Diffusion

Chapter 9 (old book)

General process of flow

Heat as the example
Ficks First law
Use of diffusion Coefficients
personal passive samplers,
SO2 accommodation coef.
Particles
Probability distribution using random movement
Diffusion distances
Ficks Second Law
Diffusion in a GC column
Diffusion in a sphere
Estimating Diffusion Coefficients
gases
water; liquids
Turbulent Diffusion
Lake system
Atmospheric System

Heat
Templow2

Temphigh1

x
The heat that flows thru a slab of material is proportional to the
cross sectional area, A, of the slab and the time, t, for a given
Temp
Heat flow is also to Temp/x for a given A and time if
Temp/x is small
q
T
A
t
x

if we think about really small thickness of x

dq
dT
kA
dt
dx

dq/dt = the rate of heat transfer with respect

to time

dT/dx = the temperature gradient

k = thermal conductivity

dq
dT
kA
dt
dx

k has the units of

Kcal / sec
meter 2 oC / meter

material

Al
Steel
Pb
air
glass

4.9x10-2
1.1x10-2
8.3x10-3
5.7x10-6
2.0x10-4

Temphigh1
Templow2
L
at steady state for a const. temp gradient across
the rod
q
T T2
k 1
tA
L

Diffusion

1b. cool

1a. hot

2b. low voltage

2a. high voltage

3b. low mass

3a. high mass

4b. low pressure

4a. high hydrostatic pressure

flux = flow area-1 time-1

a gradient drives the flow

page 184 table 9.1

Page 184 Table 9.1

Let us consider a gas diffusing in into a zone where it is constantly

collected or removed

O3
O3 O3
O3
O3
O3

[O3]

Flux O D
3

inlet
O 3
x

(moles O3 )
(time ) area ;

(moles O 3 )
[O 3 ]
D
( time)area
x

If we measure the # of moles of O3 collected over a period of time;

know the diffusion coef. for O3 in air, [O3] can be calculated

Diffusion and sticking coefficients

the average speed of gas molecules is given by
c

8RT
Mw

The rate of collisions per unit time with a wall of surface A in a

given volume is
rate =

rate

1/4 c x area x concgas

RT
A C gas
2 Mw

rate/A = # molecules time-1 area-1 = flux

if we think about the # of effective collisions, i.e. the ones that
actually stick to the wall, a factor is introduced called
sticking factor
surface recombination
accommodation coefficient

removal

rate

RT
A C gas
2 Mw

Judeikis et al. were interested in the effectiveness of coal surfaces

in the uptake of SO2 gas.

rate/A = # molecules time-1 area-1 = flux

flux = radial velocity Cgas D C/r
r

SO2
measure SO2

coal soot coating

on surface

-D d [SO2]/d r = rad. vel x [SO2]

ln {[SO2]/[SO2,o]} = rad. vel x r /D

ln {[SO2]/SO2,o]} = krate t

Removal of SO2 along a tube reactor coated with

fly ash. The accommodation coef. = 4.4x10 -4. The
total pressure was 55 torr, with O2 = 6 torr and
SO2 = 9m torr; % RH= 0

The Stokes-Einstein Equation (particles)

Let us now think of diffusion in terms of chemical potential
We can think of the driving force of diffusion as the negative
gradient of the chemical potential, i.e.
d/dx = free energy/mol /dx
The frictional force resisting the flow, due to an imbalance in
chemical potential, is the frictional coef. f (force/velocity) on
each molecule x the velocity, v, of the flow,
for a mole this force is f vNo
f v No= -d/dx
Flux has the units of moles, molecules or mass per area per
time
Flux =

moles/(cm2 time)

Conc x velocity = moles/cm3- x cm/time =

moles/(cm2 time)
We can define a diffusion velocity caused by a driving force or
chemical potential, or the concentration gradient such that:
C v = Flux
recall

10

RT
dp
P

substituting for P from PV=nRT, and n/V = C

P= CRT
d

RT
dC
C

f Nov = -d/dx
v

RT
dC / dx
f N0 C

C v = Flux =

RT
dC / dx
f N0

11

Flux

RT
dC / dx
f N0

diffusion coef D= RT/(f No)

Stokes (including Cunninghams slip factor) showed that for
unit spheres and nonturbulent viscous flow that the resisting
force on a particle flowing through a fluid is

f = 6r/Cc
where = is the viscosity of the medium (poise)
air(20oC) = 1.83x10-4 g/(cm sec) r is the
radius of the particles and
Cc = 1+/r(A+ Qe-rb/) where is the mean free
path of air = 0.067 m
particle
size (m)
0.01
0.05
0.1
0.25
0.5
1
5

Cc
22.2
4.97
2.87
1.69
1.33
1.16
1.03

12

The Randomness of Diffusion

Consider 17 boxes arranged in a row PAGE 185

FIGURE 9.2

13

page 186 figure 9.3

fit to random walk distribution

2
pn (m )
n

1/ 2

m/ 2
exp
n/ 2

Normal Gaussian Distribution

p( x)
21/ 2

x 2
exp
2
2

14

Where we would like to go with this is relate the sigma, ,

which is a basic feature of the normal distribution to the
diffusion coefficient D

p( x)
21/ 2

2
pn (m )
n

1/ 2

x 2
exp
2
2

m/ 2 2
exp

n/ 2

2 2= n/2

n /2

if we multiply this by x, the distance across a box, can

be related to an actual distance

We will then calculate the flux across from one box to

another

The concentration gradient which caused the flux

Substitute into Flux = -D dC/dt

15

BOX #

5
x

40

60

24

42

14

28

5t
4

6t
7t

8t

If we look at 5th box in seventh time step (7t),

12 particles are entering box #5 from the left and
2 from the right
at the eighth (8t) step, 7 particles leave box #5
and go back to box #4
this gives a net flux of 5 particles between the
7th and 8th steps or
Flux = 5/2t
We now define an average change in concentration per length
between adjacent boxes because for every step one box is
emptied and the adjacent one filled
C = N/x
the spatial conc. gradient dC/dx is
dC/dx = C/x = N/x2

16

If we look at time step 6, the gradient dC/dx driving the diffusion

between boxes for time step 7 is
dC/dx = -N/x2 = -(24-4)/x2
recalling that F = -D dC/dx and F= 5/(2t)
D

5 /( 2t )
20 /( x 2 )

( x ) 2
8 t

t= nt and x = n1/2/2 x
x = (2Dt)1/2
for three dimensional movement
s = (4/Dt)1/2

17

Example How long does it take for a gas molecule of

biphenyl and 0.25 m particle to diffuse from the center of a
5 cm sphere to the a walls of the sphere? Assume a
diffusion coef of 0.06 cm2/sec for biphenyl and 1.6x10-6
cm2/sec for the particle.

2.5 cm

for biphenyl

s = (4/Dt)1/2
t

S 2
3.14x 2.5 cm2

4D 4x0.06 cm2sec 1

t = 82 seconds
for the aerosol, D= 1.62x10-6 cm2/sec
(d= 0.25 m)
t = 35.5 days

in water biphenyl diffusion is much slower than in air

D10-6

so

t = tens of days
18

Ficks second law

Ficks second law attempts to express the change in
concentration with respect to time with the change in Flux
dC/dt = f (flux)
Consider an elemental volume (box) with a flux of material
in and out
F X

FO

A mass balance on the elemental volume per unit time (both

in and out)
mass= conc x vol); flux = mass/(area time)
flux x area= mass/time

19

mass= conc x vol); flux = mass/(area time)

mass/time = (conc x vol)/time
d(mass) d(conc vol)

d(time)
d (time)

= -area

flux

V dC/dt = -area flux

V = area x
division by V
dC/dt = -flux/x;
as x --> zero
1
dflux

flux

lim
dx
x o x

it appears that

dC/dt = - dflux/dx
F
C
x
t x cons tan t
x t const

F
C
x
t x cons tan t
x t const

20

C
2C
(D ) D 2
t
x
x
x

If we think of three dimensions

Fy Fz
C
F
x

t
x
y
z

(D x
)
(D y
)
(D z
)
t
x
x
y
y
z
z

2C 2C 2C
C

t
x 2 y 2 z 2

21

1. diffusion in the x direction

A solution in the x direction for a long tube, where diffusion in the
y and z direction is insignificant, is

M
C( x,t)
exp
1/ 2
2
2
(

Dt
)
4
Dt

where = (2Dt)1/2
Figure 9.5 Page 193

22

What kind of diffusion can we expect for a compound

traveling down a 30 m fused silica column (0.25mm id);
assume a flow of 1 cm3/min?

id vol of the col = (0.025cm/2)2x 30m x100cm/m;

vol =1.47cm3 ; Flow = ??
The flow time = 1.47cm3/ 1cm3 per min = 1.47 min

A typical diffusion coef= 0.07 cm2/sec,

(2Dt)1/2=

so our peak would broaden by

4 x = 4(2x0.07x1.47*60)1/2 = 14.06 cm; why 4

the carrier travels 30 m or 30x100 cm in 1.47 min

this equals 3,000 cm/1.47 min = 34 cm/sec

our peak would broaden in this time

14.06 cm /34cm/sec = ~0.4 sec

23

2. Diffusion in the Radial Direction

PAH

2C 2C 2C
C

)
t
x 2 y 2 z 2

converting to polar (radial) coordinates

x= r sincos, y = r sinsin , z = r cos
2C
C
C
2C
1
C 1 2C

D
2

cot

t
rr r sin 2 r 2
r 2 2
r 2

if diffusion is only in the radial direction

2C
C
C
D
2r
t
r
r 2

2 (C r)
(C r )
D

t
r 2

PAH

24

dr
These types of systems can be solved with numerical techniques
to calculate the C at successive depths of dr into the particle
over time
U= Cr
U(p) t t U(p) t D

t
U(p 1) 2U(p)U(p 1)
r 2

Figure 3. Modeling the uptake of deuterated pyrene by

diesel exhaust aerosol at 298K.

25

Diffusion between two parallel plates

Cout
W

Cin

Lets say that we wanted to strip a gas and not particles

Solutions to the partial differential equations take on the form

C out
A n exp n
C in n 1

C/Co= 1 - 1.52652/3 +1.5 +0.0342 4/3

where = 8 x D x L x W/(H x flow)

26

Large Stripper System

Transmission Properties

100

% Transmission

80

particles D=.00005

60

40

organic gas D=.05

20

10

20

30
40
Flow Rate (cfm)

Organic Gases (D=0.05cm2/s)

50

60

Particles (D=0.0005cm2/s)

27

Estimating Diffusion Coefficients

Factors that influence diffusion
average distance traveled between collisions,
i.e. mean free path,
more collisions for a given distance translates
into a lower mean free path
organic
air
org,air

where

1/ 2

(1 z)

1
Nair 2org,air

N= # air molecules/vol
= collision diameter of air and organic
z= molecular wt ratio of organic/air

We would predict that diffusion coefficients would decrease

with increasing (molecular weight)1/2 and effective collision
diameters squared.
Diameter2 radius2 cross sect. area of molecule
V r3or r V1/3; so r2 or area V2/3
If we assume the volume of a molecule is molar vol V

28

and molar volume =

molecular weight
in cm/mol
liquid density

Figure 9.6 top page 195

See Figure 9.6 page 195

29

Molecular weight vs Diffusion Coefficients

Page 195 Fig 9.6 bottom

30

Diffusivities in water page 196 Figure 9.7

31

Estimating Gas Phase Diffusion Coefficients (page 197)

equation on page 197 with definitions

32

Estimating molar volumes

1. molar volume, V =

molecular weight
in cm 3 /mol
liquid density

for benzene
Mw= 78, density =0.88gcm-3=89 cm3/mole
2. sum of atom size---> diffusion
for benzene
V= 6(C) +6(H) +ring
V= 6x16.5+6x2.0-20.2 = 90.8 cm3mol-1

33

Calculating liquid Diffusion Coefficients

Dw

13.26x10 5
(cm2 sec 1 )
1.14
0.589
xV

V = molar volume
= solution viscosity in centipoise (10 -2g cm1
sec-1) at the temperature of interest. The units
of poise refer to the property of fluids that
requires a shearing force of one dyne (g
cm/sec2) of two parallel layers of one cm2 at
velocity of 1 cm/sec over a gradient of one cm
log = A / T+B
For other liquids Wilke-Chang (1955) give
Dliq

7.4x10 8 ( Mw )1/ 2 T
(cm2 sec 1 )
0.6
xV

where is the solvent association term, Mw is

the molecular weight of the solvent, is the
solvent viscosity, T is the temp.

water
CH3-OH
ethanol
Heptane
Benzene

2.6
1.9
1.5
1
1

page 409 In Barrow Physical Chemistry 1962

Table 12.5

36

Reynolds Numbers
A body moving through a fluid creates
1. Inertial forces, i.e. forces due to the
acceleration or deceleration of small fluid
masses near the body
2. Viscous frictional forces due to the
viscosity of the medium
Inertial forces/viscous forces = Re#
Re# = m x vel x d/
/ m = = (kinomatic for air) =
Re# = vel x d/
= 0.00121 g/cm-1sec-1 /1.82x10-4 g/cm3= 0.151cm2sec-1
for flow in a pipe
laminar region
intermediate region
turbulent flow

1-2000
2100 - 4000
>4000

A 1 m aerosol is flowing in a 16 duct with a velocity of 3500

ft/min. What is the Re# in the duct?
Re# = duct diameter x rel. velocity of air to duct/v
Re# = vel x d/ = 3500x12x2.54/60 x 15x2.54/.151= 479000

37

Turbulent Diffusion
for molecular diffusion
x = (2Dt)1/2

td

L2
2D

If we look a molecular diffusion times

(page 201 Table 9.5)

38

For transport by advection

Flux = C v
Fad = Cv (m L-2 t-1)

adv

C
C
C

divFadv v x
vy
) vz

x
y
z

(M L-3 T-1)
For advection the time scale is simply

ta

L
v

(advection)

L L2

;
v 2D

td

L crit

L2
2D

(diffusion)

2D
v

For distances larger than L advection is more important than diffusion.

In your homework, you will calculate the critical distances for typical
air and water advection and then explain what it means.
An expression for Turbulent Flux
It is possible to develop a turbulent diffusion coef. analogous to a
molecular diffusion coef.
Lets assume that turbulent fluctuations cause a change in
concentration along with an associated flow Qex of volume between C1
and C2 over some distance Lx.

Lx

39

C2
C1
x

If Lx is small, the concentration difference C1 -C2 can be described by

the product of Lx and the slope of the curve at the point it intercepts
the plane between C1 and C2:
C1-C2 = - Lx C/x
Since this moves across some area, a, at a flow of Qex the velocity vx
= Qex/ a
Since Flux = C vx= Qex/ a ( - Lx C/x)

Fturb,x

L x Q x C
a x

Fturb,x Ex

C
C vx
x

and
Ex

C v x
C/ x

This is property of the fluid motion and not the substance

described by C
Effect of eddies on dispersion
Consider a patch of ink on a water surface that is turbulent. It is
characterized by the size of its concentration variance 2 about its
center of mass. The patch after time t will grow and be displaced

40

 = 2Et

and

2/t = 2E

Figure 9.9 page 206

41

The growth of 2 becomes faster with increasing 2.

Figure 9.10 page 207

42

Table 9.6 page 206

43

How do we determine turbulent diffusion

coefs in vertical mixing?
1) from the change in heat content
zB

c p Az
z

Tz
dz
t

; from Fickian flux

c p Az E z ( T / z )

Cp = heat capacity

substituting and solving for Ez

zB

Ez

Tz
dz

z
c p Az ( T / z )
Az ( T / z )

Az

2) Radioactive tracers
Radon-222 gas is released from
Radium-226 in sediments

44

the radon diffuses into the water, where

it is transported upward by turbulence

Broecker sets up a Ficks second law flux expression for

excess radon, i.e. radon beyond the conc. of that which
should be in equilibrium with existing Ra (hence your book
uses the word activity)
Rn/t E z

2Rn
h 2

Rn

if there is little change in Rn/t after some time

Rn/t E z

2Rn
h 2

Rn

= zero

a solution to this at Rn/t = zero

Rn (h) = Rn(h=0) exp[-(/Ez )1/2 h]

so if we plot
ln Rn(h) vs h we get a slope of ........

45

Figure 9.13 page 212

46

Parameters used to characterize vertical mixing in Lakes

In a lake water is usually stratified with the most
dense water at the bottom.
A stability time N, is introduced which describes how
how long it will take to restore a water parcel which is
moved vertically to a different density regime.

g d
N

dz

1/ 2

g= gravity acceleration
= density

47

the coef. of thermal expansion is related to the

change in density with temperature by
d/dT = -
This gives

N2 = -g dT/dz

Finally
N2 is related to the vertical eddy diffusion coef.

Ez = a (N2)

-q

48

Turbulent Diffusion in the

Atmosphere

49

Fisks 2nd law

Solutions in 1,2,3 dimensions

If we just think in two dimensions; ie there is no

diffusion in the x direction compared to y and z, and
substitute an emissions strength for X (emissions in
g/time normalized fro velocity)

50

Historically
Ky and Kz have been related to a Gausian

such that

substituting

51