Thermodynamic Chapter 1

TEMPERATURE
KI NETI C THEORY GASES

PHY414
1
ST
& 2
ND
WEEK
Zety Sharizat Hamidi
Temperature
How hot or cold an object feels when we touch it
Qualitative indication
2 concepts of temperature:
1. thermal contact : if energy can be exchanged
between them
2. Thermal equilibrium: if there are in thermal
contact and there is no net exchange of energy

Heat
The exchange of energy between 2
objects because of differences in
their temperature
Thermometer: a device calibrated to
measure the temperature of the
object.

o
K = 273.15 +
o
C
o
C = (5/9)*(
o
F-32)
o
F = (9/5)*
o
C+32
The Zeroth Law of thermodynamics
If objects A and B are
separately in thermal
equilibrium with a
third object C then A
and B are in thermal
equilibrium with each
other.

Zero law of thermodynamics
Thermometers and temperature scales
Thermometers: devices used to
measure the temperature of an
object or a system.
Energy is exchanged until the
thermometer and the system are in
the thermal equilibrium with each
other.
Consists a mass of liquid- mercury
or alcohol
Scales: Celsius: 0: the temperature
of the ice-water mixture, 100: the
steam point / boiling point of water
Thermometers and temperature scales
Measuring temperature
The constant-volume gas thermometer and Kelvin Scale
Gas thermometer: the temperature readings are
nearly independent of the substance used in the
thermometer.
Type of gas thermometer: constant-volume unit.

The Celsius and Fahrenheit scales: Celsius-Kelvin
The pressure extrapolates to zero when the
temperature is 273.15C.
Absolute zero: when temperature is 273.15 C
Absolute zero: is used as the basis for Kevin
temperature scale.

TC=T-273.15
The Celsius, Kelvin & Fahrenheit temperature
scales
Most common scale in use in US: Fahrenheit scale.
Sets the temperature of the ice point at 32F and the
temperature of the steam point at 212F.
Relationship between the Celsius and Fahrenheit
temperature scales is:

T
F
= (9/5)T
c
+32
The Celsius, Kelvin & Fahrenheit temperature
scales
Therefore;

T
c
= 5/9 (T
F
-32)
Or
T
F
=9/5 T
C

As temperature of the substances increases, its volume increases: thermal
expansion\
Consider how the atoms in solid substance behave
If the thermal expansion of an object is sufficiently small compared with the
objects initial dimensions, then the change in any dimension is, to a good
approximation, proportional to the first power of the temperature change.
Suppose an object has an initial length L
0
along some direction at some
temperature T
0
. Then the length increases by L for a change in
temperature T . So for small change in temperature,

Thermal expansion of solid and liquids
L=L
0
T

L-L
0
=L
0
(T-T
0
)

is called the coefficient of linear expansion for a given material and has units of ( C)
-1

Thermal expansion
Because the linear dimensions of an object change
due to variations in temperature, it follows that
surface area and volume of the object also change.
Consider a square of material having an initial length
on a side and therefore an initial area . As the
temperature is increased, the length of each side
increases to
L=L
0
+L
0
T

The new area A is
Consequently, we can neglect this term to get a simpler expression
So that
where
The quantity is called the coefficient of area expansion
Problem:
A circular copper ring at 20C has a hole with an area of
9.98 cm. a)What minimum temperature must it have so
that it can be slipped onto a steel metal rod having a cross-
sectional area of 10.0 cm?b) Suppose the ring and the rod
are heated simultaneously. What change in temperature of
both will allow the ring to be slipped onto the end of the
rod? (Assume no significant change in the coefficients of
linear expansion over this temperature range.)

Solution:
a) Find the temperature of the ring that will allow it
to slip onto the rod.
Substitute the desired change in area into eq.,
finding the necessary change in temperature:
Solve for T, then add this change to the initial
temperature to get the final temperature.

Temperature
How hot or cold an object feels when we touch it
Qualitative indication
2 concepts of temperature:
1. thermal contact : if energy can be exchanged
between them
2. Thermal equilibrium: if there are in thermal
contact and there is no net exchange of energy

Heat
The thermal energy that is transferred from one
object to another due to a difference in
temperatures between two objects is known as heat
or
The exchange of energy between 2 objects because
of differences in their temperature
The unit of heat is Joule (J)
Thermometer: a device calibrated to measure the
temperature of the object.

Heat

Units of heat
Specific heat capacity; definition and meaning.
Measurement of specific heat capacities of solids and liquids;
emphasis on calculation of energy transferred
Energy transfer= mcAT
Change of state; specific latent heat. Energy is needed to pull
molecules apart. Energy transfer=lAm
Mechanisms of heat transfer; heating, random interchange of
energy between bodies in thermal contact.
Electrical and mechanical working: forces moving either
charges or masses.

Heat
Energy can take on many forms and can change from
one form to another. Many different types of energy
can be converted into heat energy. Light, electrical,
mechanical, chemical, nuclear, sound and thermal
energy itself can each cause a substance to heat up by
increasing the speed of its molecules. So, put energy
into a system and it heats up, take energy away and it
cools. For example, when we are cold, we can jump
up and down to get warmer.
UNITS OF HEAT
Internal energy U is the energy associated with
the microscopic components of a system- the
atoms and molecules of the system.
The internal energy includes kinetic and potential
energy associated with the random translational,
rotational, and vibrational motion of the particles
that make up the system and any potential energy
bonding the particles together
UNITS OF HEAT
Heat is the transfer of energy between a system
and its environment due to a temperature
difference between them.
The calorie (cal) is defined as the energy
necessary to raise the temperature of 1 g of
water from 14.5 to 15.5C
The unit of heat in the U.S customary system, the
British thermal unit (Btu) was defined as the
energy required to raise the temperature of 1 lb
of water from 63 to 64 F
UNITS OF HEAT
The calorie is now defined to be exactly 4.186 J
1cal=4.186 J
Heat vs. temperature
Heat is the total energy of molecular motion in a substance
while temperature is a measure of the average energy of
molecular motion in a substance.
Heat energy depends on the speed of the particles, the
number of particles (the size or mass), and the type of
particles in an object.
Temperature does not depend on the size or type of object.
For example, the temperature of a small cup of water might
be the same as the temperature of a large tub of water, but
the tub of water has more heat because it has more water
and thus more total thermal energy.
Specific heat capacity; definition and
meaning
If a quantity of energy Q is
transferred to a substance of mass
m, changing its temperature by
T=T
f
- T
i
, the specific heat of the
substance is defined by

SI unit: Joule per kilogram-degree
Celcius (J/kg.C)
Specific heat capacity; definition and
meaning
From the definition of specific heat, we can express
the energy Q needed to raise the temperature of a
system of mass m by T as
Calorimetry
One technique for measuring the specific heat of a solid
or liquid is to raise the temperature of the substance to
some value, place it into a vessel containing cold water of
known mass and temperature, and measure the
temperature of the combination after equilibrium is
reached.
Vessels having this property are called calorimeters, and
analysis performed using such vessels is called
calorimetry.

Calorimetry
Because whatever energy is lost by one object
must gained by another, conservation energy
requires that
Q
k
=0
Where Q
k
is the energy change in the k
th
object.

Latent heat and phase change
A substance usually undergoes a change in
temperature when energy is transferred between
the substance and its environment.
In some cases, however, the transfer of energy
doesnt result in change in temperature.
This can occur when the physical characteristics
of the substance change from one to another,
commonly referred to a phase change.
Latent heat and phase change
A substance usually undergoes a change in
temperature when energy is transferred between
the substance and its environment.
In some cases, however, the transfer of energy
doesnt result in change in temperature.
This can occur when the physical characteristics
of the substance change from one to another,
commonly referred to a phase change.
Thermal contact and thermal equilibrium
Two objects are in thermal contact if energy can be
exchanged between them.
Two objects are in thermal equilibrium if they are in
thermal contact and there is no net change of energy.

The absorption of heat by solids and liquids.
Heat can be transferred from one place to another by
three methods: conduction in solids, convection of
fluids (liquids or gases), and radiation through
anything that will allow radiation to pass. The
method used to transfer heat is usually the one that
is the most efficient. If there is a temperature
difference in a system, heat will always move from
higher to lower temperatures.
CONDUCTION: Conduction occurs when two object at different temperatures
are in contact with each other. Heat flows from the warmer to the cooler object
until they are both at the same temperature. Conduction is the movement of
heat through a substance by the collision of molecules. At the place where the
two object touch, the faster-moving molecules of the warmer object collide with
the slower moving molecules of the cooler object. As they collide, the faster
molecules give up some of their energy to the slower molecules. The slower
molecules gain more thermal energy and collide with other molecules in the
cooler object. This process continues until heat energy from the warmer object
spreads throughout the cooler object. Some substances conduct heat more
easily than others. Solids are better conductor than liquids and liquids are
better conductor than gases. Metals are very good conductors of heat, while air
is very poor conductor of heat. You experience heat transfer by conduction
whenever you touch something that is hotter or colder than your skin e.g. when
you wash your hands in warm or cold water.

CONDUCTION:
A thermal infrared image
of a coffee cup filled with
a hot liquid. Notice the
rings of color showing
heat traveling from the
hot liquid through the
metal cup. You can see
this in the metal spoon as
well. This is a good
example of conduction.
CONVECTION: In liquids and gases, convection is usually
the most efficient way to transfer heat. Convection occurs
when warmer areas of a liquid or gas rise to cooler areas in
the liquid or gas. As this happens, cooler liquid or gas takes
the place of the warmer areas which have risen higher. This
cycle results in a continous circulation pattern and heat is
transferred to cooler areas. You see convection when you
boil water in a pan. The bubbles of water that rise are the
hotter parts of the water rising to the cooler area of water at
the top of the pan. You have probably heard the expression
"Hot air rises and cool air falls to take its place" - this is a
description of convection in our atmosphere. Heat energy is
transferred by the circulation of the air.

CONVECTION
This thermal infrared image
shows hot oil boiling in a pan.
The oil is transfering heat out
of the pan by convection.
Notice the hot (yellow)
centers of rising hot oil and
the cooler outlines of the
sinking oil. Image courtesy of
K.-P. Mllmann and M.
Vollmer, University of
Applied Sciences
Brandenburg/Germany.
RADIATION: Both conduction and convection require matter to transfer heat.
Radiation is a method of heat transfer that does not rely upon any contact between the
heat source and the heated object. For example, we feel heat from the sun even though we
are not touching it. Heat can be transmitted though empty space by thermal radiation.
Thermal radiation (often called infrared radiation) is a type electromagnetic radiation (or
light). Radiation is a form of energy transport consisting of electromagnetic waves
traveling at the speed of light. No mass is exchanged and no medium is required.
Objects emit radiation when high energy electrons in a higher atomic level fall down to
lower energy levels. The energy lost is emitted as light or electromagnetic radiation.
Energy that is absorbed by an atom causes its electrons to "jump" up to higher energy
levels. All objects absorb and emit radiation. ( Here is a java applet showing how an atom
absorbs and emits radiation) When the absorption of energy balances the emission of
energy, the temperature of an object stays constant. If the absorption of energy is greater
than the emission of energy, the temperature of an object rises. If the absorption of
energy is less than the emission of energy, the temperature of an object falls.

RADIATION
A thermal infrared image of the center of
our galaxy. This heat from numerous stars
and interstellar clouds traveled about
24,000 light years (about
150,000,000,000,000,000 miles!) through
space by radiation to reach our infrared
telescopes.
Heat and work
A major distinction must be made between internal energy
and heat.
These terms are not interchangeable- heat involves a
transfer of internal energy from one location to another.
Internal energy U is the energy associated with the
macroscopic components of a system- the atoms and
molecules of the system.
The internal energy includes kinetic and potential energy
associated with the random translational, rotational, and
vibration motion of the particles that makes up the system,
and any potential energy bonding the particles together.
work
Energy can be transferred to a system by heat and by
work done on the system.
In most cases of interest treated here, the system is a
volume of a gas, which is important in understanding
engines.
The work done on a gas at constant pressure is given
by
W=-PV
Where P is the pressure throughout the gas and V is
the change in volume of the gas during the process
The First Law of thermodynamics
If the system undergoes a change from an initial
state to a final state, where Q is the energy
transferred to the system by heat and W is the work
done on the system, the change in the internal
energy of the system U is given by

U=U
f
U
i
=Q+W
The 1
st
law relates changes in internal energy
Any system can exchange energy with its
surroundings in 2 general ways; as a heat or as work
Q= U+W
The law states that if an amount of heat, Q , flows
into a system, then the heat must appear as an
increase in the internal energy, U of the system and
the work, W done by the system. That is

First Law of Thermodynamics
For a closed system:

Differential form:

For an isolated system:
W Q U = A
dW dQ dU =
0 0 = A = = U Q W
Recall that an expression for the internal energy of an ideal
gas is
U=3/2 nRT
the change in the internal energy, U for a such gas is given
by
U=3/2 nRT
The molar specific heat at constant volume of a
monatomic ideal gas, C
v
is defined by
C=3/2 R
The change in internal energy of an ideal gas can then be
written
U=n C
V
T

There are several process for a closed ideal gas in
which 1
st
law of thermodynamics can be applied.
The process are:
1. isothermal
2. isochoric
3. isobaric
4. adiabatic

Thermodynamics process
Thermodynamics process
1. Constant pressure or isobaric process
2. Constant volume or isochoric process.
3. Constant temperature or isothermal process.
4. Adiabatic or no heat flow process.
a. Adiabatic process, Q=0
b. Isochoric process, W=0
c. Isobaric process, P=0
d. Isothermal process, U=0

Isothermal process is a process that occurs at
constant temperature.
Since the isothermal process is when the
temperature is constant, the internal energy does not
change and thus U = 0.
Therefore, for an isothermal process,
Q=W
Isobaric process is a process that takes place at
constant temperature.
This means when a gas is being compressed, work
done on the gas.

Isochoric/ Isovolumetric process: a process that occurs at
constant volume. Since in this process the volume of the gas
does not change, then V=0 and thus the work done in the
process, W=0
Therefore,
Q= U
Adiabatic process: is a process that occurs without any
exchange of heat between a gas system and its
surroundings, that is Q=0.
This process can occur if the gas is kept in a well-insulated
container or the process is very quickly so that there is no
time for the heat to flow in or out of the system.
Some special cases of the 1
st
law of
thermodynamics
Adiabatic process
0=U +W
U=-W
This means that in an adiabatic compression, the
work done on a gas results in corresponding increase
in its internal energy.
In adiabatic process, temperature is not constant and
pressure decrease quickly with the increase in
volume.
Adiabatic process
No transfer of energy as heat
occurs between the system and
its enviroment
Thermodynamic Processes
Isothermal Processes (AT=0):
PV=nRT, so PV=constant
AU=3/2 nRAT=0, so W=Q
Work done by gas equals heat added to gas
Adiabatic Processes (Q=0):
Could be a well-insulated process or a very fast one
AU=-W
Isotherms
Adiabats
Isobaric Processes: P=constant
Isochoric Processes: V=constant
Work done in volume changes
PdV PAdl l d F dW = = = .
} }
= =
B
A
V
V
PdV dW W
Isothermal Expansion of an Ideal Gas AB
A
B
V
V
V
V
V
V
nRT
V
dV
nRT PdV W
B
A
B
A
ln = = =
} }
Isothermal Process
Another way to get from A to B: Process
ADB
Isochoric Process (AD)
0 = W
Isobaric Process (DB)
( ) V P V V P PdV W
A B B
V
V
B
A
A = = =
}
( )
|
|
.
|
\
|
= =
B
A
B A B B
V
V
nRT V V P W 1
Note: work done for AB is NOT the
same as for ADB!

The work done by a process depends
not only on initial and final states but
also on the path followed in PV space.
Heat transfer mechanisms: conduction, convection
and radiation

The transfer of heat can only occur when there is
difference in temperature between two objects or
systems.
Heat can be transferred from one object or system to
another by 3 mechanisms:
1. Conduction
2. Convection
3. radiation
conduction
Conduction is the heat transfer mechanism that does
not involve any motion of the molecules of medium
over large distances.
Heat is transferred from molecule to molecule via
collision
Conduction can occur in solids, liquids and gases.
However, the effect is most pronounced in solids.
The ability of a material to conduct heat depends on
its atomic structure
conduction
Metals are materials that can classified as good heat
conductors.
In metals, conduction takes place by means of both
vibration of atoms and the motion of electrons.
Metal have a large number of free electrons that can
wander freely through the metals.
These electrons can transfer energy quickly from one
part of the metal to another.
This explains why metals are effective and good heat
conductors
Conduction
Heat flow rate is
proportional to
thermal conductivity
k(J/(s.m.C))
temperature difference
area
1/length scale
l
T T
kA
t
Q
2 1

=
A
A
Conductions occurs at different rates in different
conducting medium.
In general, the heat conduction through a conductor
depends on a few factors: the surface area, the
material of conductor and the temperature gradient
along it.
Consider a conductor. If Q is the heat transformed in
a time interval T from the hotter surface to the
colder one, the rate of energy transfer by conduction
through the conductor can be written as

Thermal conductivity
Thermal conductivity

Where T/ x is called temperature gradient ( the change
in temperature per unit length) and k is the thermal
conductivity of the material of the conductor.
Thermal conductor k is a measure of the ability of a
material to conduct heat which depends on the atomic
structure of the material
convection
Convection is a process of a heat transfer by the
actual motion of the medium, usually a gas or a
liquid, itself.
In convection, the molecules of the medium move
along the heat.
Therefore, the only liquids and gas can transfer heat
by convection because unlike the molecules of solids,
their molecules can move over large distances.
Convection can be categorized as natural convection
and forced convection.
natural convection
Is a process driven by buoyant force.
This process occurs due to the movement of fluid
(medium) as a result of differences in densities.
The movement of the fluid occurs based on the fact
that the hot part of the fluid expands and becomes
less dense and is displaced by colder and denser part
of the fluid as it sinks.
forced convection
Is a process driven by mechanical forces exerted by
an external device such as a pump or a fan.
Example are the forced convection generated by a
pump that circulates radiator fluid through an
automobile engine to remove excess heat and a
forced convection of a refrigerator coolant removing
energy from the inside of the refrigerator.
Convection
Buoyant uprising is
opposed by viscous drag.
Vigor of convection is
measured by the Rayleigh
number:

For a free surface fluid,
convection occurs for
Ra>1100.
k
o
3
Td g
Ra
A
=
radiation
Is a transfer of heat by electromagnetic waves.
Unlike conduction and convection, radiation does
not require a medium.
The warming of the earth by the Sun and the flow of
heat by hot objects such as a fire or an automobile
radiator to the surroundings are 2 examples of heat
transfer by radiation.
The rate at which an object radiates energy is
described in equation known as Stefan Boltzmann
law:
Radiation
4
AT e
t
Q
o =
A
A
o = 5.67 10
-8
W/m
2
.K
4
e = emissivity = 01
( )
4
2
4
1
T T A e
t
Q
=
A
A
o
Radiation into a vacuum
Radiation from an object at T
1
into a high emissivity medium at T
2
Where is the Stefan Boltzmann constant (5.67 x 10
-8
Wm
-2

K
-4
), A is the area and T is the absolute temperature of the
object. E represent the emissitivity of the surface of the
object range from 0-1
The good radiator are also good absorbers.
A body that absorbs all radiation incidents upon it is called
a blackbody.
A blackbody is an ideal absorber and also an ideal radiator.
For such a body, the value of emissitivity, e=1
radiation
radiation
Kinetic Theory of Gases

Gas have 3 physical quantities (pressure, volume and
temperature) which determine their state.
Three basic gas laws that derived the relationships
between physical quantities of a gas are Boyles law,
Charless law and Gay-Lusaac law
The kinetic theory of gases explains the properties of gases in terms of
the motion of the particles that make up the gases. The theory is based
on the following assumptions.
1. The number of molecules in the gas is large, and average separation
between them is large compared with their dimensions.
2. The molecules obey Newtons law of motion, but as a whole they
move randomly.
3. The molecules interact only through short-range forces during elastic
collisions.
4. The molecules make elastic collisions with the walls.
5. All molecules in the gas are identical.

Kinetic Theory of Gases

Avogadros number
The Avogadro constant (symbols: L, N
A
), also
called the Avogadro number, is the number of
atoms in exactly 12 grams of
12
C. A mole is
defined as this number of "entities" (usually,
atoms or molecules) of any material.
[1][2]
The
currently accepted value for this number is:
[3]

The value of Avogadro's constant was first indicated by
Johann Josef Loschmidt who, in 1865, computed the
number of particles in one cubic centimetre of gas held at
standard conditions. The term Loschmidt constant is thus
more correctly applied for this value, which can be said to
be proportional to the Avogadro number. However, in the
German language literature, "Loschmidt constant" refers
to both this quantity as well as the number of entities in a
mole.
Avogadros number
An ideal gas is a collection
of atoms or molecules that
move randomly and exert
no long range forces on
each other. Each particle of
the ideal gas is individually
point-like occupying a
negligible volume.
Ideal gases
Ideal gases
An ideal gas or perfect gas is a hypothetical gas consisting of identical particles of zero
volume, with no intermolecular forces, where the constituent atoms or molecules undergo
perfectly elastic collisions with the walls of the container and each other and are in constant
random motion. Real gases do not behave according to these exact properties, although the
approximation is often good enough to describe real gases.
These four properties that constitute an ideal gas can be easily remembered by the acronym
PRIE, which stands for;
- Point masses (molecules occupy no volume)
- Random Motion (molecules are in constant random motion)
- Intermolecular forces (there are NO intermolecular forces between the particles)
- Elastic collisions (the collisions involving the gas molecules are totally elastic)
The concept of ideal gas is useful in technology because one mole (6.02214 10
23
particles)
of an ideal gas has a volume of 22.4 liters at the standard conditions for temperature and
pressure and many common real gases approach this behaviour in these conditions.
The conditions in which a real gas will behave more and more like an ideal gas is either at
very high temperatures (as the molecules of the gas have so much energy that the
intermolecular forces and energy lost in collisions is negligable) and at very low pressures
(as the molecules of the gas rarely collide or come into close enough proximity for
intermolecular forces to be significant).
Macroscopic description of an ideal gas
An ideal gas is a collection of atoms or molecules
that move randomly and exert no-long range forces
on each other. Each particles of the idea gas is
individually point-like, occupying a negligible
volume.
One mole (mol) of any substance is that amount of
the substance that contains as many particles
(atom, molecules, or other particles) as there are
atoms in 12g of the isotope carbon-12.

Pressure, Temperature and RMS speed.
Pressure:
Imagine n moles of ideal gas molecules in a box. Let
us consider that one of them of mass m is moving
with a velocity .
The x-component of the molecule velocity is -
x
. The
change in its momentum can be written as

However, the change in momentum imparted on the
wall is the negative value of this. That is

The time taken, t between 2 collisions is the time
taken by the molecule to travel to the opposite wall
and back again, that is 2L/
x
. This means, the
average force exerted to the wall is

The magnitude of the total force exerted on the wall
caused by N gas molecules in the box

Or

Or

Therefore the exerted pressure on the wall

Where V is the volume of the box and <
2
> is the
average value of the square of
x
. However for any
molecule

And thus

Substitute equation

Or

Temperature:
It is shown that

However the number of molecules, N is equal to the
number of moles of gas, n multiplied with the
Avogadros number, N
A

Hence the average translational molecular kinetic
energy can be expressed as

Or

It shows that the molecular kinetic energy of a gas is
proportional to its temperature
Where k is the Boltzmanns constant and h =R/N
A
=
1.38 X 10
-23
JK
-1

Root mean square speed:
The quantity <
2
> is the average of the square of the
speeds of gas molecules. The root <
2
>is called the
root mean square speed or rms speed,
rms
of the gas
molecules. From the equation

Or

And thus the rms speed can be written as

Translational Kinetic Energy
mean free path
A random motion parameter
is the average distance traversed by
a molecule between collisions.
Molar specific heats of an Ideal gas.
Molar specific heat:
The molar specific heat capacity is the heat required
to raise the temperature of 1 mole of a substance by 1
K, that is given by equation:

For one mole of a gas at constant pressure, pV = R
T , therefore
C
P
=C
V
+R
The Adiabatic expansion of an ideal gas.
The Adiabatic expansion of an ideal gas

Thermodynamic Chapter 1

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TEMPERATURE

KI NETI C THEORY GASES

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