1

Laws of Thermodynamics
Overview
Key Definitions
Zeroth Law
Sign conventions related to 1
st
law

First Law and how it is related to
Cyclic process
Isolated process

4 Specific Thermodynamic Processes
2
Key Definitions
Thermodynamics - study of transfer of heat
energy

Thermodynamic system - system which can
exchange energy with its surroundings in two
ways:
heat transfer (Q) and mechanical work (W).

A system does work on its surroundings when its
volume changes. In other words; we say work done
by the system; in this case volume expands.

Process - The path taken to change the property
of the substance
3
State Variables
State variables describe the state of a system
In the macroscopic approach to
thermodynamics, variables are used to describe
the state of the system
Pressure, temperature, volume, internal energy
These are examples of state variables
The macroscopic state of an isolated system can
be specified only if the system is in thermal
equilibrium internally
For a gas in a container, this means every part of the
gas must be at the same pressure and temperature

4
Transfer Variables
Transfer variables are zero unless a
process occurs in which energy is
transferred across the boundary of a
system
Transfer variables are not associated with
any given state of the system, only with
changes in the state
Heat and work are transfer variables

5
P-V Diagram
Isotherms lines of equal temperatures
6
Zeroth Law
System
A - 32C
System B
- 32C
System
C - 32C
Surrounding -
32C
System
A - 80C
System
B - 100C
System
C - 40C
Allowed to interact
System
A - 80C
System
B - 100C
System
C - 40C
System
A - 53C
System
B - 53C
System
C - 53C
All systems
attain thermal
equilibrium
A
f
t
e
r

s
o
m
e
t
i
m
e

After sometime
All systems attain
thermal equilibrium
7
Sign Conventions
System
Q
W
Q added to the system; Q > 0
W by the system; W > 0
Both Positive (+ ve)
System
Q
W
Q removed from the system; Q < 0
W on the system; W < 0
Both Negative (- ve)
Case 1
Case 2
8
Work in Thermodynamics
Work can be done on a
deformable system, such as
a gas
Consider a cylinder with a
moveable piston
A force is applied to slowly
compress the gas
The compression is slow
enough for all the
system to remain
essentially in thermal
equilibrium
This is said to occur
quasi-statically

9
Thermodymanic System and Work done
When a system at pressure, p, expands from
volume V
1
to V
2
; it does an amount of work
W given by:



If the pressure, p, is constant during the
expansion;

=
2
1
V
V
pdV W
) V V ( p W
1 2
=
10
In any thermodynamic process, the heat added to
the system and the work done by the system
depends not only on the initial and final states
but also on the path (the series of intermediate
states through which the system passes).
A
B
A
Explain!!!!
11
PV Diagrams revisited
Used when the pressure and
volume are known at each
step of the process
The state of the gas at each
step can be plotted on a graph
called a PV diagram
This allows us to visualize
the process through which
the gas is progressing
The curve is called the path
Use the active figure to
compress the piston and
observe the resulting path

12
PV Diagrams, cont
The work done on a gas in a quasi-static
process that takes the gas from an initial
state to a final state is the negative of the
area under the curve on the PV diagram,
evaluated between the initial and final
states
This is true whether or not the pressure stays
constant
The work done does depend on the path
taken

13
Work Done By Various Paths
Each of these processes has the same
initial and final states
The work done differs in each process
The work done depends on the path

14
Heat Transfer, Example 1
The energy transfer, Q, into or
out of a system also depends
on the process
The energy reservoir is a
source of energy that is
considered to be so great that
a finite transfer of energy does
not change its temperature
The piston is pushed upward,
the gas is doing work on the
piston

15
Heat Transfer, Example 2
This gas has the same initial
volume, temperature and
pressure as the previous
example
The final states are also identical
No energy is transferred by heat
through the insulating wall
No work is done by the gas
expanding into the vacuum

16
First Law

Energy cannot be created nor it can be
destroyed but can be changed to other forms,
so the total energy of the system remains
constant before during and after the change.

1
st
law is extenstion of Law of Conservation
of Energy or the First Law of
Thermodynamics.
17
1
st
Law and Internal Energy
when heat Q is added to a system & when it
does work W, the internal energy U changes
by an amount:

U
2
U
1
= Q
(added)
W
(by)



In an infinitesimal process,

dU = dQ dW
18
NOTE:
The change in internal energy, U, in any
process depends only on the initial and the
final state not on the path.
Systems
added
results in
process
W
Q
System 1
Initial
State, U
i
System 2
System 3
System 4
Final
State, U
f
W
Q
U
i
= U
1
= Q
1
W
1
U
2
= Q
2
W
2
U
3
= Q
3
W
3
U
f
= U
4
= Q
4
W
4
Two interpretation..!!
Explain- S1 & S1-S4
19
Two Special Cases
Cyclic process - A process that eventually returns a system to
its initial state. For such a process, the final state is the same as the
initial state, and so the total internal energy change must be ZERO.


And


Isolated system - one that does no work on its surroundings
and has no heat flow to or from its surroundings

W = Q = 0 thus;

thus In other words, the internal energy of an isolated system is
CONSTANT.
1 2
U U =
W Q =
0 U =
20
4 Thermodynamic Processes
21
V
22
Internal Energies of Ideal Gases
The internal energy of an ideal gas depends only on
its temperature, not on its pressure or volume. For
other substances the internal energy of an isolated
system is constant.
The molar heat capacities C
v
and C
p
of an ideal
gas are related by:


The ratio of heat capacities denoted by and
is given by:

R C C
v p
+ =
v
p
C
C
=
23
Mechanisms of Energy Transfer
by Heat

We want to know the rate at which energy
is transferred
There are various mechanisms
responsible for the transfer:
Conduction
Convection
Radiation

24
Conduction
The transfer can be viewed on an atomic
scale
It is an exchange of kinetic energy between
microscopic particles by collisions
The microscopic particles can be atoms,
molecules or free electrons
Less energetic particles gain energy during
collisions with more energetic particles
Rate of conduction depends upon the
characteristics of the substance

25
Conduction, cont.
In general, metals are good thermal conductors
They contain large numbers of electrons that are
relatively free to move through the metal
They can transport energy from one region to another
Poor conductors include asbestos, paper, and
gases
Conduction can occur only if there is a difference
in temperature between two parts of the
conducting medium

26
Conduction, equation
The slab at right allows
energy to transfer from
the region of higher
temperature to the
region of lower
temperature
The rate of transfer is
given by:


Q dT
kA
t dx
= =
A
27
Conduction, equation
explanation
A is the cross-sectional area
x is the thickness of the slab
Or the length of a rod
is in Watts when Q is in Joules and t is
in seconds
k is the thermal conductivity of the material
Good conductors have high k values and
good insulators have low k values

28
Temperature Gradient
The quantity |dT / dx| is
called the temperature
gradient of the material
It measures the rate at
which temperature varies
with position
For a rod, the
temperature gradient can
be expressed as:


h c
dT T T
dx L

=
29
Rate of Energy Transfer in a Rod
Using the temperature gradient for the rod, the
rate of energy transfer becomes:


h c
T T
kA
L

| |
=
|
\ .
30
Compound Slab
For a compound slab containing several
materials of various thicknesses (L
1
, L
2
, ) and
various thermal conductivities (k
1
, k
2
, ) the rate
of energy transfer depends on the materials and
the temperatures at the outer edges:

( )
( )
h c
i i
i
A T T
L k

31
Some Thermal Conductivities
32
More Thermal Conductivities
33
Home Insulation
Substances are rated by their R values
R = L / k and the rate becomes




For multiple layers, the total R value is the sum of the
R values of each layer
Wind increases the energy loss by conduction in
a home

( )
h c
i
i
A T T
R

34
Convection
Energy transferred by the movement of a
substance
When the movement results from differences
in density, it is called natural convection
When the movement is forced by a fan or a
pump, it is called forced convection

35
Convection example
Air directly above the
radiator is warmed
and expands
The density of the air
decreases, and it
rises
A continuous air
current is established

36
Radiation
Radiation does not require physical
contact
All objects radiate energy continuously in
the form of electromagnetic waves due to
thermal vibrations of their molecules
Rate of radiation is given by Stefans law

37
Stefans Law
P = AeT
4
P is the rate of energy transfer, in Watts
= 5.6696 x 10
-8
W/m
2 .
K
4
A is the surface area of the object
e is a constant called the emissivity
e varies from 0 to 1
The emissivity is also equal to the absorptivity
T is the temperature in Kelvins

38
Energy Absorption and
Emission by Radiation
With its surroundings, the rate at which the
object at temperature T with surroundings
at T
o
radiates is
P
net
= Ae (T
4
T
o
4
)
When an object is in equilibrium with its
surroundings, it radiates and absorbs at the
same rate
Its temperature will not change

39
Ideal Absorbers
An ideal absorber is defined as an object
that absorbs all of the energy incident on it
e = 1
This type of object is called a black body
An ideal absorber is also an ideal radiator
of energy

40
Ideal Reflector
An ideal reflector absorbs none of the
energy incident on it
e = 0


41
The Dewar Flask
A Dewar flask is a container designed to
minimize the energy losses by conduction,
convection, and radiation
Invented by Sir James Dewar (1842 1923)
It is used to store either cold or hot liquids
for long periods of time
A Thermos bottle is a common household
equivalent of a Dewar flask

42
Dewar Flask, Details
The space between the
walls is a vacuum to
minimize energy transfer
by conduction and
convection
The silvered surface
minimizes energy transfers
by radiation
Silver is a good reflector
The size of the neck is
reduced to further
minimize energy losses

43
Extra Readings
Please read Chapters 15 18 from
University Physics, 9
th
12
th
ed
reference text or Physics for
Scientists and Engineers, 6
th
ed

This will help you understand
more.
44
Addition to Tutorial Set 06
Q1) One hundred joules of heat is added to
a gas, and the gas expands at constant
pressure. Is it possible that the internal
energy increases by 200 J? Account
for your answer with the aid of the first
law of thermodynamics

Q2) A gas is compressed isothermally, and
its internal energy increases. Is the gas
an ideal gas? Justify your answer.

45
Addition to Tutorial Set 06 cont
Q3)A material undergoes an isochoric
process that is also adiabatic. Is the
internal energy of the material at the end
of the process greater than, less than, or
the same as it was at the start? Justify
your answer.

46
Addition to Tutorial Set 06 cont
Q4) a) Is it possible for the temperature of a
substance to rise without heat flowing into
it? (b) Does the temperature of a
substance necessarily have to change
because heat flows into or out of it? In
each case, give your reasoning and use
example of an ideal gas.

47
Q5) When a solid melts at constant pressure,
the volume of the resulting liquid does not
differ much from the volume of the solid.
Using what you know about the first law of
thermodynamics and the latent heat of
fusion, describe how the internal energy of
the liquid compares to the internal energy of
the solid.
Addition to Tutorial Set 06 cont
48
Addition to Tutorial Set 06 cont
Q6) Suppose you want to heat a gas so that
its temperature will be as high as possible.
Would you heat it under conditions of
constant pressure or constant volume?
Why?