Unit-V

Applications of
Statistical Mechanics-II
 Points for the discussion
Unit -5
 Thermodynamic potentials Application of
statistical Mechanics

 Brownian motion (Thermodynamics and

Statistical Mechanics)
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 Langevin’s Theory of Brownian Motion
 Einstein's Theory of Brownian Motion
 Distribution of Brownian particles in a vertical
column
 Derivation of Ideal Gas Equation
Thermodynamic potentials
The state of a system can be completely described by Unit -5
Application of
any two of the five state variables, P,V,T,S and U. statistical Mechanics
(Thermodynamics and
Out of these , U the internal energy state variable is Statistical Mechanics)
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determined by using the reaming four as given below,
According to 1st law of thermodynamics,
 dQ = dU+pdV and dQ = T dS so, dU = TdS – pdV
There are four thermodynamic potentials:
(i) Internal energy, U
(ii) Helmholtz energy , F = U-TS
(iii) Enthalpy H = U + PV
(iv) Gibbs function
Brownian Motion
Brownian motion was first observed by in 1827 by Unit -5
Application of
Brown a botanist. statistical Mechanics
(Thermodynamics and
Statistical Mechanics)
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The phenomenon of Brownian movement can be
easily observed in a laboratory if colloidal solution is
examined under an ultra microscope.

As the direction of illumination is perpendicular to

the axis of the microscope, the suspended particles in
the solution look like bright illuminated spots.
Brownian Motion
These illuminated particles continuously move to and Unit -5
Application of
fro in a random haphazard way. statistical Mechanics
(Thermodynamics and
Statistical Mechanics)
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The particles spin, rise, sink and rise again.

The movement of the particles is continues and

spontaneous.

This non-stop random and haphazard motion of the

particles is called Brownian motion.
Brownian Motion
The motion of the particles becomes more violent with Unit -5
Application of
increase in temperature and more conspicuous in a statistical Mechanics
(Thermodynamics and
liquid of lower viscosity. Statistical Mechanics)
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Particles of smaller size appear to be more agitated

than the bigger particles.

Further, no two particles execute the same type of

motion.

The phenomenon of Brownian movement gives a

clear picture of the gaseous state of matter.
Brownian Motion
Essential Features : Unit -5
Application of
(i) The motion of each particles is completely irregular statistical Mechanics
(Thermodynamics and
and random. No two particles are found to execute Statistical Mechanics)
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the same motion.

(ii)The motion is continuous and takes place for ever.

(iii) The smaller particles appear to be more agitated

than the larger ones.

(iv) The motion is independent of the nature of the

suspended particles.
Brownian Motion
Essential Features : Unit -5
Application of
statistical Mechanics
(Thermodynamics and
(v) The motion becomes more violent on increasing the Statistical Mechanics)
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temperature.

(vi) The motion is not modified due to the shaking of

colloidal solution.

(vii) The Brownian motion cannot be observed with

particles of large size.
Brownian Motion
Essential Features : Unit -5
Application of
statistical Mechanics
(Thermodynamics and
(viii) The motion is more conspicuous in a liquid of Statistical Mechanics)
(02PY0507)
lower viscosity.

(ix) The laws kinetic theory of gases are applicable to

Brownian motion too.
Langevin’s Theory of Brownian Motion
According to Langevin, the force experienced by Unit -5
Application of
suspended particle is of two kinds : statistical Mechanics
(Thermodynamics and
(i) Frictional force proportional to the velocity Statistical Mechanics)
(02PY0507)

____(1)

(ii) Force due to all external influences of the

surrounding fluid.
Consider the motion of a particle in a special
direction say x direction. The force on the particle is
given by the equation,
Langevin’s Theory of Brownian Motion
Here represents the component of frictional Unit -5
Application of
force in x direction. F is the combined force due to statistical Mechanics
(Thermodynamics and
other influences. Multiply equation (2) by x, Statistical Mechanics)
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____(3)

 Also,

___(4)
Langevin’s Theory of Brownian Motion
We have eq.(4) Unit -5
Application of
____ (4) statistical Mechanics
(Thermodynamics and
Statistical Mechanics)
(02PY0507)
So from equation (4) we can write,
________(5)

On Substituting this value in eq.(3) we can obtain,

_____(6)

Equation (6) represents motion of a single particle.

Langevin’s Theory of Brownian Motion
For all the particle mean value can be given by, Unit -5
Application of
statistical Mechanics
(Thermodynamics and
_______(7) Statistical Mechanics)
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As the force F varies completely in an irregular

manner, it can be assumed that,

Further from the law of equi partition of velocities,

____(8)
Langevin’s Theory of Brownian Motion
Also take, Unit -5
Application of
________(8) statistical Mechanics
(Thermodynamics and
Statistical Mechanics)
(02PY0507)
Substituting these values in eq.(7) we can obtain,

Or ___(9)

The general solution of eq.(9) is,

Langevin’s Theory of Brownian Motion
Also take, Unit -5
Application of
________(8) statistical Mechanics
(Thermodynamics and
Statistical Mechanics)
(02PY0507)
Substituting these values in eq.(7) we can obtain,

Or ___(9)

The general solution of eq.(9) is,

As value of m is small, the value of (f/m) is very small
and hence is negligibly small,
So we can write, _____(10)
Langevin’s Theory of Brownian Motion
For a time interval t = 0 to t = t, integrating equation Unit -5
Application of
(10) we get , statistical Mechanics
(Thermodynamics and
Statistical Mechanics)
(02PY0507)

At t = 0 , x0 = 0 and for small values, x2 can be written

as x2,
_____(11)

In actual practice the particle makes millions of

collisions and move along zig-zag paths. The value
is only loosely related to the actual path.
Langevin’s Theory of Brownian Motion
Now according to Stokes formula, Unit -5
Application of
statistical Mechanics
(Thermodynamics and
Statistical Mechanics)
(02PY0507)

Therefore ____(12)

So we can write ____(13)

Langevin’s Theory of Brownian Motion
 from eq.(13) we write that, Unit -5
Application of
statistical Mechanics
(Thermodynamics and
_____(14) Statistical Mechanics)
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_____(15)

____(16)

The theory indicates that is not dependent on the

mass of the particle.
Einstein’s Theory of Brownian Motion
According to Einstein’s theory of translational Unit -5
Application of
Brownian motion, the particles tend to diffuse into statistical Mechanics
(Thermodynamics and
the medium in course of time. Statistical Mechanics)
(02PY0507)
The diffusion coefficient must be related to the
Brownian movement.
The diffusion coefficient can be calculated in two
different ways:
(1) From the irregular motion of the suspended
particles.
(2) From the difference in osmotic pressure cased by
the difference in concentration of the suspended
particles.
Einstein’s Theory of Brownian Motion
Osmotic pressure : Unit -5
Application of
statistical Mechanics
(Thermodynamics and
Osmotic pressure is the minimum pressure which Statistical Mechanics)
(02PY0507)
needs to be applied to a solution to prevent the inward
flow of its pure solvent across a semipermeable
membrane.

It is also defined as the measure of the tendency of a

solution to take in pure solvent by osmosis.
Einstein’s Theory of Brownian Motion
Let D be the diffusion coefficient. Unit -5
Application of
statistical Mechanics
(Thermodynamics and
Consider an imaginary cylinder with its axis along Statistical Mechanics)
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the x –axis.
The end faces P and Q are separated by a distance  .
Let n1 and n2 be molecular concentration at the end
faces of the cylinder and A the area of cross section.
P n1 n2 Q

The number of particles crossing the surface P to
right in time T = ½ n1 A 
Einstein’s Theory of Brownian Motion
Similarly the number of particles crossing the surface Unit -5
Application of
Q in opposite direction in time T = ½ n2 A  statistical Mechanics
(Thermodynamics and
“It should be noted that half the particles contained in Statistical Mechanics)
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the imaginary cylinder move towards right whereas
the other half move towards left”
The excess number of particles crossing a middle
layer to the right = ½ (n1-n2) A 
From the definition of diffusion coefficient the
number,
½ (n1-n2) A  = - D dn/dx t A
Einstein’s Theory of Brownian Motion
Here dn/dx is the concentration gradient. Unit -5
Application of
statistical Mechanics
(Thermodynamics and
But (n1-n2) = -  dn/dx Statistical Mechanics)
(02PY0507)

Therefor -½ A 2 (dn/dx) = - D (dn/dx)t A

So 2 = 2 D t , Or D = 2 / 2 t ___(1)

Now D can be calculated from the concept of osmotic

pressure at end of P and Q, then from the gas laws,
p1 = n1 kT, and p2 = n2 kT
Einstein’s Theory of Brownian Motion
Thus the cylinder experience a resultant force Unit -5
Application of
(p1-p2) A = (n1-n2) k TA along the +ve x direction statistical Mechanics
(Thermodynamics and
Statistical Mechanics)
(02PY0507)
This force is experienced by the particles contained
in the cylinder.

The number of particles in the cylinder = n A 

Where n is the mean concentration.

Therefore, the force acting on a single particle is,
f’ = (n1-n2) kT A/ n A  ____(2)
Einstein’s Theory of Brownian Motion
We have equation (2) as, Unit -5
Application of
f’ = (n1-n2) kT A/ n A  ____(2) statistical Mechanics
(Thermodynamics and
Substituting the value of (n1-n2) = -  dn/dx in eq.(2) Statistical Mechanics)

We can obtain f’ = - ( dn/dx) (kT/n) = 6 p  a v

(02PY0507)

Or we can also write ,

n v = - (kT/ 6 p  a ) (dn/dx) __(3)
Here, n v is the number of particles moving to the
right per unit area per second,

Therefore nv = -D (dn/dx) _____(4)

Einstein’s Theory of Brownian Motion
Now equating equations (3) and (4) we can obtain, Unit -5
Application of
-D (dn/dx) = - (kT/ 6 p  a ) (dn/dx) statistical Mechanics
(Thermodynamics and
Therefore , Statistical Mechanics)

D = (kT/ 6 p  a ) = (RT/N )(1/ 6 p  a )___(5)

(02PY0507)

Now putting value of D from eq.(5) in eq.(1) we can

obtain,
2 / 2 t = D = (RT/N )(1/ 6 p  a )

Therefore 2 = (RT/N )(1/ 3 p  a ) t ____(6)

Einstein’s Theory of Brownian Motion
We have equation Unit -5
Application of
2 = (RT/N )(1/ 3 p  a ) t ____(6) statistical Mechanics
(Thermodynamics and
Statistical Mechanics)

Therefore,  α t 1/2 ______(7) (02PY0507)

 α 1/  ½ ____(8)

 α T1/2 ____(9)
 Distribution of Brownian particles in a vertical column
 The Brownian particles form a gas in equilibrium Unit -5
Application of
under the action of earth’s gravitation. statistical Mechanics
(Thermodynamics and
Statistical Mechanics)
 The concertation of the particles in a vertical (02PY0507)

column decreases with height due to gravity.

 Consider two layers of the particles at heights h and

h+dh.

 Let P and P+dP be the pressures respectively and r

the density of gas at height h.
 Distribution of Brownian particles in a vertical column
Consider a unit area of the layer. Unit -5
Application of
The force due to gravity acting on the particles statistical Mechanics

between two layers = (1 x dh)r g = r g dh

(Thermodynamics and
Statistical Mechanics)
(02PY0507)

The net force on the layer = (P+dP) –P + [r g dh]

In equilibrium state, the net force must be equal to

zero.
Therefore, (P+dP) –P + [r g dh] = 0
dp + r g dh = 0
dp = - r g dh_____(1)
 Distribution of Brownian particles in a vertical column
For a perfect gas, P = n k T and dp = k T dn, Unit -5
Application of
r = mn. Where n = number of molecules per unit statistical Mechanics
(Thermodynamics and
volume and m mass of each molecule. Statistical Mechanics)
Substituting these value in equation (1) we can (02PY0507)

obtain, k T dn = - m n g dh
dn/n = - (mg/k T) dh, also k = R/N,N=Avogadro no
dn/n = - (Nmg/ RT) dh________(2)

Integrating equation (2) on both sides we can obtain,

logn = -(Nmg/ RT) h + K _____(3)
here K is constant at h= ho , n =no
 Distribution of Brownian particles in a vertical column
Therefore from equation (3) we can write that, Unit -5
Application of
logn0 = -(Nmg/ RT) h0 + K statistical Mechanics
(Thermodynamics and
so K = logn0 + (Nmg/ RT) h0 Statistical Mechanics)
Now putting value of K in equation (3) we can obtain, (02PY0507)

logn = -(Nmg/ RT) h + logn0 + (Nmg/ RT) h0

Therefore log (n/n0) = -(Nmg/ RT)(h-h0)

Hence n = n0 e [-(Nmg/ RT)(h-h0)] _____(4)

 Equation (4) shows variation in concentration with

height.
 Derivation of Ideal Gas Equation
From the kinetic theory of gases, Unit -5
Application of
 Pressure (P) = 1/3 r C2 , P = 1/3 M/V C2 statistical Mechanics
(Thermodynamics and
Statistical Mechanics)
PV = 1/3 MC2 = 1/3 NmC2 (02PY0507)
PV = 2/3 N (½ mC2)____(1)
Now consider one gram of molecule of a gas at an
absolute temperature T.
The mean K.E energy of molecules = ½ MC2
= ½ mn C2
So mean K.E energy of a molecule is
= ½ mC2 = 3/2(kT)____(2)
 Derivation of Ideal Gas Equation
Now using equation(2) in eq.(1) we can obtain, Unit -5
Application of
PV = 2/3 N (½ mC2) = 2/3 N (3/2 kT) = NkT__(3) statistical Mechanics
(Thermodynamics and
 But Nk = R then, Statistical Mechanics)
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PV = RT____(4)
Equation (4) is required equation for ideal gas.
 Try your self
Unit -5
Example : 1 A motor car tyre has a pressure of 2 Application of
atmospheres at the room temperature 27oC. If the tyre statistical Mechanics
(Thermodynamics and
suddenly burst, find the resulting temperature. Statistical Mechanics)
(02PY0507)
(Ans. -26.9 oC)

Example : 2 A quantity of dry air at 27 oC is

compressed (i) slowly and (ii) suddenly to 1/3 of its
volume. Find the change in temperature in each case,
assuming g to be 1.4 for dry air.
 Try your self
Unit -5
Example : 1 A motor car tyre has a pressure of 2 Application of
atmospheres at the room temperature 27oC. If the tyre statistical Mechanics
(Thermodynamics and
suddenly burst, find the resulting temperature. Statistical Mechanics)
(02PY0507)
(Ans. -26.9 oC)
Solution : here P1 = 2 atmosphere,
T1 = 273 + 27 = 300 K
P2 = 1 atmosphere , T2 = ? g = 1.4

Now we know that P1g-1/T1g = P1g-1/T1g

 Try your self
Solution Continue : Unit -5
Application of
Now we know that P1g-1/T1g = P1g-1/T1g statistical Mechanics
Or (P2/P1)g-1 = (T2/T1)g (Thermodynamics and
Statistical Mechanics)
(1/2)0.4 = (T2/300)1.4 (02PY0507)

2.303 x 0.4 log10(0.5) = 1.4 [log10T2-log10300] x 2.303

-0.1204 = 1.4log10T2- 3.4680
1.4log10T2 = 3.4680 - 0.1204 = 3.3476
log10T2 = 3.3476/1.4 = 2.3911, So T2 = 246.1 K
T2 = -26.9 oC
 Try your self
Unit -5
Example : 2 A quantity of dry air at 27oC is Application of
compressed (i) slowly and (ii) suddenly to 1/3 of its statistical Mechanics
(Thermodynamics and
volume. Find the change in temperature in each case, Statistical Mechanics)

assuming g to be 1.4 for dry air.

(02PY0507)

Solution : (i) when process is slow, the temperature of

the system remains constant.
(ii) When compression is sudden, the
process is adiabatic
 Try your self
Unit -5
Solution : (ii) When compression is sudden, the Application of
statistical Mechanics
process is adiabatic. (Thermodynamics and
Statistical Mechanics)
Here V1 = V and V2 = V/3, T1 = 300 K, T2 =? (02PY0507)

Now using T2 (V2)g-1 = T1 (V1)g-1

T2 = T1 (V1/V2)g-1 = 300 (3V/V)1.4-1

T2 = 300 (3)0.4 = 465.5K = 192.5 oC

So temperature of air increases = 192.5 – 27
= 165.5 oC = 165.5 K
 Try your self
Example : 3 Find efficiency of the Carnot’s engine
Unit -5
Application of
working between the steam point and ice point. statistical Mechanics
(Thermodynamics and
Solution : Statistical Mechanics)
(02PY0507)

Here T1 = 273 + 100 = 373 K (steam Point)

T2 = 273 + 0 = 273 K (ice Point)
So efficiency  = 1 –T2/T1 = 1- 273/373 = 100/373
 = 100/373 x 100 = 26.81 %
 Try your self
Unit -5
Example : 4 A certain mass of gas is expanded to Application of
three times its volume under adiabatic conditions. statistical Mechanics
(Thermodynamics and
Calculate the resulting temperature and pressure. Statistical Mechanics)
(02PY0507)
g = 1.4
Solution :
(a) For temperature Here V1 = V and V2 = 3 V ,
T1= 273 K and T2 = ?
Now T1V1g-1 = T2V2g-1
So T2 = T1 (V1 /V2) g-1 = 273 (1/3)1.4-1
T2 = 176 K = -97 oC
 Try your self
Unit -5
Solution continue: Application of
statistical Mechanics
(Thermodynamics and
(b) For pressure Here V1 = V and V2 = 3 V , Statistical Mechanics)
(02PY0507)

P1= 1 atm and P2 = ?

Now P1V1g = P2V2g
So P2 = P1 (V1 /V2) g = 1 (1/3)1.4
P2 = 0.2148 atm.
 Unit -5
Application of
statistical Mechanics
(Thermodynamics and
Statistical Mechanics)
(02PY0507)
Thank you

for

your kind attention