1.

7 Rates of Processes
Heat transfer
Qe
1. Radiation: empty space I   Ve
t
1
2. Convection: gas or liquid I  Ve  GVe
R
3. Conduction: solid, liquid or gas

Lattic vibration,
Molecular collisions
conduction electrons

ATt Q dT
Q A
x t dx

Q dT Fourier heat
 k t A conduction law
t dx

where kt: thermal conductivity

 Conductivity of an ideal gas
In a gas, the rate of heat conduction is limited by how far a molecule can travel
before it collides with another molecule.
mean free path (): average distance that a molecule can travel before it collides
with another molecule

volume of cylinder = average volume per molecule

2r    V
2

1 V
N 4r 2 N
Assume that r=1.5 Å =1.5 x 10-10 m
V kT 1 V At room temp,
  4  1026 m3   150 nm
N P 4r N
2
atmospheric pressure
  1.5  107 m
t     3  1010 s
v v rms 500 m/s
 Q 
1
U1  U 2    1 U 2  U1
2 2

  CV T2 T1
1
2
1 dT
  CV 
2 dx

Q 1 1 1 CV  1 CV 2 1 CV
kt      v
t A dT / dx 2 At 2 A t 2 V
f
CV Nk f P V
 2   v  T
V V 2T N

kt  T
 For air at room temp & atmospheric pressure

1 CV
kt  v
2V
1 V
  150 nm kt  0.031 W/mK
4r N 2

  1.5  107 m (kt)exp  0.026 W/mK

t     3  1010 s
v v rms 500 m/s

CV
f  5,  800 J/m3  K
V

Heat conduction: transport of energy

Viscosity: transport of momentum

Diffusion: transport of particles

 Viscosity

A  u x ,top  u x ,bottom  Fx u x
Fx  
z A z
Fx u x where : viscosity (unit: poise)

A z

where s: density of solid

R 3 s  f g
4
Fg 
3 f: density of fluid

Fd  6Ru

Fnet  Fg  Fd
 Diffusion

dN
J x  D Fick’s law
dx
D: diffusion coefficient

Fd
Let    6R
u

D  kT Einstein-Smoluchowski realtion

Ref) Biological Physics by Philip Nelson, Chap. 4. Random walks, Friction, Diffusion
4.1 BROWNIAN MOTION

4.1.1 Just a little more history - 원자가설?

• 1773, B. Franklin : olive oil (~5 cm3) on water

Covered about 2,000 m2

d~ 5 cm3/ 2,000 m2
d=? ~ 2.5 nm !! invisible

• Ideal gas law : pV=NkBT product NkB , not N and kB

• 1828, R. Brown : pollen grain(1 m) in water

Life process? No!
 4.1 Brownian Motion

R. Brown

Pollen grains suspended in water do a peculiar

incessant dance, visible with his microscope (1828)

At first, he assumed that the Brownian motion was some life process.
However, he concluded that this motion had nothing to do with life.
Brownian motion by molecular kinetic theory

1.매우 불규칙적이다.
2.두 입자가 충분히 가까이 있게 되어도 서로 독립적으로 움직인다.
3.작은 입자일수록 더 활발하다.
4.입자의 종류나 밀도와 무관하다.
5.점성이 적은 유체에서 더 활발하다.
6.온도가 높을수록 활발하다.
7.운동이 결코 멈추지 않는다.

By constant collisions between the pollen grains

and the water molecules agitated by their thermal
motion
Any Problems?
YES !
Brownian motion_problems with kinetic theory, 1905

1. How can a molecular collision with a enormous pollen

grain make the grain move appreciably?
molecule ~ nm , pollen grain ~ m or 1,000 nm

2. Human eyes can’t see events faster than 30/s.

molecular speed ~ 1,000 m/s
distance between molecules ~ 1 nm
# of collisions ~ 1012/s !

Albert Einstein : The two problems cancel each other.

4.1.2 Random walks lead to diffusive behavior

• Tossing a coin once per sec: head-E, tail-W (1D RW)

Observer : can notice the displacement d

when 100 heads in a row :

rare but possible
Einstein,
We cannot see the small, rapid
jerks of the pollen grain, still we
can and will see the rare large
W E
displacements.
0 d
A random walk has structure on all length scales.
The thermal motion becomes more and more important as we look at smaller
objects – and biological macromolecules are much smaller than pollen grains.
 2D Random walk
•Tossing 2 coins

7500 steps
Moving: 1/5 steps
1 sampling/25 steps

computer
simulation
300 steps
Jean Perrin’s
experiments
 1D RW
The diffusion law
How far you’re likely to go in a random walk? Find xrms
 1D RW
How far you’re likely to go in a random walk? Find xrms

x j : position after j steps, x0  0

k j  1, x j  x j 1  k j L

 xN   x N 1  k N L   x N 1   kN 
2 2 2 2
   2 L x N 1k N  L2

 x N 1 
2
  L2

 x N 2   x0 
2 2
  2L  2
  NL2
1D Diffusion Law
N  t / t
 xN 
2
 NL 
2
 D  L2 /(2 t )
 2 Dt D: diffusion constant

The diffusion law in 3D

 rN 
2
 6 Dt
 1D RW
Any individual walk will not conform to the diffusion law, even approximately

(t) (t)

xN 2  NL2 xN 2  2 Dt

The collective activity of many randomly moving actors can be effectively

predictable, even if the individual motions are not.
 From macro to micro

L2
D microscopic parameters
2t
macroscopically observable:

1. Note the initial position. However, we have

2. Wait a time t. 1 macroscopic parameter & 2
3. Note the final position. microscopic parameters.
4. Calculate x2/(2t).
5. Repeat many times. need the 2nd formula
6. Find the average of x2/(2t) : D. relating L and Δt
 The diffusion law is universal
as long as we have some distribution of
random, independent steps.

Einstein relation:  D  k BT
4.1.4 Friction is quantitatively related to diffusion

A small body suspended in fluid (1D)

f : constant external force 2nd relation

viscous friction coefficient
2m
collisions once per t  
t
v0, x : starting velocity just after a kick
macro micro
1 f
 
2
x  v0, x t   t
2m
f
 t 
2
x 
2m
x t 1 The particle acquires a net drift
 f   vdrift  f
t 2m  velocity in spite of random collisions
Viscosity

For a spherical particle,

  6 R : Stokes formula
viscosity of radius of the
the fluid particle

water  103 kg /(m  s) at room T

 Are 2 relations enough?

L2 
1. D  
2t  • 2 microscopic parameters can be computed.

2m  • But these are unobservable.
2.  
t 
third relation
 L
2

 t   v0, x   D  k BT
2
2
   L  k T
 
 3.    B
k BT   t  m
v0 , x 
2

m  Einstein Relation
1905

, D, T; measurable parameter
Einstein relation:  D  k BT

• The fluctuations in a particle’s position (D) are linked to the

dissipation (or frictional drag ς).

• kB determined by macroscopic measurements (ς, D, T) .

 Ideal gas law pV=NkBT
 N determined
 size of a molecule

• The Einstein relation is quantitative and universal.

• Einstein estimated that a 1μm sphere in water would take a minute to

wander a mean square displacement of 5μm.
 Actually doable!
 Jean Perrin et. al. did the experiments.
4.2 EXCURSION:EINSTEINS’S ROLE
• Realizing what problems were important :
the reality of molecules
• Interdisciplinary interest
• Find new, testable, quantitative predictions

• If molecules are real, then they have a real, finite size,

which manifests itself in many different ways :
He found 4 more independent determinations of Nmole.

• Matter consists of discrete particles, and light does

as well (light-quantum).