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Assumptions of Kinetic theory :

(i) Assumptions regarding the molecule :

(a) Every gas consists of extremely small particles

known as molecules. The molecules of a given

gas are all identical but are different than those

another gas.

(b) The molecules of a gas are identical, spherical,

rigid and perfectly elastic point masses.

(c) Their size is negligible in comparison to inter

molecular distance (109 m)

(ii) Assumptions regarding volume :

The volume of molecules is negligible in

comparison to the volume of gas. (The volume

of molecules is only 0.014 % of the volume of

gas.)

(iii) Assumptions regarding motion :

(a) Molecules of a gas keep on moving randomly in

all

possible

direction

with

all

possible

velocities.

(b) The speed of gas molecules lie between zero

and infinity (very high speed).

(c) The number of molecules moving with most

probable speeds is maximum.

(iv) Assumptions regarding collision :

(a) The gas molecules keep on colliding among

themselves as well as with the walls of

containing vessel. These collision are perfectly

elastic. (i.e. the total energy before collision =

total energy after the collisions).

(b) Molecules move in a straight line with constant

speeds during successive collisions.

(c) The distance covered by the molecules between

two successive collisions is known as free path

and mean of all free paths is known as mean

free path.

(d) The time spent is a collision between two

molecules is negligible in comparison to time

between two successive collisions.

(e) The number of collisions per unit volume in a

gas remains constant.

(v) Assumptions regarding force :

(a) No attractive or repulsive force acts between

gas molecules.

ineffective due to extremely small masses and

very high speed of molecules.

(vi) Assumptions regarding pressure :

Molecules constantly collide with the walls of

container due to which their momentum

changes. This change in momentum is

transferred to the walls of the container.

Consequently pressure is exerted by gas

molecules on the walls of container.

(vii)Assumptions regarding density :

The density of gas is constant at all points of

the container.

2. SOME DEFINITIONS

Definition :

(i) Gram mol. or Kilogram mol. :

(a) The quantity of matter in which the number of

molecules is equal to the Avogadro's number,

is defined as gram mol.

(b) The molecular weight of any substance

expressed in kilogram is defined as 1 kilogram

mol of that substance.

(c) The molecular weight of any substance

expressed in grams is defined as 1 gram mol of

that substance.

(d) 1 Kg mol of H2 = 2 kg.,

1 Kg mol of N2 = 28 kg.

1 Kg mol of O2 = 32 kg.,

1 Kg mol of CO2 = 44 kg.

(e) No. of molecules in 1 mol

=

Number of mols.

Mass of gas

Molecular wt. of gas

m

M

(g) The mass of 1 mol of a gas is equal to its

molecular weight.

or

n=

(a) The number of molecules present in 1 mol of a

gas is defined as Avogadro's number.

(b) NA = 6.01 1023 per gm. mol.

= 6.02 1026 per Kgm. mol.

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48

(a) Molar volume Vm : The volume of 1 mol of gas

is known as molar volume (Vm).

(b) Vm =

V

n

(a) The quantity in 1 mol of matter is its molecular

OF A GAS

molecule at any instant of time.

(2) Instantaneous

< v > = v=

= 1 atmosphere.

| v | | v 1 | + | v 2 |+ ... | v N |

=

N

N

8RT

RT

kT

=1.59

=1.59

M

M

m

the speed with which maximum number of

molecules travel.

absolute zero temperature (i.e. 0 K).

vmp =

2RT

=

M

2kT

m

squares of instantaneous velocities of all the

molecules.

becomes zero.

< v2 > = v 2 =

v 2 v12 + v 22 + ...v 2N

=

N

N

vrms =

molecules of the gas

N0 = Avogadro's constant = 6.023 1023

v

v + v + ... v N

= 1 2

=0

N

N

of

Speed

(| v |):

weight.

speed

v2

=

N

v12 + v 22 + ...v 2N

N

3RT

3kT

3PV

=

=

=

M

m

nM

3P

d

vs =

C

RT

, where = P

M

CV

T = Temperature in Kelvin

N = Total number of molecules

d = Density of gas = nM/v

n = No. of moles

Examples

based on

Ex.1

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What is the rms speed of Helium gas molecules

at STP.

KINETIC THEORY OF GASES

49

Sol.

Ex.4

vrms is given by

3RT

M

vrms =

At STP, T = 273K,

M = 4 gm/mol = .004 kg/mol

R = 8.31 J/molK.

Crms

1.7 10 6

The rms speed of oxygen at room temperature is

about 500 m/s. The rms speed of Hydrogen at

the same temperature is about

(A) 125 m/s

(B) 2000 m/s

(C) 8000 m/s

(D) 31 m/s

Sol.[B] RMS speed is given by

Ex.2

vrms =

Ex.5

3RT

M

1

M

( v rms ) 0

=

( v rms ) H

(C rms )T

= (C rms )T =

(C rms )T

(C rms )T

= 2

(T2 / T1 )

480

= 2

120

molecules (O2) at a certain temperature T

3RT / M

the new temperature T' = 2T

and oxygen (O2) dissociates in atomic oxygen,

then molecular weight M' = M/2

The new rms speed

v' =

3 , 3, 4, 6 m/s, the root mean square velocity

will be(A) 4

(B) 16

(C) 8

(D) 13 3 /4

Sol.[A] Q vrms =

MH

M0

1

500

2

=

=

( v rms ) H

32

4

Ex.3

doubled and oxygen gas dissociates in to

atomic oxygen. Is the rms speed remains

unchanged

(A) Yes

(B) No.

(C) Nothing can be said

(D) None of these

At constant temperature

vrms

3RT

M

Sol.[B] Q Crms =

3 8.31 273

.004

vrms=

120 K to 480 K. The root mean square velocity of

the gas molecules is '', at 480K it becomes

(A) 4

(B) 2

(C) /2

(D) /4

v12 + v 22 + v 32 + v 24

4

4.

1/ 2

vrms =

vrms =

64

4

= 4m/s

3R 2T

M/2

3RT

M

v' = 2v

4

1/ 2

v' = 2

3RT '

=

M'

1/ 2

MAXWELL'S LAW OF

VELOCITY DISTRIBUTION

MOLECULAR

the range from 0 to .

(b) The curve between number of molecule per

unit velocity range and velocity at different

temperature is as shown.

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50

4.

T = 300 K

T = 1000 K

T = 2000 K

dn

dv

5.

vmp

vmp

vmp

2L

vx

t =

velocity range is constant however the velocity

of each molecule is changing.

Results :

(a) Different molecules have different velocities.

(b) As the temperature increases, the number of

molecules having higher velocities increases.

(c) At a given temperature, the velocity which

maximum number of molecules possess, is

called most probable velocity (vmp).

(d) With the increase in the temperature, the most

probable velocity increases.

(e) Area under the curve represent the total number

of molecules.

5. CALCULATION OF PRESSURE OF GAS

change in momentum of the wall = equal in

magnitude but opposite in direction to that of

molecule P = 2mvx

The distance travelled parallel to the

x-direction = L. Thus, the time between two

successive collisions with the shaded wall is

vx

2L

The momentum imparted per unit time to the

n=

6.

F = nP =

7.

=F=

8.

vx

mv 2x

2mvx =

2L

L

m 2 m

vx =

L

L

2

x

be equal, we have

v 2x = v 2y = v 2z =

1

( v 2x + v 2y + v 2z )

3

1

1 m 2

v

= v2 F =

3

3 L

9.

sample, F =

X

L

any direction

1 mN v 2

3 L N

L

Z

1. Consider an ideal gas enclosed in a cubical

vessel of edge 'L'

2.

v = v x i + v y j+ v z k

3.

with velocity vx.

(a) momentum before collision = mvx

(b) momentum after collision = mvx

(assuming elastic collision)

change in momentum of the molecule

= mvx mvx = 2mvx

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1 mN v 2

3 L3

N

L

2

1 m0 v

P=

3 V N

where,m0 = Total mass of the gas = mN

P=

m = mass of each molecule

P=

m

1 v2

(d = density = 0 )

d

3

N

V

P=

1

d v 2rms

3

or PV =

Q (vrms =

v2

)

N

1

1

m0 v 2rms or PV = Nm v 2rms

3

3

KINETIC THEORY OF GASES

51

=

1 mN 2

v rms

3 V

1

Energy E = v 2rms

2

1

m v 2rms

2

Total energy = E0 =

P=

1

Nm v 2rms

2

Nm v 2rms = 2E0

PV =

2

2

E0 or P = E

3

3

1

1

1

mv12 + mv 22 + .... + mv 2n

2

2

2

So energy is basically the sum of energies of

all molecules which represents translational

kinetic energy.

11. Dependence of pressure :

(a) P n (Total number of moles)

(b) P m ( Total mass of the gas)

(c) P v 2rms

(d) P 1/V (V = Volume)

(e) P d (d = Density)

(f) P E (E = Energy per unit volume)

Examples

based on

Ex.6

Sol.

for molecules of all gases at a given

temperature ?

(A) Mass

(B) Speed

(C) Momentum

(D) Kinetic energy

Sol.[D] Kinetic energy according to kinetic theory of

gases is given by,

Ex.8

A flask of 103 m3 volume contains 3 1022

molecules of oxygen at a certain temperature.

The mass of one molecule of oxygen is

5.3 1026 Kg and rms velocity of its molecules

at the same temperature is 400 m/s. Calculate

the pressure of the gas.

Pressure of the gas

P=

Here

3

RT

2

R is a universal constant and temperature

remains same for all gases. So kinetic energy is

same for molecules of all gases at a given

temperature.

E=

Ex.9

1 mN 2

v rms

3 V

V = 103m3 N = 3 1022

m = 5.3 1026 Kg vrms = 400 m/s

1 5.3 10 26 3 10 22 (400) 2

P=

3

10 3

2E

. Here E refers to

3V

(D) 4P0/ 2

1 Nm 2

v rms (m = mass of each molecule,

3 V

V = volume of the gas)

Now , m' = 1/2 m

v'rms = 2vrms

Sol.[B] P0 =

P=

the mass of each molecule is halved and speeds

are double, then resulting pressure will be (B) 2P0

(A) 4P0

(C) P0

Ex.7

v 2 + v 22 + ... + v 2n

1

mN 1

2

N

P' =

Ex.10

(C) Vibrational kinetic energy

(D) Total kinetic energy

1 Nm 2

1 Nm.4v 2rms

= 2.

v rms = 2P0

3 V

3

2V

the walls of containers by H2 and Ne gas

molecules kept at same volume and

temperature is

(A) 10 : 1

(B) 1 : 10

(C) 1 : 10

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(D) 10 : 1

KINETIC THEORY OF GASES

52

number of collisions per second are given by

2.

vx

Now, vx = vrms/ 3

2L

'L' and 'T' is same of both. Then, Ratio of speed

given by

v rms,H 2

v rms, Ne

M Ne

=

M H2

20

=

2

10 :1

and O2 at same temperature. If the number of

molecules of these gases is also equal then the

ratio of pressure exerted by these will be (A) 1 : 1

(B) 4 : 1

(C) 8 : 1

(D) 16 : 1

Sol.[A] Pressure of the gas

1 nM 2

1 nM 3RT nRT

P=

=

v rms =

.

3 V

3 V

V

M

Given, nH = nO TH = TO

Ex.11

VH = VO

2

PH = PO

2

a pressure of 1.0 105 newton/metre2 is

1.98kg/m3. Find the root mean square velocity

of its molecules at 0C. Pressure is constant

(A) 39 metre/sec

(B) 3.09 metre/sec

(C) 389 metre/sec (D) 38.9 metre/sec

Sol.[C] We know that

1

P = v2

3

Ex.12

7. DEGREE OF FREEDOM

store energy is called degrees of freedom. It can

also be referred as the number of modes in which

motion of gas molecule takes place.

Degree of Freedom

Translational Rotational Vibrational Total

Monatomic

Diatomic

Triatomic /

Triangular

Triatomic Linear

ENERGY

1.

2.

3.

1/ 2

3P

P = 1.0 105 N/m2

vrms =

4.

3PV

1 nM 2

v rms or v2rms =

P=

3 V

nM

(n = no. of moles)

Q PV = nRT

v2rms =

3PV

or vrms =

M

equilibrium all its energy is divided equally

among it's all possible degrees of freedom.

At temperature T K, each degree of freedom

contributes on an average 1/2 KT of energy per

molecule and 1/2 RT of energy per mole.

If 'f' is the number of degrees of freedom, mean

energy of a molecule at temperature T is

fRT

fKT

and Total energy per mole =

E=

2

2

Total internal energy

U = Potential energy + Kinetic energy

3 1.0 105

vrms =

1.98

vrms = 389 m/s

1.

speed of molecules of a gas is zero at 0 K.A

temperature less than 0 K is not possible

because at this temperature velocity becomes

an imaginary quantity. So, the temperature at

which rms speed of gas molecule is zero is

called absolute zero or zero Kelvin.

3PV

M

U = Kinetic energy

fRT

=

(per mole)

2

5. For translatory motion of any gas, f = 3

Mean translatory KE per molecule = (3/2) KT

Mean translatory KE per mole = (3/2) RT

Mean translatory KE per gram = (3/2) (RT/M)

6.

As we already have

P = (2/3) E

Where E Energy per unit volume = (3/2) P

Mean translatory KE in unit volume of a gas is

(3/2)P, where 'P' is the pressure of the gas.

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53

7.

Total energy

E0 = (3/2) PV ......... (for volume V)

1.

2.

3.

kinetic energy of one mole of a gas

(6.023 1023 molecules)

E = (1/2) Mv2rms = (3/2) RT

Mean translatory KE of one molecule = (3/2) KT

If 'M' is the molecular wt in kg, i.e. mass of one

mole of gas, then mean KE of one gram of gas

Ex.15

translational kinetic energy of a molecule in a

gas equal to the kinetic energy of an electron

accelerated from rest through a potential

difference of 5 volt.

(B) 3.865 103K

(A) 386.5 103K

(D) 38.65 103 K

(C) .38 103K

Sol.[D] K.E. of the electron is

5 eV = 5 1.6 1019J

But K.E. = 3/2 KT

3 RT 3 KT

=

=

2 m

2 M

Where m = mass of each molecule in kg.

Examples

based on

Ex.13

3

1

Sol.[A] KT = mve2

2

2

Where ve = escape velocity of earth = 11.1 km/sec

m = mass of 1 molecule of oxygen

= 5.34 1026

T=

T=

3 1.38 10 23

T = 38. 65 103 K

At what temperature will the root mean square

velocity of oxygen molecules be sufficient so as

the escape from the earth ?

(B) 16 105K

(A) 1.6 105 K

5

(D) 160 105 K

(C) .16 10 K

5 1.6 10 19 2

T=

REAL GAS

Ideal Gas

Real Gas

ideal gas equation

the ideal gas equation

Boyle's, Charle's and

laws.

state of pressure and

temperature

mv e2

3K

5.32 10 26 (11.1 10 3 )

of state is PV = RT

3 (1.38 10 23 )

state is

P+

T = 1.6 10 K

Ex.14

10.2 eV above its ground state. What

temperature is needed to excite hydrogen atoms

to first excited level

(B) .788 104 K

(A) 7.88 104

4

(C) 78.8 10 K

(D) 788 104 K

Sol.[A] K.E. Per atom = 3/2 KT

K.E. of the hydrogen atom = 10.2 eV

10.2 eV = 10.2 (1.6 1019) Joule

2 K.E. per atom

T=

3

K

2 10.2 1.6 10 19

3

1.38 10 23

Where k = 1.38 1023 J/mole. K

T = 7.88 104 K

T=

(V b) = RT

V2

Their

specific

heat

is

proportional

to

independent of

directly

temperature

temperature (Cv T)

depends

upon

only

temperature

Their

energy

as

dU = CvdT

internal

well

dU = CvdT +

as

a

V2

volume

dV

gases

behave

like

ideal gases

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54

Graphically

1.

pressure of a given mass of gas is inversely

P/T

1/P

i.e. P

or PV = Constant.

P/T

Graphically,

1/T

T

P

V

1/V

1/P

PV

P or 1/P

Using all the laws above, an equation for n

moles of an ideal gas can be written in the

form.

Where, n = No. of moles

N = No. of molecules = N0n

N0 = Avogadro's constant

K = Botzmann's constant = (R/N0)

PV

V

2.

4.

PV

t(C)

T or 1/T

1

(T = Constant)

V

m

M

m = Total mass of the gas

M = Molecular wt.

No. of moles =

absolute temperature.

i.e. V T (P = Constant) Temperature is in

Kelvin.

PV = m

Graphically

R

T = mrT

M

R

M

Note : If mass of gas is also changed, then

Boyle's, Charle's and Gay-Lussac's laws cannot

be applied. However we can use the relation,

V

1/V

T

V

T

1/T

V

V/T

P1V1

PV

= 2 2

n1T1

n 2 T2

V/T

5.

T or 1/T

V or 1/V

t(C)

" The pressure exerted by a mixture of several

gases equals the sum of pressures exerted by

3.

or

P1 P2

=

T1 T2

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component gases

KINETIC THEORY OF GASES

55

6.

Avogadro's Law :

At the same temperature and pressure, equal

volumes of all gases contain equal number of

Examples

based on

Ex.17

molecules or moles

Imp. Facts :

(a) At = T = 273 K and P = 1atm, (STP), 22.4 litre

of each gas has N0 = 6.023 1023 molecules or

Sol.

T1

[Here T1 = 273 + 37 = 310 K and

T2

T2 = 273 + 23 = 296 K]

310

= 1500

296

= 1570.95 litre

V2 = V1

(c) This implies that 32 gm oxygen (O2), 28 gm

Nitrogen (N2), 2 gm Hydrogen (H2) etc. occupy

the same volume = 22.4 litres at STP.

When two gases at the same pressure and

temperature are allowed to diffuse into each

Examples

based on

Ex.18

inversely proportional to the square root of the

density of the gas

i.e. D

1

d

Sol.

Where, D = Rate of diffusion, d =

Examples

based on

Ex.16

2

300 [Here T1 = 273 + 27 = 300 K]

1

= 600 K

= 600 273

= 327C

900 cc. What pressure is needed to do this if the

temperature is kept constant ?

Examples

based on

Ex.19

P1V1 = P2V2

V1

V2

= (1 atm)

P2

T1

P1

Boyle's law

P2 = P1

1 atm when the volume is 100 ml and its

temperature is 27C. What will be the

temperature of the gas if the pressure becomes

2 atm and volume remains 100 ml.

Here volume remains constant, so

T2 =

D1

d1

=

D2

d2

Sol.

Gay-Lussac's law

P1 P2

=

T1 T2

density of gas.

is inhaled by a person whose body temperature

is 37C, if the pressure and mass stay constant,

what will be the volume of the gas in the lungs

of the person.

Here pressure and amount of the gas are kept

constant. Therefore,

V1 V2

=

T1 T2

7.

Charle's law

Sol.

1000

900

= 1.11 atm

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A vessel of volume 2 103 m3 contains

0.1 mol of hydrogen gas and 0.2 mol of

helium. If the temperature of the mixture is

300 K calculate the pressure due to component

gases and the mixture

According to Dalton law

Pmixture = PH + PHe

RT

(nH + nHe )

=

V

8.31 300

=

(0.1 + 0.2) = 3.75 105 N/m2

2 10 3

KINETIC THEORY OF GASES

56

Examples

based on

PV

represents

KT

(A) Mass of the gas

(B) Kinetic energy of the gas

(C) Number of moles of the gas

(D) Number of molecules in the gas

Sol.[D] By ideal gas equation

PV = nRT

But R = NAK

PV = nNAKT

and N = nNA represent number of molecules

Ex.20

Sol.

total number of collisions

The quantity

so

Ex.21

PV

=N

KT

When the volume is 100 mL and the

temperature is 35C. What must be its

temperature if the pressure become 720 mm of

Hg and its volume 200 mL.

Here PV = RT

PV

= R (constant)

T

or

P1V1

PV

= 2 2

T1

T2

so

V1 = 100 mL,T1 = 35C = 273 + 35 = 308 K

P2 = 720 mm of Hg,V2 = 200 mL

Substitute the above values in the equation,

we get

760 100 720 200

=

308

T2

720 200 308

760 100

= 584 K

= 584 273

= 311C

T2 =

in N different collision during time t. Mean

free path will be -

=

vt

N

1

2 2 n

number of molecules in a unit volume of the

gas.

(vii) If m is the mass of a molecule, then

=

2 2 mn

2 2

and the pressure as

=

kT

2 2 P

P = pressure.

(i) The path traversed in a straight line by a

molecule of a gas before it collides with another

molecules is called free path.

(ii) The average distance travelled in between two

successive collisions by a molecule is called

1 + 2 + 3 + ... + N

N

(ix) Therefore

1

i.e. the mean free path is

(x) For constant volume and hence constant

P

is

number density n of gas molecules,

T

constant so that will not depend on P and T.

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57

to change with P or T then

1

i.e. T at constant pressure and at

P

constant temperature.

On increasing the temperature at constant

pressure the mean free path increases and on

increasing the pressure at constant temperature

the mean free path decreases.

Examples

based on

Ex.22

The relation between mean free path of

molecules of a gas and its density is 1

(A)

(B)

(C)

Sol.[B]

m

2

(D)

i.e.

(ii) In order to explain the behaviour of real gases

following two modification are considered in

ideal gas equation :

(A) Non- zero size of molecules : A certain portion

of volume of a gas is covered by the molecules

themselves. Therefore the space available for

the freely motion of molecules of a gas will be

slightly less than the volume V of a gas. This

decreases in volume of a gas will be (V b). b

is about four times the actual volume occupied

by the molecules.

(B) Intermolecular force : Attractive force acts

between molecules of real gases. Due to this

molecules do not exert that force on the wall

which they would have exerted in absence of

intermolecular force. Therefore the observed

pressure P of the gas will be less than the

pressure in absence of intermolecular force.

This decrease in pressure is assumed to be

a

equal 2 , where 'a' is a constant.

V

Therefore pressure of a real gas will be

a

RT

, where P is observed

P =

( V b)

V2

pressure.

mentioned modifications in ideal gas equation

is called Vander wall's equation or real gas

equation. It is as follows :

P+

a

V2

(V b) = RT

temperatures behave like ideal gases.

(v) a and b are constants and value are different for

different gases.

(vi) a is a constant for a gas.

Unit of a = (pressure volume2)

= (N m4)

Dimensions of a = M1 L5 T2

(vii) b is a constant for a gas. The value of b is four

times the volume occupied by the molecules.

Unit of b is unit of volume = m3

Dimensions of b = M0 L3 T0

(viii) Pressure exerted by real gases is less then the

pressure exerted by ideal gases.

(ix) Specific heat of real gas increases with

increases of temperature.

14. CRITICAL POINT OR CRITICAL CONSTANT

(i) Critical temperature (TC) : Temperature below

which a gas can be liquefied only by increase in

pressure and above which no liquification is

(ii) Critical pressure (PC): The minimum pressure

required to liquefy a gas when it is at critical

temperature (TC)

(iii) Critical (specific) volume (VC) : The volume of

unit mass of a gas at critical pressure and

temperature.

(iv) Triple point : The temperature at which all the

three states of matter coexist in equilibrium

Corporate Office: CP Tower, Road No.1, IPIA, Kota (Raj.), Ph: 0744-2434159

8a

TC =

27Rb

8a 2

b and VC = 3b

PC =

27

(Where a and b are constant)

58

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