PHYSICS XII Chapter # 15

MOLECULAR THEORY OF GASES

TEMPERATURE:
DEFINITION:
“The quantitative determination of degree of hotness or coldness of a body is
called its temperature”. It is denoted by “T”.
Temperature is a measure of average translational kinetic energy of the molecules
of a body.
SI UNIT: KELVIN (K)

SCALES OF MEASURING TEMPERATURE:

1) Celsius scale: (centigrade Scale):
It has two fixed point called lower fixed point & upper fixed point .Lower point is
the melting point of ice (00C) and upper point is the boiling point of water (1000
C), at standard pressure. It is divided into 100 equal intervals.
2) Fahrenheit Scale:
In this scale ice point of water i-e lower fixed point is 320 F and upper fixed point is
2120 F i-e boiling point of water. It is divided into 180 equal intervals. The degree
of Fahrenheit scale is smaller than the degree of Celsius scale.
NOTE: * At -400 both Celsius scale and Fahrenheit Scale coincide.
* 1div on Celsius scale=1.8 div on Fahrenheit scale.
3) Kelvin Scale: (Absolute Scale)
The thermodynamic temperature is measured in KELVIN. It is standard unit of
temperature. This scale takes 273(k) as ice point & 373(k) as boiling point there
two points are divided into 100 equal intervals in this scale. The lowest
temperature on this scale is 0K =– 273 0C called the “absolute zero” which is the
zero of Kelvin scale.

Celsius scale Fahrenheit scale Kelvin scale

(0C) (0F) (K)
Steam point 100 212 373
or
UPPER FIXED POINT
Ice point 0 32 273
Or
LOWER FIXED POINT
Absolute Zero -273 -460 0

Absolute Zero:
“The zero of kelvin scale is called the Absolute zero. It is the lowest attainable
temperature at which the volume of a gas becomes equal to zero”.
At zero Kelvin the volume of gas becomes zero and all the motion ceases to exist
means K.E is also zero.
DERIVATION:

In order to derive the empirical formulae among Celsius, Fahrenheit and kelvin
scales, let the three thermometers be placed in a bath tub and mercury in each
thermometer rises to the same level.

Temp on one scale – F.P = Temp on second scale – F.P

B.P – F.P B.P – F.P

TC – 0 = TF – 32 = TK – 273

100-0 212-32 373-273

By solving these we get,

1) TF to TC :

TC=5/9 (TF-32)

2) TC to TF :

TF= (9/5×TC) + 32

3) TC to TK :

TK= TC+273

THERMAL EQUILIBRIUM:
When two bodies at different temperatures are brought in thermal contact with
each other the heat starts flowing from the hot body to the cold body till the
temperature of both bodies becomes equal then they are said to be in thermal
equilibrium.
THERMOMETRIC PROPERTIES:
Property of a substance which changes uniformly with the change of temperature.

THE ZERO TH LAW OF THERMODYNAMICS:

Statement:
When two bodies ‘A’ and ‘B’ are in thermal equilibrium with a third body ‘C’, then
They all are in thermal equilibrium with each other. A B C

TRIPLE POINT OF WATER:

The triple point of water is a unique physical phenomenon where water exists in
equilibrium as a solid (ice), liquid (water), and vapor (steam) simultaneously. This
occurs at a specific temperature and pressure where all three phases coexist in
thermodynamic equilibrium.
Explanation:
At the triple point of water, the temperature and pressure conditions are precisely
0.01°C (273.16 K) and 611.657 pascals (6.11657 mbar), respectively. Under these
conditions:
• Ice can exist alongside liquid water and water vapor without either phase
predominating over the others.
• If any slight change occurs in temperature or pressure, the equilibrium shifts,
causing water to either freeze or vaporize until a new equilibrium is reached.
In the diagram:
• The point where the
three lines (solid, liquid,
and vapor phases) meet
represents the triple
point.
• At this exact point, the
temperatures and
pressures allow for the
coexistence of ice,
liquid water, and water
vapor.

GAS LAWS:
Boyle’s law:
Statement:
The volume of a given mass of a gas is inversely proportional to the pressure of the gas
provided the temperature of gas remains constant .
Mathematically, V ∝ 1/P
PV= constant
In the relation of volume and pressure the mass remains same .However if the mass of the
gas varies then PV will be proportional to the mass (m),
PV∝ m
 PV= (constant) m
𝑃𝑉
=constant
𝑚

𝑉1 𝑃1 𝑉2 𝑃2
For initial and final state of a gas: = =constant
𝑚1 𝑚2
Graphically:
P
Graph b/w P & V at constant temperature is hyperbolic curve

(Real gases obey Boyle’s law at low pressure)

CHARLES’ LAW:
Statement I:
The volume of a given mass of a gas is directly proportional to the temperature when the
pressure is kept constant .
Mathematically, V∝ T
V/T = constant
For initial and final state of a gas:
V1/T1=V2/T2=constant
The direct relation of temperature and volume is valid until the mass remains constant
however if mass varies then the ratio will be proportional to mass.
𝑉
∝m
𝑇

𝑉
= (constant) m
𝑇

𝑉
=constant
𝑇𝑚

Graphically:

Graph b/w T &V is a straight line. At very

low temperature (-273 0C) or (0K)
volume of a gas become zero.

Avogadro’s law :
Avogadro's Law describes the relationship between the volume of a gas and the
amount of substance (in terms of moles) when temperature and pressure are held
constant. It states that equal volumes of gases at the same temperature and pressure
contain equal numbers of molecules.
Explanation:
1. Equal Volume Concept: According to Avogadro's Law, under constant
temperature and pressure, volume of a gas is directly proportional to number of
moles of the gas.
 2. Mathematical Representation: The law can be mathematically represented as:
V ∝n
where V is the volume of the gas, and n is the amount of substance measured
in moles.
3. Proportional Relationship: This means that if you double the amount of gas
(moles), the volume of the gas will also double, assuming constant temperature
and pressure.
V/n = k
Thus,
V1/n1 =V2/n2
This equation says that when the
number of particles in a gas
changes from n1 to n2, the
volume also changes from V1 to
V2.

IDEAL GAS EQUATION:

The purpose of creating Ideal gas law was to show the relationship between pressure,
volume, moles of gas, and temperature. It is a hypothetical or speculative equation for an
ideal gas. Pressure and volume have an inverse relationship; however, temperature has a
direct relationship. The equation for the Ideal Gas Law is:
P×V=n×R×T
Where,
‘P’ denotes the ideal gas pressure. ‘V’ denotes the volume of the ideal gas. ‘n’ represents the
quantity of ideal gas measured in moles. ‘R’ is the proportionality constant or the gas
constant and ‘T’ stands for the ideal gas temperature.
Derivation Of Ideal Gas Equation:
Let us consider,
The pressure exerted by the gas: P
The volume of the gas: V
Temperature: T
The number of moles of gas: n
Universal gas constant: R
According to Boyle’s Law, At constant n & T, the volume makes an inverse relation with the
pressure exerted by a gas.
i.e.
V ∝ 1/P ————————-(i)
According to Charles’ Law, When P & n are constant, the volume of gas directly relates to the
temperature.
i.e.
V∝T ————————-(ii)
According to Avogadro’s Law, When P & T are constant, then the volume of gas makes a
direct relation with the number of moles of gas.
i.e.
V∝n ———————–(iii)
Combining all the three equations, we have-
V ∝ nT/P
or
PV = nRT
Where R is the Universal gas constant, which has a value of 8.314 J/mol-K
Hence derived.

KINETIC MOLECULAR THEORY OF GASES:

The Properties of matter in bulk can be predicted on molecular basic by kinetic molecular
theory. Following assumptions are made to set up a model
1. A gas consist of particles called molecules. Depending on the gas each molecule will
consist of an atom or group of atoms-All the molecules of a gas in a stable state are
considered identical
2. The volume of a gas contains a large number of molecules. (about 3x1025 molecules of
in 1 m3 at S.T.P)
3. Molecules of a gas always remain in form of random motion, during their motion they
collide with each other and with the walls of container. Their collisions are perfectly
elastic.
4. The molecules are separated by distance large as compared to their own dimensions
.The diameter of a molecules consider as a sphere, is about 3x10-1 0m.
5. Molecules exert no forces on one another except during collision during two successive
collision molecules moves in a straight line-
6. Laws of Newton are applicable to the motion of molecules.

INTERPRETATION OF PRESSURE OF A GAS IN TERMS OF K.M.T

MATHEMATICAL EXPRESSION:

Consideration:
To calculate the pressure of an ideal gas, consider a cube of length of each side is ‘L”
containing ‘N’ numbers of molecules each of mass “m” .
A molecule will have a velocity ‘V’ at any instant and this will have components Vx, Vy
and Vz in the direction of their axes or in the direction of the edges of a cube.
Assumption,
For simplicity consider the motiom of molecules in x- direction.
So the molecule moves from left face of the cube with velocity ‘Vx ’ and collide with the right
face of the cube and bounce back and its velocity become ‘-Vx ’.

1) FOR CHANGE IN MOMENTUM:

Momentum before collision =mVx
Momentum after collision = -mVx
Change in momentum= Momentum after collision - Momentum before collision
= - m𝐕𝐱 - m𝐕𝐱

Change in momentum= - 𝟐𝐦𝐕𝐱

2) DISTANCE TRAVELED BY MOLECULE DURING ONE COLLISION ALONG X-AXIS:

If the distance travelled by the molecules during one collision is ‘S’ and ‘t’ is the time taken
b/w two successive collision on right face, consider the motion in x-direction only.
Also, we know that S = vt
If S= 2L , v =Vx
𝟐𝑳
t=
𝑽𝒙

3) FORCE EXERTED BY MOLECULES ON WALLS:

As, Force =Net rate of change of momentum, this is the force exerted by the wall of container
on the molecule
2mV x
𝐹=−
2𝐿
Vx
The force exerted by molecule on the wall of the container is

2mV x
𝐹= 2𝐿
Vx

Force on N molecules, 𝐹𝑥 = 𝐹1 +𝐹2 +……………𝐹

m m m
𝐹𝑥 = V21x + 2
V2x +………….+ 2
VNx
𝐿 𝐿 𝐿
m
𝐹𝑥 = (V21x + V2x
2
+………….+ VNx
2
)
𝐿

PRESSURE EXERTED BY MOLECULES:

Pressure of a gas can be defined as “Average force exerted by the molecules of a gas on
the walls of a container during collision per unit area of the container.”
𝑷 = 𝑭/𝑨
Area= 𝑳𝟐

m
∑𝑁 2
𝑖=1 𝑉𝑥
𝐿
𝑷𝒙 =
𝑳𝟐
 𝐦 ∑𝑁 2
𝑖=1 𝑉𝑥
𝑃𝑥 = (1)
𝑳𝟑

Let , 𝒏𝒗 be the number of molecules per unit volume, which is known as NUMBER
DENSITY(𝒏𝒗 )

𝑵
𝒏𝒗 =
𝑳𝟑
𝑵
𝑳𝟑 =
𝒏𝒗
Putting value of L in eq (1) ,
3

𝟐
𝐦 ∑𝑵
𝒊=𝟏 𝑽𝒙
𝑷= 𝑵
𝒏𝒗

𝟐
𝐦𝒏𝒗 ∑𝑵
𝒊=𝟏 𝑽𝒙
𝑷=
𝑵

Let ρ be the density of gas, ρ = 𝐦 𝒏𝒗

𝑵 𝟐
∑ 𝑽𝒙
So, eq (2) becomes, 𝑷 = ρ 𝒊=𝟏
𝑵

Now pressure of ‘N’ the molecules in x-direction,

𝐕𝟐𝟏𝐱 +𝐕𝟐𝟐𝐱 +𝐕𝟐𝟑𝐱+ −−−− + 𝐕𝟐𝐍𝐱

P=ρ ( 𝑵
) (2)

since, mean square velocity of all the molecules along x –direction is, ̅𝑽𝟐𝒙
𝟐
∑𝑵
̅𝑽𝟐𝒙 = 𝒊=𝟏 𝑽𝒙 =(𝐕 𝟏𝐱+𝐕 𝟐𝐱+𝐕 𝟑𝐱+ −−−− + 𝐕 𝐍𝐱)
𝟐 𝟐 𝟐 𝟐

𝑵 𝑵

So, eq 2 becomes, ̅ 𝟐𝒙
P=𝝆𝑽 (3)
The net velocity of the molecules could be expressed as 𝑉̅ 2 ,
𝑉̅ 2 = 𝑉̅𝑥2 + 𝑉̅𝑦2 + 𝑉̅𝑧2
Since the molecules are in random motion, 𝑉 ̅𝑥2 = 𝑉̅𝑦2 = 𝑉̅𝑧2

Therefore 𝑉̅ 2 = 𝑉̅𝑥2 + 𝑉̅𝑥2 + 𝑉̅𝑥2

𝑉̅ 2 = 3 𝑉̅𝑥2

1/3 𝑉̅ 2 ̅𝑥2
=𝑉
̅𝑥2 in eq(3) we get,
Put, 𝑉 𝟏
P= ̅𝟐
𝝆𝑽
𝟑
The above equation gives pressure of a gas in terms of mean square speed of gas
molecules and the density of gas. Pressure of a gas is directly proportional to density
of the gas and mean square velocity of the gas.

RELATIONSHIP BETWEEN TEMPERATURE AND AVERAGE TRANSLATIONAL

KINETIC ENERGY OF AN IDEAL GAS:

Q: Show that average translational kinetic energy of an ideal gas is directly

proportional to absolute temperature. OR
𝟏 𝟑
Show that: 𝟐
𝐦𝐕 𝟐 =𝟐 KT OR K.E ∝ T

Proof: According to K.M.T. Pressure of a gas is given by,

𝟏
P= ̅𝟐
𝝆𝑽 --------------------- (1)
𝟑
Density of gas is given by, 𝜌= m 𝑛𝑣
𝑵
𝒏𝒗 =
𝑽
So,
𝑵𝒎
𝝆= 𝑽
𝟏 𝑵𝒎
putting the value of 𝝆 in eq (1), P= ( ) ̅𝟐
𝑽
𝟑 𝑽
𝟐 𝟏
= ̅𝟐)
(N) ( m𝑽 ----------------- (2)
𝟑 𝟐

According to general gas law,

PV=nRT
𝟐 𝟏
Now eq (2) becomes, nRT= ̅𝟐)
(N) ( m𝑽 ----------------- (3)
𝟑 𝟐
If: NA = Avogadro’s no, which is the no of molecules present in a mole of a gas, and
𝑵
𝑵𝑨 =
𝒏
Where,
N = no of molecules
n = no of moles
𝑵 𝟐 𝟏
put n = N/NA in eq (3), we get RT= ̅𝟐)
(N) ( m𝑽
𝑵𝑨 𝟑 𝟐
𝑹 𝟐 𝟏
T= ̅𝟐)
( m𝑽
𝑵𝑨 𝟑 𝟐
𝑅
Where, =K = Boltzmann constant
𝑁𝐴
𝟐 𝟏
Put ‘K’ in above equation , KT= ̅𝟐)
( m𝑽
𝟑 𝟐

𝟑 𝟏
̅𝟐
KT= 𝟐 m𝑽
𝟐
𝟏
Where, ̅ 𝟐 =K.E= Average transnational kinetic energy
m𝑽
𝟐
T = Absolute temperature
𝟑
K = constant
𝟐
 𝟑
K.E= 𝟐 KT
So, K.E = (const) T
K.E ∝ T (absolute temperature)

𝟏
̅𝟐 ∝ T
m𝒗
𝟐

Hence it is proved that average translational kinetic energy of an ideal gas is

directly proportional to absolute temperature.

RELATIONSHIP OF MEAN SQUARE SPEED AND TEMPERATURE OF A GAS:

𝟑
As, K.E= 𝟐 KT

𝟏 𝟑
𝒎 ̅𝑽𝟐 = 𝟐
KTm
𝟐

̅𝑽𝟐 = 𝟑𝑲𝑻
𝒎

𝟑𝑲𝑻
Taking square root on both sides, we get, 𝑽𝒓𝒎𝒔 = √
𝒎

Where, 𝑽𝒓𝒎𝒔 =root mean square speed of gas molecules.

𝒎 =mass of a gas molecule.

𝑽𝒓𝒎𝒔 ∝ √𝑻
The above equation shows that root mean square speed of gas molecules is directly
proportional to temperature of gas.

FORMULA FOR 𝑽𝒓𝒎𝒔 :

𝟏) 𝑽𝒓𝒎𝒔 in terms of mass of gas molecule is given by :

𝟑𝑲𝑻
𝑽𝒓𝒎𝒔 = √
𝒎
𝟐) 𝑽𝒓𝒎𝒔 in terms of molar mass is given by:
𝑹
we know that, 𝐾 = 𝑵
𝑨

𝟑𝑲𝑻
𝑽𝒓𝒎𝒔 = √
𝒎
𝟑𝑹𝑻
𝑽𝒓𝒎𝒔 = √
𝒎 𝑵𝑨

but , 𝑴 = 𝒎 𝑵𝑨 ,
 Where, M is the molar mass which is defined as mass of one mole of a gas expressed
in grams.
Thus, 𝟑𝑹𝑻
𝑽 =√ 𝒓𝒎𝒔 𝑴

𝟑) 𝑽𝒓𝒎𝒔 in terms of pressure & density of gas is given by:

we know that,
𝟏
P= ̅𝟐
𝝆𝑽
𝟑
̅ 𝟐 = 𝟑𝑷
𝑽
𝝆
Taking square root on both sides, we get,

𝟑𝑷
𝑽𝒓𝒎𝒔 = √
𝝆

DEDUCE GAS LAWS FROM THE FORMULA OF PRESSURE OF GASES:

1)DEDUCTION OF BOYLE’S LAW FROM THE FORMULA OF PRESSURE OF

GASES:
From K.M.T, Pressure of gases,
𝟏
P= ̅𝟐
𝝆𝑽
𝟑
And 𝜌= m 𝑛𝑣
𝑁
𝑛𝑣 =
𝑉
So,
𝑵𝒎
𝝆=
𝑽
𝟏 𝑵𝒎
putting the value of 𝝆 in eq (1), P= ( ) ̅𝟐
𝑽
𝟑 𝑽

Multiply and divide above expression by ‘2’,

𝟐 𝟏
PV= ̅𝟐)
(N) ( m𝑽
𝟑 𝟐

𝟐
PV= (N) (K.E) (1)
𝟑
𝟑
Where, K.E= KT put in eq (1),
𝟐
𝟐 𝟑
PV= (N) ( KT)
𝟑 𝟐

PV = NKT (2)
In eq (2) , NKT = constant
As,
Temperature in Boyle’s Law is constant
K is Boltzmann constant
N is no of molecules in a gas sample
 So, eq 2 becomes, PV=constant

𝐜𝐨𝐧𝐬𝐭𝐚𝐧𝐭
𝑷=
𝑽
𝟏
𝑷∝ (Which is Boyle’s Law)
𝑽

2)DEDUCTION OF CHARLES’ LAW FROM THE FORMULA OF PRESSURE OF

GASES:
From K.M.T, Pressure of gases,
𝟏
P= ̅𝟐
𝝆𝑽
𝟑
And 𝝆= 𝐦 𝒏𝒗
𝑵
𝒏𝒗 =
𝑽
So,
𝑵𝒎
𝝆=
𝑽
𝟏 𝑵𝒎
putting the value of 𝝆 in eq (1), P= ( ) ̅𝟐
𝑽
𝟑 𝑽

Multiply and divide above expression by ‘2’,

𝟐 𝟏
PV= ̅𝟐)
(N) ( m𝑽
𝟑 𝟐

𝟐
PV= (N) (K.E) (1)
𝟑

𝟑
Where, K.E= KT put in eq (1),
𝟐
𝟐 𝟑
𝑷𝑽 = (N) ( KT)
𝟑 𝟐

P 𝑽 = NKT
𝑽 𝑵𝑲
Rewrite above eq, = (2)
𝑻 𝑷
𝑵𝑲
In eq (2), 𝑷
= constant
As,
Pressure in Charles’ Law is constant
K is Boltzmann constant
N is no of molecules in a gas sample

𝑽
So, eq 2 becomes, =constant
𝑻

𝑽 = ( Constant) T
𝑽 ∝ T (which is Charles’ Law)