATION
DIAGRAM
Atmosphere
( Ambient )
T2,TR,TC
Q2, QR
W

Refrigeration
Process
T1,TS,TH

Q1,Q
S

EQUATIONS
Q1 Q2 Q&1 Q&2

T1 T2 T1 T2
Q1 , Q2 J or KJ
Q&1 , Q&2 J/s or KJ/s =W or KW
Power, P Q&1 Q&2 , J/s or KJ/s = W or KW
Usual measured of the effectiveness of refrigerator
is called COP.
Q2
T2
Heat absorbed at lower temperature QR
COP

W
W
W T1 T2