What is Dispersion?

to disperse = to spread widely

1 Dispersion is a form of mixing, and the act of distributing one

substance in another.

2 Dispersion also is a system containing a dispersed substance in

a medium (e.g., colloidal dispersions).

Mixing on several length scales

Dispersion is a process that involves

• molecular mixing due to diffusion
• macroscopic mixing due to laminar or turbulent flow, eddy or
vortex formation

diffusion and dispersion are similar mathematically but different

physically.

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Pollen Clouds

Birch pollen from Denmark traveled across the North Sea to

England this year (May 2006)

Dust Clouds from Africa

Global travel of dust carries microbes across oceans and

continents.

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Fog, Clouds, etc.
Water droplets dispersed in air appear as fog/clouds (and they
create rainbows).

Solutions, Suspensions, and Emulsions

Goal: Stable Dispersion

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Soot, Smoke, etc.

Goal: Quantitative description of dispersion

Good news: you already know the math!

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Mathematical Similarity...
1
e −( x − a )
2
1 −( x − a )
2
c∝ 4 Ex t
c∝ e 4 Dt
4πEx t
4πDt

Spreading of a pulse from an instantaneous

source located at x = a.

Example: Muskrats from Bohemia

r 2 = 4 Et

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Randomness!
• In diffusion, there are random encounters with molecules or
particles.

• In dispersion, there are random encounters with wind

streams, turbulence, trees in a forest, etc.

1 1 −( x − a )
2
−( x − a ) c∝ 4 Ex t
2
c∝ e 4 Dt
4πEx t
e
4πDt

Diffusion and Dispersion Coefficients

⎡ length 2 ⎤
Units are the same: D≡⎢ ⎥≡E
⎣ time ⎦
However, there are some important differences:
Diffusivity
• Usually independent of direction
• Strongly depends on chemical interactions

Dispersion Coefficient
• Ex ≠ Ey ≠ Ez

• Independent of chemistry
• Strong function of position
• Much larger than diffusivity
• Must be measured

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Dispersion in more than one dimension

1 ⎡ − ( x − a )2 ⎤
c∝ exp ⎢ ⎥
2 ( πt )
12
Ex ⎢⎣ 4 E x t ⎥⎦

1 ⎡ ( x − a1 )2 ( y − a2 )2 ⎤
c∝ exp ⎢ − − ⎥
4 ( πt ) Ex E y ⎢⎣ 4 E x t 4 E y t ⎥⎦

1 ⎡ ( x − a1 )2 ( y − a2 )2 ( z − a3 )2 ⎤
c∝ exp ⎢ − − − ⎥
8 ( πt )
32
Ex E y Ez ⎢⎣ 4 Ext 4Eyt 4 Ez t ⎥
⎦

Dispersion with flow in the x-direction

Consider that
• uniform velocity in x-direction is υo
• when t = 0, instantaneous source of solute occurs at the
point {x,y,z} = {0,0,0}

a1 = υot
a2 = a3 = 0

⎡ x − υo t ( ) ⎤
2
1 y2 z2 ⎥
c∝ exp ⎢ − − −
8 ( πt ) ⎢ 4 E y t 4 Ez t ⎥
32
Ex E y Ez 4 Ex t
⎣ ⎦

⎡ x − υot ( ) ⎤
2
M y2 z2 ⎥
c= exp ⎢ − − −
8 ( πt ) ⎢ 4 E y t 4 Ez t ⎥
32
Ex E y Ez 4 Ext
⎣ ⎦
M ≡ Mass of solute in pulse

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Taylor Dispersion (dispersion in laminar flow)

Injected pulse

Assumptions
• Dilute solutions (even for initial pulse)
• Laminar flow is unchanged by pulse
• Radial diffusion & axial convection only
⎛ LD ⎞
7.2⎜⎜ 2 0 ⎟⎟ >> 1
⎝ R0 υ ⎠

valid for long, thin tubes

Pulse dynamics

Injected pulse Concentration profile

observed here

What shape will the profile have at the beginning? at the end?
What is the effect of the diffusivity on the pulse?

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Mass Balance within Tube

∂c ⎡ 1 ∂ ⎛ ∂c ⎞ ⎤ ∂ ( cυ z ) ⎡ ⎛ r ⎞2 ⎤
= D⎢ ⎜ r ⎟⎥ − ; υ z = 2υ0 ⎢1 − ⎜ ⎟ ⎥
∂t ⎣ r ∂r ⎝ ∂r ⎠ ⎦ ∂z
⎢⎣ ⎝ R0 ⎠ ⎥⎦

M πR02 ( − z −υ0t )
2
4 Ez t
c= e
4πEz t
R0
1
; c=
πR0 ∫ 2πrc dr
( )
2
R0 υ0 0

Ez =
48D

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Taylor-Aris Dispersion
(Previous Taylor dispersion including the Aris correction for axial
diffusion)

Diffusion in axial and radial direction

∂c ⎡ 1 ∂ ⎛ ∂c ⎞ ∂ 2 c ⎤ ∂ ( cυ z ) ⎡ ⎛ r ⎞2 ⎤
= D⎢ ⎜r ⎟+ 2 ⎥ − ; υ z = 2υ ⎢1 − ⎜ ⎟ ⎥
0

∂t ⎣ r ∂r ⎝ ∂r ⎠ ∂z ⎦ ∂z ⎢⎣ ⎝ R0 ⎠ ⎥⎦

axial diffusion

M πR02 −( z −υ0t )2 4 Ez t same

c= e
4πEz t

( Rυ )
2
0

= D+
0
Ez
48 D
new term

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Determining Diffusivities from Dispersion
Measurements
First glance at the literature shows much activity, e.g.,

• Funazukuri et al., “Binary Diffusion Coefficients in

Supercritical Fluids: Recent Progress in Measurements and
Correlations for Binary Diffusion Coefficients”, Journal of
Supercritical Fluids 38 (2006) 201-210.
• Funazukuri et al., “Binary Diffusion Coefficients of Acetone in
Carbon Dioxide at 308.2 and 313.2 K in the Pressure Range
from 7.9 to 40 MPa”, International Journal of Thermophysics
21 (2000) 651-669.
• Callendar and Leaist, “Diffusion Coefficients for Binary,
Ternary, and Polydisperse Solutions from Peak-Width
Analysis of Taylor Dispersion Profiles”, Journal of Solution
Chemistry 35 (2006) 353-379.
• Belongia and Baygents, “Measurements on the Diffusion
Coefficient of Colloidal Particles by Taylor-Aris Dispersion”,
Journal of Colloid and Interface Science 195 (1997) 19-31.

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 FTD = “Fitting in the Time Domain”

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Theory

Goal of FTD method is to minimize the root-mean-square error:

Diffusivities

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Summary
• Dispersion and diffusion have very different physical origins
and proceed at very different speeds.

• Dispersion and diffusion can be described by the same

mathematics because they involve randomness (giving
Gaussian distributions)

• Dispersion is not only an effect that we observe, it is also a

tool used, e.g., to measure diffusion coefficients.

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