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You are on page 1of 44

AND PALLAVI JOSHI

INTRODUCTION

The actual atomic theory got established more

than 150 years later.

Kinetic theory explains the behaviour of gases

based on the idea that the gas consists of rapidly

moving atoms or molecules.

The kinetic theory was developed in the

nineteenth century by Maxwell,Boltzmann and

others.

It gives a molecular interpretation of pressure and

temperature of a gas laws and Avagadro’s

hypothesis.

It also relates measurable properties of gases

such as viscosity,conduction and diffusion .

It correctly explains specific heat capacities of

many gases.

BEHAVIOUR OF GASES

From above fig.we come to know that

properties of gases are easier to understand

. than those of solids and liquids. This is

mainly because in a gas ,molecules are far

from each other and their mutual interactions

are negligible except when two molecules

collides

EXPANSION OF GASES &GAS LAWS

In the case of gases,thermal expasion is

very large as compared to that of solids

and liquids.It is found that the volume of

a solid or liquid practically remains the

same,even when a large pressure is

applied.however,the volume of a gas

changes appreciably,when it’s pressure is

changed even by a small amount.

Therefore to describe the condition of a

gas its volume,pressure and temperature

must be specified. A change of one affects

the others

The gas laws are the study of the relation

between any two of these quantities,when

the third kept constant.The three Gas laws

are the studies of

(1)effect of pressure on the volume of a

given mass of a gas at constant

temperature.

(2)effect of temperature on the volume of a

given mass of a gas at constant pressure

and

(3)effect of temperature on the pressure of

a given mass of gas at constant volume.

BOYLE’S LAW

This law was discovered by Robert Boyle in

1662 and it is most fundamental laws

It states-”the temperature remaining

constant,the volume of a given mass of a

gas is inversely proportional to the

pressure.It is called Boyle’s law

mathematically, if temperature of the gas

is constant,then

PV =CONSTANT OR

V=1

P

In general if P1 and V1 are the initial

pressure and volume of a gas and P2

and V2,their final values,then

P1V1=P2V2

V at constant temperatures T1 and T2,

SUCH THAT T2>T1

CHARLES LAW

Around 1787,A.C.Charles studied the

variation in volume of a gas with

temperature and formulated the following

law:

“The pressure remaining constant, the

volume of a given mass of a gas increases

or decreases by a constant fraction of it’s

volume at 0 C for each rise or fall of 1 C in

temperature.”

V T=CONSTANT

The above equation tells that the graph betweenV

and T for a given mass of gas at constant pressure

must be straight line as shown dotted in fig.

GAY LUSSAC’S LAW

pressure of a gas with temperature and

arrived at the following result:

“The volume remaining constant ,the

pressure of a given mass of a gas increases

or decreases by a constant fraction of its

pressure at 0 C for each rise or fall of 1 C in

temperature”.

p/t = constant

PERFECT GAS

EQUATION

In practice, the gases do not obey the gas laws at all values of

pressure and temperature. It is because of the intermolecular

forces between the gas molecules.

Perfect gas equation

Let P1,V1,T1,be its initial pressure,volume and

temperature respectively and P2,V2,andT2 be their

final values. The change of the state of gas from the

state (P1,V1,T1,)to(P2,V2,T2)may be supposed to be

taking place in the following two steps:

STEP 1

Suppose that the temperature of the

gas remains constant at T1 and the

pressure is changed from P1 to P2 so

that volume of the gas changes from

V1 to, say V’.Since the temperature of

the gas remains constant , from

Boyle’s law, we have

P1V1=P2V2 ………….. (1.09)

STEP 2

Now,the pressure,volume and the

temperature of the gas are P2,V’,and T1

respectively.Suppose that the pressure

of the gas is kept constant at P2 and

temperature of the gas is changed from

T1 to T2,so that volume changes from

V’ to V2.Since the pressure of the gas

remains constant, from charles’ law , we

have

V’/T1=V2/T2

OR V’=V2*T1/T2

Substituting for V’in the equation(1.09),

we have

P1V1=P2*(V2*T1/T2) OR

P1V1/T1=P2V2/T2 OR

PV/T=constant …….(1.10)

in above equation,for 1 mole of gas, the

constant is denoted by R and is called

universal gas constant.

PV=RT ………..(1.11)

this equation called perfect gas equation.

KINETIC THEORY OF GASES

A gasis a collection of a large number of a

molecules,which are in continuous rapid

motion. The gas molecules have a size of

two into ten rest to minus ten meters.But it’s distance

between gas molecules is much bigger than it’s

size.Therefore the gas molecules can be considered

as to be moving freely with respect to each other.Due

to change in velocities the gas molecules collides.

Rudolph Claussius and JamesClark Maxwell developed

the Kinetic theory of gases in order to explains gas laws

in terms of the motion of the gas molecules.

The theory is based on following assumptions as regards

to the motion of molecules and the nature of gases:

All gases consist of molecules.The molecules of a gas

are all alike and differ from those of other gases.

The molecules of a gas are very small in size as

compared to the distance between them.

The molecules of a gas behaves as perfect spheres

The molecules are always in random motion.

The molecules do not exert any force on each other

except during collisions.

PRESSURE OF A IDEAL GAS

containing vessels due to continuous

collisions of the molecules against the

wall.

consider a gas enclosed in a cube

.suppose that the edges OA,OC,OE of

the vessels are along X,Y,andZ axis

respectively shown in fig

FIG.13.4 Elastic collision of a gas molecule with the wall of

the container.

A molecule with velocity (VX.VY,VZ) hits the planer

wall parallel to yz-plane of area A.Since the collision

is elastic,the molecule rebound with the same

velocity;its y and z components of velocity does not

change in the collision but the x-component

reverses sign. That is, after collision is (-VX,

VY,VZ).The change in momentum of the molecule is:

-mvx-(mvx)=-2mvx.By the principle of conservation of

momentum, the momentum imparted to the wall in

the collision=2mvx.

To calculate the force on the wall,

we need to calculate momentum imparted to the

wall per unit time.In small interval t

A molecule with x-component of velocity Vx will

the wall if it is within the distance Vx t from the

wall.That is ,all molecules within the volume

AVx t only can hit the wall in time.But ,on the

average,half of these are moving towards the

wall and the other half away from the wall.Thus

the number of molecules with

velocity(Vx,Vy,Vz)hitting the wall in time t is

1/2AVx tn where n is the no. of

molecules per unit volume.The totol

momentum transferred to the wall by these

molecules in t is:

Q=(2mVx)(1/2nAVx t)……….(13.10)

The force on the wall is the rate of

momentum transfer Q/ t and pressure is

force per unit area:

P=Q/(A t)=nmVx2……………………(13.11)

P=nmV2x……………….(13.12)

where V2x is the average of V2x.

Now gas is isotropic.

V2x=V2y=v2z=(1/3)v2x+V2y+v2x=(1/3)v2

Where V is the speed and V2x denotes the

mean of squared speed.Thus

P=1/3nmv2

KINETIC INTERPRITATION OF

TEMPERATURE

Equation (13.14) can be written as

PV=(1/3)nVmV2………..(13.15A)

PV=(2/3)NX1/2mV2………(13.15B)

Where N(=nV)is the number of

molecules in the sample.

The quantity in the bracket is the average

translational kinetic energy of the molecules in

the gas . Since the internal energy E of an ideal

gas is purely kinetic,

E=N*(1/2)mv2…………………..(13.16)

Equation (13.15) then gives:

PV=(2/3)E…………(13.17)

we now ready for the kinetic interpritation of

temperature. Combining Eq(13.17) with the ideal

gas Eq(13.3), we get

E=(3/2)KbNT …..(13.18)

i.e., the average kinetic energy of a molecule

is proportional to the the absolute temperature of

the gas.The two domains are connected by the

Boltzmann constant.

we note that eq(13.18) tell us that internal energy

of an ideal gas depend upon only on temperature,

not on volume or pressure.

For a mixture of non reactive ideal gases,the total

pressure gets contribution from each gas in the

mixture.Eq(13.14) becomes

P=(1/3)[n1m1V21+n2m2v22+…]

(13.20)

1/2m1v21=1/2m1v22=(3/2KbT)

SO THAT P=(n1+n2+…)KbT………(13.21)

Which is Dalton’s Law of Partial pressures.

LAW OF EQUIPARTITON OF

ENERGY

The kinetic energy of a single molecule is

ET=1/2mv2x+1/2mv2y+1/2mv2z

(13.22)

For a gas in thermal equilibrium at

temperature T the average value of

energy denoted by<ET>IS

<ET>=<1/2mV2X>+<1/2mV2Y>+<1/2mv2

z>=3/2KbT (13.23)

<1/2mV2Z>=1/2KbT

Molecules of monoatomic gas like argon

have only translational degrees of

freedom.But what about a diatomic gas

such as o2 or N2?A molecule of o2 has

three translational degrees of freedom.

But in addition it can also rotate about it’s

centre of mass.Fig 13.6 shows two

independent axes of rotation 1 and

2,normal to the axis joining the two

oxygen atoms about which the molecule

can rotate.

Eachquadratic term occuring in the

expression for the energy is a mode of

absorption of energy by the molecule .We

have seen that in thermal equilibrium at

absolute temperature T,for each

translation mode of motion,the average

energy is 1/2kbT. A most elegant principle

of classical statistical mechanics states

that this is so for each mode of

energy:translational,rotational and

vibrational.that is equally distributed with

all energy modes this is known as law of

equipartition of energy.

SPECIFIC HEAT CAPACITY

MONOATOMIC GASES

The molecule of monoatomic

gas has only three translational

degrees of freedom. Thus ,the

average energy of a molecule at

temperature T is (3/2)KbT.The total

internal energy of a mole of such a

gas is

U=3/2KbT*Na=3/2RT

The Molar specific heat at constant

volume,Cv is

Cv(monoatomic gas=

dU/dT=3/2RT

for an ideal gas

Cp-Cv=R

where Cp is the molar specific heat

at constant pressure,thus,

Cp=5/2R

DIATOMIC GASES

As explained earlier ,a diatomic molecule

treated as a rigid rotator like a dumbbell

has 5 degrees of freedom: 3 translational

and 2 rotational.

using the law of equipartition of

energy, the total internal energy of a mole

of such a gas is

U=5/2KbT*Na=5/2RT

THE molar specific heat is given by

Cv=5/2R,Cp=7/2R

POLYATOMIC GASES

Ingeneral a polyatomic molecule has

3 translational,3 rotational degrees of

freedom and a certain number(f) of

vibritional modes. According to law of

equipartition of energy,it is easily

seen that one mole of such a gas has

U=(3/2kbT+3/2KbT+FKbT)NA

Predicted values of specific

heat capacities of gases

Nature Cv Cp Cp-Cv ?

of (j/mol/k (j/mol/k

gases (j/mol/k )

Monoat )12.5 20.8 8.31 1.67

omic

diatomi 20.8 29.1 8.31 1.40

c

triatomi 24.93 33.24 8.31 1.33

c

SPECIFIC HEAT CAPACITY OF

SOLIDS

We can determine the law of equilipartition of

energy to determine specific heat of solids.

Consider a solid of Natoms, each vibrating

about in its mean position. For a mole of

solid,N=Na,the total internal energy is

U=3KbT*Na=3RT

Now at constant pressure

c=deltaQ/deltaT=deltaU/deltaT=3R

SPECIFIC HEAT CAPACITY OF

SOLIDS

SUBSTAN SPECIFIC MOLAR

CE HEAT SPECIFIC

<J/KG/K> HEAT(J/K

G/K)

ALUMINIU 900.0 24.4

M

CARBON 506.5 6.1

MEAN FREE PATH

Molecules in a gas have rather large

speeds of the order of the speed of

sound.The top of a cloud of smoke

holds together for hours.this happens

because molecule in a gas have a

finite though small size so they are

bound to undergone collisions.as a

result move straight unhindered their

path keep getting incessantly

deflected.

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