1.chapter-1 - Kinetic Theory of Gases

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Institute for NET/JRF, GATE, IIT‐JAM, JEST, TIFR and GRE in PHYSICAL SCIENCES
1. Kinetic Theory of Gases

1.1 Basic Assumption of Kinetic Theory:
1. Any infinitely small volume of a gas contains a large number of molecule.
2. A gas is made up identical molecule which behaves as rigid, perfectly elastic, hard
sphere.
3. The molecules continuously move about in random directions. All directions of motion
are equally probable.
4. The size of the molecules is much less than the average distance between them.
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5. The molecule of a gas exert no force on each other except when they collide.
6. The collision between molecules and with walls are perfectly elastic.
7. The direction of molecular velocities are assumed to be distribute uniformly.
8. The molecules move with all speeds ranging from 0 to ∞.
9. The time of collision is much less than the time between collisions.
1.1.1 Pressure Exerted by a Gas
Suppose there are n molecules per cubic meter each of mass m, and its is assumed that ni
no. of molecule have velocity vi .
zi
Mathematically
∑ ni = n and vi2 = vix2 + viy2 + viz2
where vix viy and viz are x, y, z component of velocity of gases.
vi2
From assume of kinetic theory of gases v ix2 = viy2 = viz2 =
3
suppose molecules are kept in the cubic container of parameter L .
fi
A molecule moving in the x direction will have momentum mvix normal to face of the
cube before collision
ΔPix = mv ix − (− mv ix ) = 2mv ix
ni 2mvix ni 2mvix2 ni mvix2

Force acting on the wall by molecule is f ix = = ==
Δt 2L L
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mni vix2
Pressure exert on the wall of container by molecule Pix =
L3
so that pressure in the x direction expected by all group
m
Px = ∑ Pix = ∑ ni vix2
L3
Average value of v2 is given by
∑n v 2
i ix ∑n v 2
i ix
v x2 = i
= i =1
∑n n
ks
i
For three dimensional system vx2 + v y2 + vz2 = v 2 and
v2
for isotropic system v 2
x = v 2
y = v 2
z =
3
So Px can be written as
2
m 1m 1 mn v
Px = 3 n v x2 , P = Px = n v2 P=
L 3 L3 3 V
1
PV = mN v 2
zi
3
where V is volume of the container and v 2 is average value of square of velocity.
1.2 Gas Law for Ideal Gases:

1.2.1 Boyle’s Law
At constant temperature (T ) , the pressure ( P ) of a given mass a gas is inversely
proportional to its volume (V)

fi
1
P∝
V
1.2.2 Charle’s Law
At constant pressure ( P ) the volume of a given mass of a gas is proportional to its
temperature (T)
V ∝T

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1.2.3 Avogadro’s Law

At the same temperature and pressure, equal volume of all gases contain equal number of
molecules (N).
N1 = N2
1.2.4 Graham’s Law of Diffusion
When two gases at the same pressure and temperature are allowed to diffuse into each
other, the rate of diffusion (r) at each gas is inversely proportional to square root at
density of gas (ρ)
ks
r1 ρ2
=
r2 ρ1
Dalton’s Law of Partial Pressure: The sum of pressure exerted (P) by each gas occupying
the same volume as that of the mixture (P1, P2, P3,….)
P = P1 + P2 + P3 +….
1.2.5 Ideal Gas Equation:
Consider a sample of an Ideal gas at pressure P, volume V and temperature T the gas
follows the equation
zi
PV = nRT
Where n is number of molecules and R is proportionality constant known as gas constant
R = 8.314 J/mol/K
R 8.314
Boltzmann constant K is ratio between R to Avogadro number NA k B = =
N A 6.03 × 1023
k B = 1.3 × 10 −23 J / K
fi
Example: Find the maximum attainable temperature of ideal gas in each process given
by p = p 0 − αV 2 ; where p 0 , α and β are positive constants, and V is the volume of one
mole of gas.
Solution: P = P0 − αV 2 (i)
Number of mole of gas = 1

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RT
We know PV = nRT ⇒P= put in (i)
V
RT P0V αV 3
= P0 − αV 2 ⇒T = − (ii)
V R R
dT P 3αV 2
For T maximum, =0 ⇒ 0 − =0
dV R R
P0 2 P0
V = put in (ii) one will get Tmax = P0
3α 3 3α
ks
Example: Two thermally insulated vessel 1 and 2 are filled with air. They are connected
by a short tube with a value. The volume of vessels and the pressure and temperate of air
in them are (V1 , P1 , T1 ) and ( V2 , P2 , T2 ) respectively. Calculate the air temperate and
pressure established after opening of value if air follow Ideal gas equation.
P1V1
Solution: For vessel (1) P1V1 = n1 RT1 n1 =
RT1
P2V2
For vessel (2) P2V2 = n2 RT2 n2 =
RT2
zi
After opening the value let pressure volume and temperature is P, V, T
PV = nRT
V = V1 + V2
P1V1 P2V2
n = n1 + n2 = +
RT1 RT2
Hence system is isolated then
fi
Energy of (1) + energy of (2) = energy of composite
3 3 3
n1 KT1 + n2 KT2 = (n1 + n2 )KT
2 2 2
n1T1 + n2T2 = (n1 + n2 ) / T .
n1T1 + n2T2
T=
n1 + n2

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P1V1 (P V )
T1 + 2 2 T2
RT1 RT2 ( PV
1 1 + P2V2 )
= ⇒ T = T1T2
1 1T2 + P2V2T1
P1V1 P2V2 PV
+
RT1 RT2
nRT P1V1 + P2V2

PV = nRT P= P=
V V1 + V2
Example: A horizontal cylinder closed from one end is rotated with a constant angular
velocity ω about a vertical axis passing through the open end of the cylinder. The outside
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air pressure is equal to p 0 , the temperature to T , and the molar mass of air to M . Find the
air pressure as a function of the distance r from the rotation axis. The molar mass is
assumed to be independent of r .
Solution: Force equation of dr element.
dF = (dm )rω 2 if S is cross section area then
dF ⎛ dm ⎞ 2 ⎛ S ⎞
dP = =⎜ ⎟ rω dm = ⎜ 2 ⎟dP
S ⎝ S ⎠ ⎝ rω ⎠
Also we know
zi
⎛ dm ⎞ ω
P(Sdr ) = ⎜ ⎟ RT
⎝M ⎠
M, T
RT ⎛ S ⎞
PS (dr ) = ⎜ ⎟dP P0 S
M ⎝ rω 2 ⎠ r
r P dP This end is
Mω 2 ∫ rdr = RT ∫ open in air
0 P0 P
Mω 2 r 2
fi
P
= RT ln
2 P0
Mω 2 r 2
P = P0 e 2 RT

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1 2
Example: Prove that PA = mN v 2 and E = k BT = kBT in two dimension.
2 2
Solution: A molecule moving in the x direction will have momentum mvix normal to face
of the cube before collision

ΔPix = mvix − (− mvix ) = 2mvix
ni 2mvix ni 2mvix2 ni mvix2

Force acting on the wall by molecule is f ix = = ==
Δt 2L L
ks
mni vix2
Pressure exert on the wall of container by molecule Pix =
L3
So that pressure in the x direction expected by all group
m
Px = ∑ Pix = 3
∑ ni vix2
L
Average value of v 2 is given by
∑n v 2
i ix ∑nv 2
i ix
v x2 = i
= i =1
∑n i n
zi
v2
For two dimensional system v 2
+ v 2
= v 2
and v 2
x = v 2
y =
2
x y
So Px can be written as
2
m 1 m 1 mn v
Px = 2 n v x2 , P = Px = n v2 P=
L 2 L2 2 A
1
PA = mN v 2
2
fi

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1.3 Kinetic Interpretation of Temperature

According to assumption of Kinetic theory of gases, there is only translation motion of
the molecule and there is not any potential acting between them, so
Average energy E of gases are equivalent to Average translation energy of a molecule
1
E = m v2
2
1 2 ⎛1 ⎞ 2
Pressure at P as P = mn v 2 = n⎜ m v 2 ⎟ = n E
3 3 ⎝2 ⎠ 3
ks
2 2 N
PV = Vn E PV = N E where n = number density
3 3 V
3 RT 3⎛ R ⎞
E = and E = ⎜ ⎟T
2 NA 2⎝ NA ⎠
3
E = K BT where k B is Boltzman constant
2
So average kinetic energy is given by
3
E = k BT where T is absolute temperature.
zi
2
Example: It is possible to treat electromagnetic radiation in container whose wall is
mirrors, as a gas of particle (photons) with a constant speed c and whose energy is related
to their momentum p which is directed parallel to their velocity by E = pc .Show that if
1
container is full of radiation the equation of state is PV = E
3
1 1 1 G G
Solution: Pressure P = nm v 2 = n mv ⋅ v = n p ⋅ v
fi
3 3 3
For Photon v = c and velocity is parallel to momentum, so
1 1N
P = n Pc ⇒ P= pc
3 3V
1 1
PV = Npc ⇒ PV = E
3 3

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1.4 Maxwell-Boltzmann Distribution Law: z

Distribution of Molecular velocity in perfect gas. dv
Maxwell-Boltzmann distribution law is applicable for Ideal v

gas where molecules have no vibrational or rotational y
energies.
In the equilibrium state of the molecules have complete x
random motion and probability that a molecule has a given velocity component is
independent of other two components.
ks
In given figure dv is volume element in velocity space for a molecule at velocity
G
v ≡ (v x , v y , v z ) .
v 2 = v x2 + v y2 + v z2
We need to calculate number of molecules simultaneously having component in the range
v x to v x + dv x , v y to v y + dv y and v z to v z + dv z
It is assumptions in Maxwell-Boltzmann distribution law is that probability that molecule

selected at random has velocities in a given range is a function purely at the magnitude of
zi
velocity and the width of the interval.
So fraction of molecule having velocity component in the range v x to v x + dv x , v y to
v y + dv y and v z to v z + dv z is f (v x )dv x , f (v y )dv y and f (vz )dvz respectively.
= f (v x ) f (v y ) f (v z )dv x dv y dv z
dN
N
where dN is number of molecule having between velocity v to v + dv and N is total
fi
number of molecules.
dN = N f (v x ) f (v y ) f (v z )dv x dv y dv z
Number of molecule having velocity vx to vx + dvx, vy to vy + dvy and vz to vz + dvz is same
as number of molecule having velocity v to v + dv.
So N f (v x ) f (v y ) f (v z )dv x dv y dv z = N F (v 2 ) dv x dv y dv z

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G
F is some function of v 2 (magnitude of velocity) and for fixed value of v , F ( v 2 ) is
constant.
So dF (v 2 ) = 0 is equivalent to d [ f (v x ) f (v y ) f (v z )] = 0
f ′ ( vx ) dvx f ( v y ) f ( vz ) + f ′ ( v y ) dv y f ( vx ) f ( vz ) + f ′ ( vz ) dvz f ( vx ) f ( v y ) = 0
Dividing both side with f(vx) f(vy) f(vz)

f ′ (v x ) f ′ (v y ) f ′ (v z )
dv x + dv y + dv z = 0 (i)
f (v x ) f (v y ) f (v z )
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v 2 = constant v x2 + v y2 + v z2 = v 2
vxdvx + vydvy + vzdvz = 0 (ii)
by method of Lagrange’s method of undetermined multiplies multiply by 2β in equation
(ii) and add in equation (i)
⎛ f ′ (v x ) ⎞ ⎛ f ′ (v y ) ⎞ ⎛ f ′ (v z ) ⎞
⎜⎜ + 2 β v x ⎟⎟dv x + ⎜⎜ + 2 β v y ⎟⎟dv y + ⎜⎜ + 2 β v z ⎟⎟dv z = 0
⎝ f (v x ) ⎠ ⎝ f (v y ) ⎠ ⎝ f (v z ) ⎠
hence v x , v y and v z are independent
zi
f ′ ( vx ) f ′ ( vy ) f ′ ( vz )
+ 2 β vx = 0 ⇒ + 2β vy = 0 ⇒ + 2 β vz = 0
f ( vx ) f ( vy ) f ( vz )
f (v x ) = Ax e − βvx f (v y ) = Ay e − βv y f (v z ) = Az e − βvz
2 2 2
f (v x ), f (v y ), f (v z ) are probability density, so

∞ ∞ ∞
∫ f (v x )dv x = 1, ∫ f (v y )dv y = 1, ∫ f (v )dv

z z = 1,
−∞ −∞ −∞
fi
Use the integration
∞
1 n +1
∫ e v dv =
2
−βv n
n +1
( ) 2
0
2β 2
∞ ∞
∫ e − β vx dvx = 1 = Ax 2 ⋅ ∫ e− β vx dvx = 1
2 2
Ax
−∞ 0

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1/ 2 1/ 2 1/ 2
⎛β ⎞ ⎛β ⎞ ⎛β ⎞
Ax = ⎜ ⎟ Similarly, Ay = ⎜ ⎟ Az = ⎜ ⎟
⎝π ⎠ ⎝π ⎠ ⎝π ⎠
1/ 2 1/ 2 1/ 2
⎛β ⎞ ⎛β ⎞ ⎛β ⎞
f (v x ) = ⎜ ⎟ − β v x2
, f (v y ) = ⎜ ⎟ − β v 2y
, f (v z ) = ⎜ ⎟ e − βvz
2
e e
⎝π ⎠ ⎝π ⎠ ⎝π ⎠
3/ 2
dN ⎛ β ⎞
e − β (v x + v y + v z )dv x dv y dv z
2 2 2
=⎜ ⎟
N ⎝π ⎠
where − ∞ < v x < ∞ , − ∞ < vy < ∞ , − ∞ < vz < ∞
ks
1.4.1 The Distribution in Term of Magnitude
v 2 = v x2 + v y2 + v z2 which is equation of sphere and dv x dv y dv z can be replace by 4πv 2 dv
3/ 2
dN ⎛ β ⎞
f (v )dv =
2
=⎜ ⎟ 4πe − βv v 2 dv 0<v<∞
N ⎝π ⎠
1.4.2 To Determine Value of β in Term of Temperature T.
Mean square velocity v 2 ( ) can be calculated by
∞
∫ v f (v )dv
2 2
zi
0
3/ 2 ∞ 3/ 2
⎛β ⎞ ⎛β ⎞ 1
4π ⎜ ⎟ ∫v 4π ⎜ ⎟
− βv 2
4
e dv ⇒ 5/ 2
⎝π ⎠ 0 ⎝π ⎠ 2β 5/ 2
3/ 2
⎛β ⎞ 1 3 1 3 1
4π ⎜ ⎟ ⋅ π ⇒ v2 = ⋅
⎝π ⎠ 2β 5/ 2
2 2 2 β
Now average energy of temperature T equivalent to
3 1
fi
k BT = m v 2
2 2 T1
3 1 31 m T2
kBT = m =β =
2 2 2β 2 k BT f (v )
3/ 2 (
m vx2 + v 2y + vz2 )
⎛ m ⎞ −
So f ( vx , v y , vz ) = ⎜ ⎟ e 2 k BT
dvx dv y dvz
⎝ 2π k BT ⎠ v
T1 < T1

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3/ 2 mv 2
⎛ m ⎞ −
f ( v ) dv = 4π ⎜ ⎟
2
ve 2 k BT
dv
⎝ 2π k BT ⎠
1.4.2 Average Velocity
∞ 3/ 2 mv 2
⎛ m ⎞ − 8k B T
v = ∫ vf (v ) dv = 4π ⎜ ⎟ ∫e
2 k BT
v3 dv =
0 ⎝ 2π k BT ⎠ πm
1.4.3 Root Mean Square Velocity
1/ 2
[v ]
2 1/ 2 ⎡∞ ⎤
= ⎢ ∫ v 2 f (v )dv ⎥
ks
⎣0 ⎦
1/ 2 1/ 2
⎡ ⎛ m ⎞3/ 2 ⎤ ⎡ ∞ − mv ⎤
2
3k BT
= ⎢ 4π ⎜ ⎟ ⎥ ⎢ ∫ e 2 kBT v 2 dv ⎥ =
⎢⎣ ⎝ 2π k BT ⎠ ⎥⎦ ⎢⎣ 0 ⎥⎦ m
df 2k B T
1.4.4 Most Probable Velocity v p : = 0 ⇒ vp =
dv m
zi
fi

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1
Example: For Maxwellian gas find the v ×
v
3/ 2 ∞ 1/ 2
8k BT 1 ⎛ m ⎞ 1 ⎛ 2m ⎞
Solution: v =
πm
⇒
v
= 4π ⎜ ⎟
⎝ 2π k BT ⎠
∫0 v f ( v ) dv = ⎜⎝ π kBT ⎟⎠
1 4
⇒ v × =
v π
Example: If vx and vy are x and y component of velocity then find the average value of
(av x + bv y )2
ks
(av x + bv y )2 = a 2 v x2 + b 2 v y2 + 2 ab v x ⋅ v y
= a 2 v x2 + b 2 v y2 + 2ab v x v y
3/ 2 ∞ ∞ ∞ (
m vx2 + v 2y + vz2 )
⎛ m ⎞ −
vx = ⎜ ∫ ∫ ∫ve
2 k BT
⎟ dvx dv y dvz = 0
⎝ 2π k BT ⎠
x
−∞ −∞ −∞
3/ 2 ∞ ∞ ∞ (
m vx2 + v 2y + vz2 )
⎛ m ⎞ − k BT
=⎜ ∫ ∫ ∫ve dvx dv y dvz =
2 2 2 kBT
v ⎟
⎝ 2π k BT ⎠
x x
−∞ −∞ −∞
m
k BT
zi
Similarly, v y = 0 v y2 =
m
(av x + bv y )2 = a 2 v x2 + b 2 v y2 + 2ab v x v y
+ b2 B + 0 = B ( a 2 + b2 )
k BT kT kT
= a2
m m m
Example: Write down expression of energy distribution function for Maxwellian gas
between E and E + dE . Hence find E down E 2 .
fi
1 2 dE
Solution: E = mv , dv =
2 (2mE )1/ 2
3/ 2 mv 2
⎛ m ⎞ −
f ( v ) dv = 4π ⎜ ⎟ e 2 k BT
v 2 dv put value of v and dv
⎝ 2π k BT ⎠
E
2 1 −
f ( E ) dE = e k BT
E1/ 2 dE 0< E <∞
π ( k BT )
3/ 2

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∞
3
E = ∫ Ef (E ) dE E = k BT
0
2
∞
E 2
= ∫ E 2 f ( E ) dE ,
0
∞ E
2 1 −
2 2 5 3 15
E2 = ∫ E2 . ( k BT ) . . π = . ( k BT )
2
e k BT
E1/ 2 dE =
π ( k BT )
3/ 2
0 π 2 2 2
Example: Write down expression of energy distribution function for Maxwellian gas
between E and E + dE in two dimensional system . Hence find E .
ks
1 2 dE
E= mv , dv =
2 (2mE )1/ 2
2/2 mv 2
⎛ m ⎞ −
f ( v ) dv = 2π ⎜ ⎟ e 2 k BT
vdv put value of v and dv
⎝ 2π k BT ⎠
E
1 −
f (E )dE = e K BT dE 0<E<∞
(k BT )
∞
E = ∫ Ef (E ) dE ⇒ E = k BT
0
zi
Example: Using the Maxwell distribution function, calculate the mean velocity
projection v x the mean value of the modulus of the modulus of this projection vx if
the mass of each molecule is equal to m and the gas temperature is T .

Solution: We know Mean Velocity
1/ 2
⎛ m ⎞
m 2
∞ − vx
∫
2 k BT
vx N ⎜ ⎟ e dvx
∞ v dN −∞
⎝ 2π k BT ⎠
fi
= vx = ∫ x
= =0
−∞ N N
1/ 2
⎛ m ⎞ − 2 kBT vx2
m
∞
∫−∞ x ⎜⎜⎝ 2πk BT ⎟⎟⎠ e
v N dvx
Mean speed vx =
N
1/ 2
⎛ m ⎞ − 2 kBT vx2
m
∞
2∫ v x N ⎜⎜ ⎟⎟ e dvx
vx =
0
⎝ 2πk BT ⎠ ⇒ vx =
2 k BT
N πm


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fiziks

1. Kinetic Theory of Gases

ni 2mvix ni 2mvix2 ni mvix2

Head office Branch office

For three dimensional system vx2 + v y2 + vz2 = v 2 and

1.2 Gas Law for Ideal Gases:

proportional to its volume (V)

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1.2.3 Avogadro’s Law

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nRT P1V1 + P2V2

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of the cube before collision

ni 2mvix ni 2mvix2 ni mvix2

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1.3 Kinetic Interpretation of Temperature

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1.4 Maxwell-Boltzmann Distribution Law: z

Maxwell-Boltzmann distribution law is applicable for Ideal v

It is assumptions in Maxwell-Boltzmann distribution law is that probability that molecule

v y + dv y and v z to v z + dv z is f (v x )dv x , f (v y )dv y and f (vz )dvz respectively.

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Dividing both side with f(vx) f(vy) f(vz)

f (v x ), f (v y ), f (v z ) are probability density, so

∫ f (v x )dv x = 1, ∫ f (v y )dv y = 1, ∫ f (v )dv

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the mass of each molecule is equal to m and the gas temperature is T .

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