GP111

Elementary Thermodynamics

Kinetic Theory of Gases and the Ideal Gas Law

Prof. Primal Fernando
primal@eng.pdn.ac.lk
Ph: (081) 2393608, 071-
8450438 1
• Hypothesis

• Theory How these concepts are related to each other?

• Law

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Scientific Hypothesis:
1. A proposed answer to a research question

2. A tentative explanation for an observation or

phenomena that can be tested through
experimentation.

3
Scientific Theory:
A general principle supported by a substantial body
of evidence offered to provide an explanation of
observed facts and as a basis for future discussion or
investigation.
Lincoln, Boxshall, and Clark (1990)

Scientific Law:
A scientific law is a description of a natural
relationship or principle, often expressed in
mathematical terms.

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L A W (fact)

When proven that it

always works

THEORY

When supported
over time

HYPOTHESIS

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 THEORY LAW

• Explanatory principle • Concise, descriptive principle

• Based more on inference • Based more on observation
• Based on lots of evidence • Based on lots of evidence
• Can change w/ new evidence • Can change w/ new evidence

(May Become)
HYPOTHESIS

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List examples of scientific theories
and laws….

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 Law
Ideal gas law: PV=nRT
Describes the relationship between pressure, volume,
moles, and temperature of a gas.
Law of conservation of matter: First clearly stated
by 18th century chemist Antoine Lavoisier, this law
describes that in a closed system, matter is neither
created or destroyed.
 Law of superposition:
Describes the general principle that in undeformed
layers of rock, the oldest rock will be at the bottom.
 Newton’s second law of motion: F=ma
Describes the relationship between force, mass, and
acceleration.
Theory
Kinetic molecular theory: Matter consists of
tiny particles in constant motion, whose speed is
proportional to the absolute temperature.
Explains gas laws.
 Atomic theory: All matter is composed of
elements made from indestructible particles
called atoms. Explains why matter is conserved
in chemical reactions.
 Theory of evolution by natural selection:
Competition for limited resources results in
differential reproductive success. Only species
best adapted to their environment survive and
pass on hereditable traits. Explains the
phenomenon of evolution, the fossil record, and
the diversity of species on Earth.
 Theory of plate tectonics: Earth’s crust is
divided into plates that move. Explains why
earthquakes and volcanoes occur in certain
zones.
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 Boyle’s Law: The pressure of a given mass of an ideal gas is inversely
proportional to its volume at a constant temperature

1
P ; T, n kept constant
V
New Experiments
7 investigations deal Physico-Mechanicall,
with changes in Touching the Spring
pressure as a result of of the Air, and its
changes in volume Effects... (1662)
9
Boyle’s law and diving

• For every 10 m of depth,

diver experiencing one
additional atmosphere of
pressure

• If a diver holds his or her

breath at 20 m and rises to
the surface quickly, the
outside pressure drops to 1
atm.

• Because the pressure is

decreasing by a factor of 3,
the volume will expand by
a factor of 3, causing Always exhale when rising!
damage to internal organs.

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Charles’ Law: The volume of an fixed amount of ideal gas at constant
pressure is directly proportional to the absolute temperature.

• The Expansion of Gases by Heat. In

Annales de Chimie 43, 137 (1802)
– First published by Gay-Lussac
who attributed it to
unpublished work of Charles’
in 1780s.

V  T ; P, n kept constant

Gay - Lussac's law, P  T ; V, n kept constant

PV
Combined gas law,  Constant
T

Image retrieved from: http://www.freshney.org/ptonline/data/biography/jlgl.htm

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Charles’ Law.

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Particle hypothesis

• Everything made up of particles.

• Axiom (or postulate): Everything is made-up of indivisible units

called particles that are never still (in constant movement).

• Matter in the Universe is made of particles that we call atoms.

• Each of these atoms are made up of more fundamental particles

called electrons, protons, and neutrons

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Kinetic Molecular Theory
(Early Ideas about Molecular Motion)
• Bernoulli (1738): Hydrodynamica
• Gases consist of great numbers of molecules moving in all
directions
• Impact on a surface causes gas pressure
• Heat is the kinetic energy of their motion
• Herapath (1821):
• Gas particle momentum is a measure of the absolute temperature
of the gas
• Waterston (1843):
• Gas pressure is a function of the number of molecules per unit
volume, molecular mass, and molecular mean-squared velocity
• Published posthumously (1892) as “On the physics of media that are
composed of free and perfectly elastic molecules in a state of motion"
• Both Herapath and Waterston failed peer review when attempting to get
their ideas published by the Royal Society of London

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Kinetic Molecular Theory
• Krönig (1850)
• Included only translational particle motion
• Gundzüge einer Theorie der Gase Ann. Phys. 79, 368, 500
• Clausius (1857)
• Included translational, rotational, and vibrational particle
motion
• The size of a particle is negligibly small relative to its
container
• Changes in particle motion due to collisions are infinitesimal
relative to time between successive collisions.
• The influence of the molecular forces must be infinitesimal.
• Heat is the average kinetic energy of molecules.
– Published: "Über die bewegende Kraft der Wärme" ("On the Moving
Force of Heat and the Laws of Heat which may be Deduced
Therefrom”, Annalen der Physik 100, 353-380

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Kinetic Molecular Theory

• Additions, Clarifications, and Modifications by:

– Maxwell (1859):
• Maxwell distribution: gives the proportion of molecules having
a certain velocity in a specific range
– Boltzmann (1890s):
• Associated the kinetic energy of particles with their degrees of
freedom
• Described distribution of particle speeds in gases
– Einstein (1905) and Smoluchowski (1906)
• Brownian Motion – evidence for the existence of atoms and
molecules

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Timeline of Gas Laws and KMT

Boyle’s Charles’
Law Law

Bernoulli Clausius’
Hydrodynamica first “complete” version of
(initial ideas about Kinetic Molecular Theory
particle motion)

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The kinetic molecular theory of gases

Explains the laws that describe the behavior of gases and it

was developed during the nineteenth century by Boltzmann,
Clausius, and Maxwell

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“Modern” Kinetic Molecular Theory

– Gases consist of very small particles in constant, random motion,

traveling in straight lines and obeying Newton laws.
– Gas particles are perfectly spherical in shape and elastic in nature.
– Gas particles move rapidly and constantly collide with each other
and the walls of the container in perfectly elastic collisions.
– The volume of individual gas particles is negligible relative to the
volume of the container (they are points).
– Interactions among molecules are negligible, except during
collisions.
– The time during collision of molecule with the container's wall is
negligible as comparable to the time between successive
collisions.
– The average kinetic energy of the gas particles depends only on
the temperature of the system.

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Particles in an ideal gas…
– have no volume.
– have elastic collisions (the energy of motion
remains unchanged during collisions).
– are in constant, random, straight-line motion.
– don’t attract or repel each other.

Courtesy Christy Johannesson www.nisd.net/communicationsarts/pages/chem

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Force on the wall

• Consider a one particle hitting on the

wall at a velocity of ‘v’.
• The momentum of the molecule will
be ‘mv’.
• If it rebounds elastically its
momentum will be ‘-mv’
mv  ( mv ) 2mv
F  Rate of change of momentum  
t t

‘t ‘is the time taken by molecule up and down

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Pressure on the wall mv  ( mv) 2mv
F  Rate of change of momentum  
t t
2l
t
v
mv 2
F
l

F F mv 2 mv 2
Prssure on the wall  P    
Area wh lwh V

If number of molecules (particles)travelling in the box is ‘N’,

Nmv 2
Prssure on the wall  P 
V
Since these particles move randomly in three dimensions, one-third of
them on the average strike the right wall. Therefore, the total pressure is:,
Nmv 2
Prssure on the wall  P 
3V
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Avogadro's Number NA

The number of atoms per mole is known as Avogadro's number NA,

after the Italian scientist Amedeo Avogadro (1776–1856):

N A  6.022  10 23 mol-1
The number of moles n contained in any sample is the number
of particles N in the sample,
N m
n 
NA M

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Ideal gas law Nmv 2
Prssure on the wall  P 
3V
1
PV  Nmv 2
3
1 2
KE  mv
2
Equipartition theorem,

Number of degrees of freedom k B  Boltzmann constant

KE  k BT
2
f T  Kelvin temperature
KE  k BT
2

Degree of freedom =3 (3 ways particle can moves in the box)

1 2 3
KE  mv  k BT
2 2

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The Equipartition Theorem

• The Equipartition theorem states that energy is shared equally amongst all
energetically accessible degrees of freedom of a system.

• This is not a particularly surprising result, and can be thought of as another

way of saying that a system will generally try to maximize its entropy (i.e.
how ‘spread out’ the energy is in the system) by distributing the available
energy evenly amongst all the accessible modes of motion.

• The Equipartition theorem can go further than simply predicting that the
available energy will be shared evenly amongst the accessible modes of
motion, and can make quantitative predictions about how much energy will
appear in each degree of freedom.

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Degree of freedom
A degree of freedom of a physical system is an independent parameter that
is necessary to characterize the state of a physical system.

Degrees of freedom of a gas molecule is the number of ways of its total

energy can distribute or utilize.

In three-dimensional space, three degrees of freedom are associated with

the movement of a particle.  A diatomic gas molecule has 6 degrees of
freedom (translations, rotations, and vibrations).

For a general, non-linear molecule, all 3 rotational degrees of freedom are

considered, resulting in the decomposition:

3N=3+3+(3N − 6)
N-atom molecule has (3N − 6) vibrational degrees of freedom for N > 2.

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Degree of freedom…..

• For mono atomic gas such as Ar: 3-degres of freedom (3-centre of

mass motions)
• For diatomic gas such as O2: 6-degrees of freedom (3-centre of
mass motions+2-rotational degrees of freedom+1 vibrational
motion)
• CO2: 9-degrees of freedom
• NH3: 12-degrees of freedom

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Degrees of freedom - Monatomic gases

z • Molecule can rotate in its x, y and z axis.


1 2
• Rotational KE, KE  I
2
y
• Moment of inertia I, KE  1  2 Mr 2  2
x 25 
Translational energy

• Size of the molecule is negligible,

Ideal Gas therefore r is negligible and energy due
to rotation is negligible.

The size of an atom is about an angstrom (10 -10 m).

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 Degrees of freedom - Diatomic gases
• Three translational degrees of freedom: x, y, z
• Three rotational degrees of freedom: about x, y and z axes. Rotational energy via x
axis is negligible (r0). Therefore two degrees of freedom.
• One vibrational degrees of freedom: At very high temperatures (>3000 K) bond
become flexible and oscillating starts on this particular bond. At low temperatures
(< 3000 K) this can be neglected.
• At higher temperatures total degrees of freedoms = 6
At low temperatures total number of degrees of freedoms (rigid rotator model) = 5

Figure from “Understanding Properties

of Matter” by M. de Podesta
Diatomic gases have two atoms per molecule: e.g. H2, O2, N2, CO, Cl2.
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Ideal gas law…….
1
PV  Nmv 2
3

1 2 3
KE  mv  k BT
2 2

PV  k B NT

Universal gas constant R is defined as, Ru  N a k B

Ru  (6.022  10 23 mol-1 )  (1.38066  10 23 JK 1 )  8.3143 JK 1mol-1

Ru N
PV  NT  RuT
Na Na

PV  nRuT

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Deviations of real gases from ideal gases

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Water vapor an ideal gas?

N
1 bar  10 5 2
 10 5 Pa
m
10 6
 Pa  0.1 MPa
10
10 5
 kPa  100 kPa
1000

Low pressures (< 10 kPa) ! Yes

High pressures ! No

Percentage of
error
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Compressibility factor - A measure of deviation from ideal gas behavior.
P
PR 
Pcr
T
TR 
Tcr
Pv v actual
Z 
RT videal

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Boyle’s law: PV=constant @ a constant temperature

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Charles’ law : V/T=constant @ a constant pressure

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Absolute temperature

1 2 3
KE  mv  k BT
2 2

2 1 2
T  mv 
3k B 2 

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Example: A cylinder contains a mixture of H2 and O2 molecules. Which
molecules are moving faster when the mixture is in thermodynamic
equilibrium? By what factor? Assume each of the gas behaving as ideal
gas.
1 3
KE  mv 2  k BT
2 2
3k BT 3k BT
v2  v
m m

3k BT
vH 2 mH 2 vH 2 mO2
 
vO2 3k BT vO2 mH 2
mO2

vH 2 32
 4
vO2 2

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Molecular Speed versus Molar Mass

To have the same average kinetic energy, heavier molecules must have a
slower average speed

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Internal KE of a gas particle

• Monatomic, KE  3 k BT
2

• Diatomic at higher temperature, KE  6 k BT

2

• Diatomic at lower temperature, KE  5 k BT

2

• Polyatomic, KE  6 k BT
2

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Internal energy of a gas particles, U

1 
U   KE  PE     KE   N f  kT 
2 
PE = 0
random random

N, number of particles,
f, degrees of freedom

• Monatomic, U  N 3 k BT
2
• Diatomic at higher temperature,U  N 62 k T B

• Diatomic at lower temperature, U  N 52 k T

B

• Polyatomic, U  N 6 k BT
2

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Some physical insight to internal energy

Internal energy is defined earlier as the sum of all the microscopic

forms of energy of a system. It is related to molecular structure and
degree of molecular activity can be viewed as the sum of the kinetic
energy and potential energies of the molecules.

For better understanding of internal energy

We should study that in molecular level

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 Internal Energy Associated with Kinetic Energy
• Molecules of a gas move through space with some velocity, and thus
possess some kinetic energy (KE) – This is known as the translational
energy

• Atoms of poly atomic molecules rotate about an axis – The energy

associated with this rotation is the rotational KE (electrons at outer orbits
have large KE)

• The atoms of poly atomic molecule may also vibrate their common centre
of mass – The energy associated with this back-and–forth motion is the
vibrational KE.

• Electrons spin about their axis – The energy associated with this motion is
the spin energy (other particles in the nucleus also possess spin energy)

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Internal Energy Associated with Kinetic Energy….

• The portion of the internal energy of a system associated with the KE

of the molecules is called the sensible energy.

• Average velocity and the degree of activity of a molecule is

proportional to the temperature of the gas – At higher temperatures,
molecules will possess higher KE - As a result system will have
higher internal energy.

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Internal Energy Associated with Binding Forces
• Binding forces: between molecules of a substance, between the atoms
within a molecule, between the particles within an atom and its nucleus.

• We can expect strongest binding forces in solids and weakest in gasses.

• If sufficient energy is added to molecules of solids or liquid: they will

overcome molecular forces and breakaway turning into gasses – This is
called phase change process.

• Energy at gas phase has higher energy because with added energy
compared to solid and liquid.

• The internal energy associated with the phase change is called latent
energy

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Internal Energy Associated with Chemical Energy

• The internal energy associated with atomic bonds in a molecule is

called chemical energy.

• During a chemical reaction such as a combustion process some

chemical bonds are destroyed while some are formed – Results……
Internal energy changes

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Nuclear Energy

• Tremendous amount of energy is associated with the strong bonds

within the nucleus of the atom – is called nuclear energy

• It is dealt with fusion or fission reactions, reactions

• A chemical reaction involves change in electron structure of a atom,

while atomic reaction involves change in core or nucleus – chemical
reaction preserve the identity of the atom but nuclear reaction losses
the identity of the atom.

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More on Nuclear Energy

• A complete fission of 1kg of U-235 releases 6.731010 kJ of heat.

• That is more than the heat release when burning 3000 tons of coal.

47
Example 1: A nuclear powered car

A average car consumes about 5 l of gasoline a day, and the capacity of the
fuel tank of a car is 50 l. Therefore a car needs to be re-fueled once every 10
days. Also the density of gasoline ranges from 0.68 to 0.78 kg/l, and its
lower heating value is about 44,000 kJ/kg (that is, 44,000 kJ of heat is
released when 1kg of gasoline is completely burned). Suppose, all the
problems associated with the radioactivity and waste disposal of nuclear
fuels are resolved, and the car is to be powered by U-235, if new car comes
equipped with 0.1 kg of U-235 as fuel, determine if this car will ever need
to refueling under average driving conditions. (Note: A complete fission of
1kg of U-235 releases 6.731010kJ of heat)

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Example 1: Solution
• In brief

– Fuel consumption per day= 5 l

– Capacity of the tank = 50 l
– Heating value of gasoline = 44,000 kJ/kg
– Density of gasoline = 0.68 – 0.78 kg/l
– Energy release by U-235 = 6.731010kJ/kg
– Nuclear fuel charge (U-235) = 0.1kg

• Assumptions

– Density of fuel =0.75kg/l

– Nuclear fuel completely convert to thermal energy

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Example 1: Solution..

• Analysis

– Daily energy need=44,000kJ/kg(gassoline mass)

– Daily energy need=44,000kJ/kg(gassoline density  gasoline volume)

– Daily energy need=44,000kJ/kg(0.75kg/l5 l)=165,000 kJ

– The energy release complete fission of 0.1 kg of U-235=

6.731010kJ/kg0.1kg = 6.73109kJ

– Number of days=Energy release by nuclear fuel/daily energy need

= 6.73109kJ/ 165,000 kJ=40,790 days≈112 years

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Example 2:

a) Consider a nuclear power plant that produces 1000 MW of power

and has a conversion efficiency of 30 percent (that is, for each unit of
fuel used, the plant produces 0.3 unit of electrical energy). Assuming
continuous operation, determine the amount of nuclear fuel
consumed by this plant per year. (Note: A complete fission of 1kg of
U-235 releases 6.731010kJ of heat).

a) Repeat the problem for a coal power plant that burns coal whose
heating value is 28,000 kJ/kg.

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Example 2: Solution

a) In brief
– A 1000-MW power plant is powered by nuclear fuel. The amount
of nuclear fuel consumed per year is to be determined

– Assumptions

1. The power plant operates continuously.

2. The conversion efficiency of the power plant remains constant.
3. The nuclear fuel is uranium.
4. The uranium undergoes complete fission in the plant (this is not
the case in practice)

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Example 2: Solution..

Energy consumption rate  Power production/Efficiency

 (1000 MW)/0.3  3333 MW  3.333 106 kJ/s

Annual energy consumption  ( Energy consumtion rate)(1 year)

 (3.333  10 6 kJ/s)(365  24  3600 s/year)
 1.051 1014 kJ/year

Annual energy consumption 1.051 1014 kJ/year

Annual fuel consumption  
Heating value of fuel 6.73  1010 kJ/kg
 1562 kg/year

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Example 2: Solution..

Annual energy consumption 1.051  1014 kJ/year

Annual fuel consumptio n  
Heating value of fuel 28,000 kJ/kg
 3.754  10 9 kg/year
 3,754,000 tons/year

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Energy and environment

• The conversion of energy from one to another affects environment

• Fossil fuel such as oil, coal and natural gas powering the industrial
world.

• Pollutants emits from the combustion of fossil fuel responsible for

acid rains, global warming…..

• Large part is contributed by motor vehicles-release of HC, NOx,

CO..

55
Ozone and Smog

• You probably families with urban smog: This made-up mostly with
ground level O3. ( do not confuse with harmful ground level O3 and
useful O3 layer at high of the atmosphere that will protect us from
harmful UV)

• O3 at ground level has lots of health effects: irritates eyes, effects for
lungs, wheezing, headache, asthma………….

• Smog contains other numerous chemicals, CO, particulate mater such as

shoot and dust, volatile organic compounds (VOC) such as
hydrocarbons…

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 Ozone and Smog

• NOx and HC react in the

presence of sunlight on a hot
calm day, which form
ground level O3, which is the O3
primary component of smog.

NOx
HC

57
Acid rains

• Fossil fuels are mixtures of various chemicals, including small amounts of

sulfur.

• Sulfur in fossil fuels reacts with oxygen and form SO2.

• SOx and NOx react with water vapour and other chemicals at high in the
atmosphere in the presence of sunlight produce nitric and sulfuric acids.
They are washed to soil by rain or snow

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Acid rains

SO x

NO x

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The green house effect

• Simple example to understand

– When you leave your car under direct sunlight, you probably have
noticed that the interiors of the car get much warmer than outside.

– This is because glass at thickness encountered in practice transmit

over 90% of radiation in the visible range and is practically opaque
(nontransparent) to radiation in the longer wave length infrared
region.

– Therefore, glass allows the solar radiation to enter freely but blocks
the infrared radiation emitted by the interior surface.

60
The green house effect in large scale

• The surface of the earth, which warms up during the day as a results of
absorption of solar energy, cools down at night by radiating parts of its
energy into deep space as infrared radiation. CO2, water vapour, and
trace amounts of some other gasses such as methane and nitrogen
oxide, act like a blanket and keep the earth warm at night by blocking
the heat radiated from the earth.

• They are called green house gases. Water Vapour is usually taken out
from this, since that come down as rain or snow.

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