Diffusion Microscopic Theory

Microscopic Theory of Diffusion

Absolute temperature T
Kinetic energy associated with a particle moving along each axis = kT/2
Mass m ,velocity vx along the X axis

KE = mvx 2

< mvx 2 > = kT/2

<vx2 > =kT/m

<vx2 >1/2 = (kT/m)

eg .Lysozyme particle
Particles in vacuum; aqueous medium water molecule interruption wandering
around of particles random walk
 Characterizing diffusive spreading One dimensional random walk

Motion of particles along one axis only

Particle starts at time t=0 at distance x=0
Random walk characteristics:
1. Each particle steps to the right or left once every seconds, moving at a velocity vx , a
distance = vx t
2. The probability of going to the right/ left at each step is .
3. The particles by interacting with molecules of water, forget what they did on the
previous leg of their journey.
4. Successive steps are statistically independent. Walk not biased
5. Each particle moves independently of all other particles ;do not interact with each other
Striking consequences
1.Particles move nowhere on the average
2.Root mean square displacement is proportional to the square root of time (not to the
time)
Establishing consequences

Considering an ensemble of N particles

Position of the ith particle after the nth step = xi ( n)
Position of the particle after the nth step differs from its position after the n-1th step
by (Rule 1)

xi (n) = x i (n-1)

Rule 2 : The + sign will apply to roughly half the particles and sign to the other
half

Mean displacement of the particles after the nth step

<x(n)> =1/N ( xi(n)

 Expressing xi (n) in terms of xi (n-1),
<x(n)> = 1/N ( (xi (n-1) )
= 1/N ( (xi (n-1)

<x(n)> = < x(n-1)> Mean position does not vary from step to step

Calculating Particle Spread

Measure of spread root mean square displacement <x2(n))>

(square of negative numbers non zero values)

xi 2(n) = xi 2(n-1) 2 xi (n-1) + 2

0
Computing the mean,

< x 2(n) > = 1/N xi 2(n) = 1/N (xi 2(n-1) 2 xi (n-1) + 2)

< x 2(n) > = < x2(n-1)> + 2

Since xi(0)= 0 for all particles i
<x2(0)> =0
Thus,
<x2(1)> = 2
<x2(2)> = 2 2
<x2(n)> = n 2
Therefore the mean square displacement increases with step number n
The root mean square displacement increases with n
The particles execute n steps in a time t = n ;n proportional to t
Hence mean square displacement t
Rms displacement t

Spreading increases as the square root of time

N= t /
< x2(t) > = (t/ )2
= (2 / )t
Assuming (2 / = )D
<x2> = 2Dt
Small molecule in water, D = 10 -5 cm2/s