Interfacial Engineering

PECE515
Calcutta University
SEDIMENTATION &
DIFFUSION
Dr. Sudeshna Saha
Assistant Professor
Chemical Engineering Department
Jadavpur University
Why are they important?
• Affect many colloidal phenomena
• Electrokinetic phenomena
• Kinetics of coagulation
• Sedimentation occurs under the influence of gravity,
considerably faster in centrifuge.
• Ultracentrifuge indispensable for colloidal dispersions
• Diffusion more dominant in colloidal size range
• Equilibrium between gravitational or centrifugal force and
diffusion also very important
 diffusion focuses on the determination of the mass or molecular
particles.

SEDIMENTATION: SOME BASIC 2.2 SEDIMENTATION: SOME BASIC CONSIDERATIONS

66 HIEMENZ AND R
CONSIDERATIONS
T o see how sedimentation occurs, consider the gravitational forces t
of volume Vand density p 2 that is submerged in a fluid of density p I .
Figure 2.2a for a spherical particle, but the discussion is independen

the particle. The particle experiences a force F, due to gravity, taken to be

downward direction. At the same time a buoyant force F, acts in the opposite d
force
Netequal
forceto the difference
acting on thebetween
particlethese forces results in the acceleration of t

This force will pull the particle downward - that is, F,,, will have the same sign
gravitational force Buoyancy force
p l , and the particle is said to sediment. If, on the other hand, p I > p 2 , then th
move upward, which is called creaming.
ρ2> ρ1 - Sedimentation
2.2a Friction Factor and Stationary Settling Velocity
ρ2< ρ1 - Creaming
As the net velocity of the particle is increased,
FIG. 2.2 Thethe viscous
forces force
acting on a spherical Fv
particle opposing
due i
to gravity and v
alone; and (b) due to gravity and the viscosity of the medium b2> p l ) .
increases. Soon this force, shown in Figure The 2.2b,forces acting the
equals on a net
spherical
driving particleforce r
due to gravity and viscosity: (a) due to
the motion. Once the forces acting on the particle balance, the particle experien
gravity alone; and (b) due to gravity and
acceleration and a stationary state velocity isthereached.
viscosity ofItthe may mediumbe shownρ2> ρ1 that, ). un
state conditions and for small velocities, the force of resistance is proportional
ary state velocity v:
 move upward, which is called creaming.
2.2a Friction Factor and Stationary Settling Veloci
Friction
2.2a
Factor
As theFriction
and
Factor
net velocity ofand
Stationary
the Stationary
Settling
Settling Velocity
particle is increased, the viscous
Velocity
increases.
As Soon this
the net velocity force,
of the shown
particle in Figure
is increased, the2.2b, equals
viscous force the
Fv
the net
As the motion.
SoonOnce
velocity
increases. of the
this theparticle
force,forces acting
shownis on 2.2b,
inincreased,
Figure thethe
particle
viscous
equals balance,
the net drivt
acceleration
force
theFv opposing
motion. and
Once amotion
itsthe stationary
forcesalso state
increases
acting velocity
on the isbalance,
- reaches
particle reached.
to a theItpartic
ma
stationary stateand
acceleration velocity-
state conditions and particle
for small
a stationary novelocity
state longer is
experiences
velocities, the force
reached. of resista
It may be show
acceleration
state conditions
ary state andv:
velocity for small velocities, the force of resistance is pro
ary stationary
Under state velocity v: for small for small velocities
state
Fv
Fv
=fv
=fv
where the proportionality constant
f f is
where the proportionality constant f is called the friction factor.
where the proportionality constant is called called
the the
friction friction
factor. fa
Th
dimensions
dimensions mass
mass timetime - I , skgin
- I , kg s SIin SI units.
units. We consider
We consider som
some aspects
Above
(2)equation independent
(2) forspherical
for spherical particles
particles inoftheanythe
in particular
following
following geometry.
section.
section. However, Howeve
Equati
any
Theany particular
stationary
particularstate geometry.
velocity
geometry. The is The stationary
positive
stationary forstate state velocity
sedimentation
velocity and is pos
is positive for
negative
tive
tiveforfor
for creaming.
creaming.
creaming.
Since theSince
net the
Since thenetnet
force offorce
gravity
forceof and gravitythe and
of gravity the
viscous viscous
andforce
the are force
equal
viscous are equa
force
conditions,
under stationary Equations (1) and (2) may be equated to give
state conditions,
conditions, Equations (1) and (2) may be equated to give

The stationary state is quite rapidly achieved, so Equation (3) de

 Mass-to-Friction-Factor
2.2b Mass-to-Friction-Factor Ratio Ratio
Equation (3) may also be written

m l - -
9 g = f v m is the mass of the particle (ρ2V)

where rn is the mass of the particle (p21/). This equation has the fo
• It is It
1. independent
is independentof particle shape.
of particle shape.
• 2. It assumes
It assumes that that the bulk
the bulk density density
of the of thecomponents
pure pure components
applies to no
(i.e., thesolvation).
settling units (i.e., no solvation).
It permits
• 3. the evaluation
It permits the evaluation of av situation
of v for for a situation
in which
in the
which the
mass-to-friction-factor
( m / f )is known. ratio (m/f)is known.
It permits
• 4. the evaluation
It permits of ( m of
the evaluation / f )(in
ma/ fsituation for which
)in a situation for which
v is known.
The stationary sedimentation velocity of a particle is an exper
for some systems, so item 4 summarizes much of our interest in se
it is the ratio ( m / f ) rather than m alone that is obtained from s
 irection.Because
dE/dt = of
Conversely, internal
67r7v;Rs friction,is some
if the particle moving of inthe one translational
direction, the k
SEDIMENTATION
y a over
force a inperiod
the of
opposite AND
time. DIFFUSION
For
direction. the physical
This force situation
is given pictured
by Stokes’s in
The
showStokes's
product of the
thatalsothe equals Law
rate ofthe
viscous for
energy Spheres
force F, exerted by the particle on t
dE/dt
the fluid rate dissipation
at which work is done is given on the by fluid
F =Because 67r7Rsvof internal friction, some of the translational kinetic e
forcedE/dt times = a distance
67r7v;Rs equals energy, so a force times a veloc
Because of internal friction, some of the 68
hereoverthe a subscripts
dissipation. period of
Thus, for
time. weFForand
have v two
the are no
physical longer needed,
situation
different ways pictured
of provided in Figure
expressing wet
translational kinetic energy of flow
The
show
n opposing product
associatedthat the of
rate
directions.
with the
of
the
dissipates over a period of time. viscous
energy
(Note
presence force
dissipation
that
of Fa F,
and exerted
dE/dt
v
sphericalare is by
given
vectors
particle theby particle
and,
in the therefo
flowi on
the
magnitude fluid
expressions mustalso be equals
gives specified the forrateeach.)*
at which work is done on the flui
dE/dt = 67r7v;Rs
force
The
times
product
a
of
distance
the viscous
equals
force
energy,
Fv
so a force times a velo
The product of
dissipation. the viscous
Thus, we have forcetwoF, exerted
different by theways particle
of on the flu
expressing
.3bthe Sedimentation
exerted by the particleEquation on the fluid and
fluid also equals the rate at which work is done on the fluid by th
associated
Itthe
forceis velocity
clear
times
with
vz ofthe
that
a distance
the presence
theforce
fluid also
acting
equals
of a
equals
on
energy,
spherical
the fluid acts
the
so
particle in
a force times a velocity eq
in
oppositionthe flow
quation
rate
expressions
fluid (7)flowing
at
is expresses,
which work
gives in is
theforpositive
done a spherical
on the fluid particle,
direction,by the the general
sphere resists result
theraf
dissipation.
the particle. Thus, we have two different ways of expressing the
woassociated
direction.ofwith
aspects the theresult
Conversely, are important:
presence ofparticle
if the a sphericalis moving
particleininone the direction,
flowing liq
by a force
expressions in the
gives opposite direction. This
1. For small, stationary-state velocities, the viscous force on a force is given by Stokes
It is tional
clear thatto the the force
velocity.
Stoke’s acting
Law on the fluidFIG. 2.3 acts
Distortion in opposition
of flow streamlines around
F = 67r7Rsv Distortion of sphere
flow streamlines
fluid
2.
is
For flowing
a spherical in the positive
particle, the direction,
friction the
factor is given resistsby the
where
It is the
clear
For a spherical
direction. subscripts
that the forcefor F
actingand onv are
the no
around
fluid a
longer
acts spherical
particle if the particle is moving in one direction
Conversely, solving in
anyneeded,
opposition
differential particle.
provided
equation is to the
the adequ
that describe the problem. Since the disturba
fluid
in is
opposingflowing in the
directions. positive
(Note direction,
that F the
and sphere
v are theresists
particle, it the
at vectors isand, flow to b
ther
by aj force in the opposite direction. Thisspatial force variableis givenat by Stok
centered convenient di

direction. = 6n: r?R, r originating the center of th

magnitudeConversely,must be specified if the particle is movingdescribed
for each.)* in one in terms direction,
of this variable. the flu
1. The thickness of each successive laye
It was just from
eliminated notedEquation
that the(4),
caseyielding
of spherical
a resultparticles
that permitsis one
th.einmass
which
of athe
sph
eliminated
be evaluatedfrom
fromEquation (4),yielding
sedimentation a result
data alone. To that
see how permits th.e mass
thi:s works, weofrea
be
(3),
Sedimentation Equation
(3),evaluated from sedimentation
using Equation
usingparticle,
spherical Equation
evaluatedata
(8) to Equation f(9)
(8) to(3)evaluate
Equation
alone.
and To seeashow
(4/3)7rR; a thi:s works,for
substitution
may be solved for the stationa
becomesf and (4/3)7rR; as a substitution
w

spherical particle, Equation (3) becomes 2 R3P2 - P l ) g

v = --
9 7
Equation (9) may be solved for andthe
forstationary-state
the radius of sedimentation
the spherical velocity
particle
Equation (9) may be solved for the stationary-state sedimentation velocit
v =- 2-R3P2 - P l ) g
v = 9- 2-R3P27 - P l ) g
and
Since the9 radius
for the 7 to
of
particle thewhich
spherical
Since particle
the particle
it applies to which
is a sphere, it applies
above equationis a sp
mayfor
and alsothebe usedoftothe
radius calculate
the the
mass
spherical mass
and
particle and friction
friction factor
factor of ofparticle:
the the
70 HIEMENZ AN
particle:

Since the particle 4 which it*Vectors

to 4applies isare
a denotedEquation
sphere, by bold(1letters
1) mayand their
also be
m = p 2 - 7 r R 5 = differentiation
-rp2
the mass and friction
3 factor of3 the particle: is not used when only the magn
Since the particle to which it applies is a sphere, Equation (1 1) may also
andand friction factor of the particle:
the mass
*Vectors are denoted by bold letters and their magnitudes by colrresponding rom
differentiation is not used when only the magnitudes are important.
*Vectors are denoted by bold letters and their magnitudes by colrresponding
differentiation is not used when only the magnitudes are important.
 this particle were solvated, it would swell to a larger ra
Effectsfactor.ofSmall Nonsphericity
asymmetrical particles and Solvation
rotate through ev
because of Brownian motion. Figure 2.4 shows that a
the tumbling
Actual particles particle
can deviate from the will
Stokesalso
modelhave a radius
by being either larger than
solvated, asymmetrical, or both.
An increase in f is associated with this situation as
in which case f increases so that a particle of mass m will display a smaller
sedimentation it is convenient
tively,velocity than it would if to consider
it were the following
an unsolvated sphere. ratios:
f/fn
• f is the friction In
1. factor Equation
of the actual (14), fis
particle. the friction factor of the
• The fo is the friction factor for an unsolvated sphere given by Stokes’s
2.
law to equal 6𝛑𝜼Ro
The fo is the friction factor for an unsolvated
6nyR, in the present notation. This is the lowe
• The ratio f / f o measures the amount by which the actual friction factor
with the required mass.
exceeds the minimum value.
• The f * is the 3.friction
Thefactor
ratio f o measures
for fa/ spherical particle the amount
having the sameby which
volume as the solvatedminimum value.
particle of mass m
• The ratio f*/fo measures
4. The fthe increase
* is in f due tofactor
the friction solvation.
for a spherical p
solvated
• The ratio f/f* measures the increase
particle in fof
due rn.
to asymmetry
mass
5 . The ratio f */fo measures the increase in f due
 The results in
enclosed of an
a sedimentation
armoredThe experiment
customary
steel in designate
to
chamber afor
sedimentation centrifugal
safety. field
coefficient
this are convent
depends
At limiting
these va
speeo
terms of what is known as aat
sedimentation coefficient. This quantity isand
defin
Ultracentrifuge :generally
Sedimentation
several different concentrations,
labeled with respect to tempe t
drldt customary
tation to designate
coefficient this
measured limiting
at (or valu
corr
Coefficient
s=-
2.4 b Sedimentation
w‘r Coefficient
generally
Under labeled with
stationary respect
state to tempera
conditions, the
tation
of coefficient
resistance will measured
be equal. at (or correc
Therefore, accelw

z:)z:)
that is, it equals the sedimentation velocity
The results of a sedimentation experiment in a centrifugal per unit of centrifugal
The results
system, this of ahas
ratio sedimentation
the Under
units m s - experiment
stationary
’ / m s P 2 or in conditions,
state
seconds.a centrifugal
In the
practice, field
thefoq
field are conventionally reported in terms of what is known
terms
defined of
to what
be I .O is known
svedberg
as a sedimentation coefficient of
(1 as
.O a
S) sedimentation
resistance
after T . will be
Svedberg, equal.
the dr
coefficient. This
Therefore,
originator quu
of thew2
m ~ - - w
pioneer in its use (Nobel Prize, 1926). Sedimentation coefficients
2 r = f - are usual
dt
unit. sIf =the- drldt
location of a particle along its settling path is dr measured as a fun
m ~ - - w 2 r = f -
sedimentation w‘rcoefficient is wherefis
readily evaluatedthe friction factor
by integrating for the( 15)
dtEquation settu
to yield is at radial position r, at time t , and at
limits of integration. The component

system,
U’S I
that is, it equals the sedimentation
n

this
n

$
dt = ratio has to
velocityfactor
wherefis the friction per for
unitthe
ofsettlin
cen
units m s - ’ / m s P 2or seconds. In p
theyield
defined to be I .O svedberg (1 .O S) after T . Svedberg, the origi
pioneer in its use (Nobel Prize, 1926). Sedimentation coefficie
or
unit. If the location of a particle along its settling path is mea
sedimentation coefficient is readily evaluated by integrating Eq
limits of integration. Thedepends
component position r, at
is at radialconsequently, it ist

I
The sedimentation coefficient on concentration;

$
at several different
n
concentrations,
n
and the results are extrapolated to zero c
customary to designate this limiting value by a superscript zero. Experimen
U’S dt =
sedimentation alone can be interpreted. Example 2.3 illustrates the use of these relationships.
* * *
EXAMPLE 2.3 Sedimentation in an Ultracentrifuge. What should be the speed of an ultracen-
trifuge so that the boundary associated with the sedimentation of a particle of molecular weight
60,000g mole-’ moves from rl = 6.314cm to r2 = 6.367cm in 10 min? The densities of the
particle and the medium are 0.728and 0.998g cm - 3 , respectively, and the friction factor of the
molecule is 5.3 * 10-“ kg s-‘.
Solution: First we calculate the particle mass by dividing the molecular weight by Avogadro’s
number:
rn = 60,000/6.02-
1023= 9.97- 1 O-20 g molecule-’
molecule-’
= 9.97.10-~~kg
Equation (19)allows us to calculate the sedimentation coefficient:
s = ( d f ) [l - ( p 1 / p 2 ) ]= (9.97.10-23/5.3.10-11)
[l - (0.998/0.728)]
= 6.98.10-13s = 6.98S
Equation (17)can now be solved for o2

-
or w = 4.47 103 rad s-‘. Dividing by 27r converts this to revolutions per second: w = 711
revolutions per second, or 42,700rpm. rn
* * *

In the preceding sections of this chapter, we have considered sedimentation as if it were the
only process that influenced the spatial distribution of particles. If this were the case, all
systems of dispersed particles, even gases, would eventually settle out. In practice, convection
 potential.
flux of
be component. In
material
assumed to equal the context
through
unity. of a diffusion,
cross
Substituting section
Equationthe potential
equals
(28) dilutethe to
into Equation be used
product(27) is
of the
gives its chem
conc
ith
This is often Since
called the we are interested
thermodynamic in
force infinitely
for diffusion. It systems,
is necessary the
to activity
divide by coe
Avth
partial
As
sion
be alreadymolal
velocity:
assumed noted,Gibbs
to equal the free
driving
unity.
energy
force of the
underlying component
diffusion canof interest.
be thought Thus,
of as the
gadro’s number NAsince p, is aSubstituting
molar quantity. Equation (28) into show
Thermodynamics Equation
that (27) gives
driving
in origin.forceA very (pergeneral
particle)waydiffusion
to describe may be written
a force as it as the negative g
is to write
Diffusion
This is =often
potential.
p, =ps)In+called
the l nCoefficient
SEDIMENTATIONAND DIFFUSION
SEDIMENTATIONAND DIFFUSION
cvdiff the of +diffusion,
a, =thermodynamic
R Tcontext py and
R T l n (y,c,)
the
force forFrictionFactor:
potential to be used
diffusion. It is is the chemical
necessary
spherical particles, the time required for the particle to diffuse a unit distance is directly
81

(2
pot
to divide
81

Thermodynamic Description of Diffusion

spherical particles, the time required for the this
particle
time to diffuse a unit distance is itdirectly
NAsince
proportional to its radius. For small molecules, is experimentally accessible; be-
partial
gadro’s
where
comes
k,molal
number
is
proportional
Gibbs
Boltzrnann’s
experimentally
free
p, energy
is a molar
constant
to its inconvenient
radius. For small
of
R/N,. the
molecules,
for particles
component
quantity.
Under
this
at the
stationary
timeend
upper
of
Thermodynamics interest.
state Thus,
show
conditions,
is experimentally
the force
thatthis
of the colloidalaccessible;
range.
magn
it be-

Combining Equations (30) and ( 3 1) and comparing with

comes experimentally inconvenient for particles at the upper end of the colloidal range.
Equation (22
driving
equal to force
a,, cj, (perofparticle)
+
viscous diffusion
resistance, may givenbebywritten as
+
2.5b Diffusion Coefficient and Friction Factor:
where and
the force y,are the activity,
Diffusion Coefficient
2.5bThermodynamic concentration,
and Friction
Description and
Factor:
of Diffusion activity
f v according to Equation (2). Therefo
coefficient, respectively, of th
where
result = is
p, k, ps)Boltzrnann’s
component. Since
n a,are=
R T l we constant
py RR/N,.
Tinl ninfinitely
Thermodynamic Description of Diffusion
(y,c,)
Under stationary state conditions,
As already noted, the driving force underlying diffusion can be thought of as thermodynamic
ith interested dilute systems, the activity thismaf
coefficient
magnitude of the velocity of diffusion equals
in As already
origin. noted,
A very the driving
general way toforce underlying
describe a forcediffusion
is to writecanitbeasthought of as gradient
the negative thermodynamic
of a

equal
This to
is the
potential.

be assumed
potential.
partial
partial
driving toforce
often
In A
in origin. thevery

equal
molalInGibbs
molal
force
of
called viscous
unity.
the context
(perGibbs the
general
context
resistance,
thermodynamic
way to describe
of diffusion,

Substituting
of diffusion,
free energy
Equationgiven(28)
by finto
force v according
a forcetoisbetoused
the potential
for
the potentialoftointerest.
of the component
freediffusion
particle) energy of
maythebecomponent Equation
be used Thus, to Equation
diffusion.
writeis ittheaschemical
the negative

(27)
potential

gives
is the chemical (2). Th
It is necessa
gradient of a
p,, the
potential
the magnitude
written as of interest. Thus, the magnitude of the
thethe
of p,,

magnitude
gadro’s of
number the velocity
NA sinceof diffusion
p, is a molar
where a,, cj, and y,are the activity, concentration, equals
driving force (per particle) diffusion may be written as

quantity. Thermodynamics
and activity show th
coefficient, respective
This is often called the thermodynamic force for diffusion. It is necessary to divide by Avo-

ith component.
+
Since we are interested in infinitely dilute systems, the activity coeffic
+
This is
gadro’s often called
number NAsince thep,thermodynamic forceThermodynamics
is a molar quantity. is necessary
for diffusion. It show that to divide by Avo-

This p,is +often + called the thermodynamic force for diffusion. It is necessary to di
gadro’s number NAsince p, is a molar quantity. Thermodynamics show that
+ +
be
where
=
p, = ps)

assumed
p, = ps)

the
R T
R T l n a, = py
ps)
to equalhas
R T l n a, = py

subscript
l n
unity.
been
a, =
R T l n (y,c,)
py
Substituting
R T l n (y,c,)

omitted from
R T l n
Equation
the
(y,c,)
(28) into Equation
concentration of the
(28)
(28)
(27)
solute c gives this
because
gadro’s
It
where k, number
should
ithwhere
be NAsince
noted
is Boltzrnann’s
a,, cj, and
component. y,are
Since we the
that p, is
constant aR/N,.
this molar
activity, concentration,
are interested quantity.
derivation
Under Thermodynamics
where a,, cj, and y,are the activity, concentration, and activity coefficient, respectively, of the

contains
stationary
and activity
in infinitely dilute systems,coefficient,
statenoconditions,
the activityrespectively, show
of the
coefficient may
this that
assumptioris force abou
will b
the only
be ith
quantity involved in the relationship. Finally, we make the following observatio
component.
assumed Since
to equal we Substituting
unity. are interestedEquation
in infinitely
(28)dilute systems, (27)
into Equation the activity
gives coefficient may

+ +
be assumed to equal unity. Substituting Equation (28) into Equation (27) gives
equal to thesubscript
force of viscous resistance, given bythe according to Equation
f v concentration (2). Therefore, th
cles,
where ofHowever,
flux p,
where
the
magnitude = of
material
a,, ps) R when
Thas
through
cj, andinvolved
the l n been
a,
y,are the
velocity a
of
the
= pyparticles
omitted
cross R
section
activity,
diffusion Tfrom
l
equals n are
(y,c,)
equals assumed
the producttoofbe
concentration, and
where k, is Boltzrnann’s constant R/N,. Under stationary state conditions, this force will beits spherical,
of the solute
concentration
activity we
c can
becaus
and
coefficien its
the
for
siononly
f,
where
equal
quantity
k, isforce
to the

and
velocity:
equal to the
magnitude
Boltzrnann’s

the
of viscousconstant
force
of the in
resistance,

resulting
of viscous
velocity the
R/N,.
given

equation
resistance,
of diffusion relationship.
Under
by f v stationary
according state

for Finally,
to Equation

the diffusion we make

(2). this
conditions, Therefore,
the
force will

coefficient
given by f v according to Equation (2). Therefore, the
equals following
the be

is the obser
well
ith component.
flux material Since we
through are interested
magnitude of the velocity of diffusion equals

of a cross section equalsin infinitely

the product dilute
of systems,
its concentrationthe act a
where k,
relation.
where is Boltzrnann’s
a,,cvdiff
cj, and y,are the constant
activity, R/N,. Under stationary state conditions, this forc
concentration, and activity coefficient, respec
be
sion assumed
=
thewhere
to
the subscript
only quantity
equal
has been
involved
unity.
in theomitted
Substituting
from the
relationship. concentration
Finally, we make of
Equation
by
thethe
f v (28)
where the subscript has been omitted from the concentration of the solute c because this is now
velocity:
equal Many
to the force of viscous resistance, given according
following
into
to Equation
Equation
because this The
solute cobservation. is now
(2). (27)
There
ith
theofonly
flux

component.
flux
sion
of
quantity
material
the
involved
through

Since relationships
in the
a cross

we
relationship.
section

are
equals the

interested 82this
of
Finally, we make
product

in chapter
of its the
have
concentration

infinitely dilute involved

following observation. The
and its diffu-

systems,
of material through a cross section equals the product of its concentration and its diffu-
velocity:
the the frictio
activity coe
Combining
magnitude
where Equations
of
sion velocity:

the the
subscript has
= cvdiff (30)
velocity
been and
of ( 3 1)
diffusion
omitted from and comparing
equals
the concentration with Equation
of the (22) leads
solute c because
(31) to the imp
this is Eq
no
now,
be =
assumed
Combining
result has
cvdiffbeen
to
= cvdiff
equalan unknown
unity. quantity
Substituting except
Equation for
(28) spherical
into Equation
Equations (30) and ( 3 1) and comparing with Equation (22) leads to the important
Combining Equations (30) and ( 3 1) and comparing with Equation (22) leads to the important
result particles.
(31)
(27) gives
the only quantity involved in the relationship. Finally, we make the following observation. Th
result

impasse
Combining and
flux of materialEquationspoints(30)
through a out
crossandthe ( 3 complementarity
section 1) and
equals comparing
the productwith between
of Equation
its sedimentation
(22) leads
concentration and itstodiff
th
For example, substitutionand substituting (32)Equation (32) into
It should be noted that this derivation contains no assumptioris about the shape of the parti-

ments.
result of Equation into (4)gives
It should
cles, However,be noted
when thethatparticles
this derivation contains
are assumed nospherical,
to be assumptioris about
we can the shape
substitute of the parti-
Equation (8)
sion velocity:
forcles,
f,andHowever, whenequation
the resulting the particles arediffusion
for the assumed coefficient
to be spherical,
is thewe can substitute
well-known Equation (8)
Stokes-Einstein

where k, is Boltzrnann’s constant R/N,. Under stationary state conditio

for f,and the resulting equation for the diffusion coefficient is the well-known Stokes-Einstein
relation.
relation.
Many of the relationships of this chapter have involved the friction factor f,which, until
(32)f,
where the subscript has been omitted from the concentration of the solutetoc because th
now, has Many
beenofan
theunknown
relationships of this
quantity chapter
except have involved
for spherical the friction
particles. Equationfactor which,this
breaks until

equal =to
now, has
impasse
impasse
It should
ments.
where the
andbeen
force
an out
points
of
unknown
cvdiff
is Boltzrnann’s
k,quantity
For and
be
points
example,
viscous
that thisconstant
notedinvolved resistance,
derivation
substitution
R/N,.
out the complementarity
contains
of Equation (32)
given
quantity exceptbetween
the complementarity
between
by
for spherical
f v k,Ts
according
particles. and
sedimentation
sedimentation
no assumptioris
into (4)
Under
gives
stationary
Equation
Equatio
(32) measure-
diffusion
and diffusion measure-
about
state the shape
conditions,
(3
breaks this

ofthis
the
the only
Combining
magnitude Equations
of the
in the
and (of
velocity
relationship.
3 1)diffusion
and assumed m
comparing =
Finally,
ments. For example, substitution of Equation (32) into (4)gives

(30) with
equals
we make
Equation we the
(22)can following
leads observa
to the importa
cles,
equal
flux However,
ofto the
material when
force ofthe
through particles
viscous
a cross are
resistance,
section equalsto
given be
by
the fspherical,
v
311according
product - of (its
P
to substitute
Equation
concentration
I h 2 ) l
(2).
Equat
and T
result
f,
for
Itsion and be
magnitude
should the
velocity: resulting
ofnoted thatequation
the velocity for the diffusion
thisofderivation
diffusion equals coefficient
contains no assumptioris about theStokes-E
is the well-known shape
relation.
solventIf towebeassume
identicalthat
to that of the free
solvation solvent.
occurs In the eventpositions
at numerous that the solvated
along the spe
in
ofdensity from itsparticle
the solvated bulk counterpart, the ratioas
may be written / p 1 may
p 2the sumbeofreplaced by (Tl/T2),
the volume of the whu
Effect
are
thethe partialof
volume of Solvation
specific
the volumes of the components, and measure the volume per un
bound (subscript b ) solvent:
the indicated components in the solution at the indicated concentration and hence
The ratio f * / f o equals unity when M , , ~= 0 and increa
volume changesofthat
volume accompany
solvated the interaction.
particle
Equation (38), using the more familiar
quired. We +
V2 Vl,b
= examine
densities.
We continue toofdiscuss
an application solvationbi
this relationship
Asymmetry as well as solvation can cause a friction
ThisWe can arebeexplicitly
rearrangedlooking for the
as Next effect
let us of solvation
consider on t'he
the ratiof/f*, friction
which, factortoof
according

2) 2(Ejl
particle asymmetry is handledofby the second
particle asymmetryratioonfly. By Stokes's
the friction law,saw
factor. We thein ra
S
v2+ vl,b v2 +
friction factors of solvated to unsolvated
a,. This ratio equals = the cube
are reasonable
(1 root Jean
of the= v2[1
volume +
spheresf*/f,
Perrin derived
is equal
models for many
ratioexpressions
to the ratio
asymmetric
of the solvated
of their
particles.
for thetoratiof/f*
unsolvate f
or the ratio of the equatorial semiaxis to the semiaxis of r
where M , , is ~ the mass of bound sions were obtained:
solvent and the last equality requires th
for prolate ellipsoids ( b / a < l ) ,
solvent to be identical to that First, of the free solvent. In the event that the
in density from its bulk counterpart, the ratio
The ratiopartial
are the f * / f o equals unity
specific when Mof, , the
volumes
(
[l -p 2 / p 1 may be replaced by
~= 0 and increases with increasing solvat
components, and measure the vo
quired. We examine an application of this relationship below.
the Asymmetry
indicated components in thecan
as well as solvation solution
cause a at the indicated
friction facto:r to haveconcentration
a value oth
volume
Next let uschanges
consider that accompany
the ratiof/f*, the according
which, interaction. We continue
to Equati'on to discus
(14), accounts for
Equation
of (38), using
particle asymmetry on the more
the friction
Second, familiar
factor. Wedensities.
for oblate saw in Section
ellipsoids > lthat
( b / a 1.5 ) , ellipsoids of
We are models
are reasonable explicitly looking
for many for theparticles.
asymmetric effect of solvation on t'he fricti
Jean Perrin
particle asymmetry derived isexpressions
handled for by the
theratiof/f*
second for ratioellipsoids
fly. ofByrevolution
Stokes'si
the ratio of
friction the equatorial
factors of solvatedsemiaxis to the semiaxis
to unsolvated of revolutionisbequal
spheresf*/f, / a . Thetofollowi
the r
sions were obtained:
a,. This
First, ratio equals
for prolate the cube
ellipsoids ( b / aroot
< l )of
, the volume ratio of the solvated
or
 the region
the below
particles in the
the cross
--x insection of
v isinterest.
which (22)
direction.
Equations theGradually
and sedimentation
(80) velocity
the
into Equation and c is the concentrati
concentration
(79) gives of the
(1 - r i)g c
Back-diffusion occursEquations = D z
dc
at a rate (22)
that increases
and (80) intowith the
Equation buildup of a concentrat
(79) gives
the
Whenregion
EQUILIBRIUM
f below
equilibrium isthe cross
finally section
BETWEEN
reached,
v c = D--
d C
we of
may interest.
SEDIMENTATION
write
d XdC
100 Back-diffusion occursv cat=aD-- rate that increases with HIEMENZ
the buildup AND
of
AND
where Jsed
When If
The Jdlff
is
the DIFFUSION
the
equilibrium
is given
flux
by
across
Sedimentation
is
Equation
If the
occurs
we
finally
area
in
substitute
(22),
adue
d
reached,
and
X
the to
value
Jsed
sedimentation
centrifugal
we
by
for field,
the
may rate on
of
write
and
the JdIffis
other
sedimentation the
hand,
under flux
g duE
must
gravity,
in Equation (4): If we (1
substitute
- ri)gthe
c =value z for the rate of sedimentation under gra
D dc
and for Equation
JsedJsed
where = is
(83) f area
vcthe flux across the (1 -due
ri)g = D dc z
toc sedimentation and JdIffisthe flux due
The Jdlffis given by Equation
which v is the sedimentation
in100
f
If the(22), and
Sedimentation
velocity Jsed by
occurs in a centrifugal field, on the other hand, g
and c is the concentration
in Equation (4): HIEMENZat theRAJA
AND plan
Equations (22) and (80) If the
into Sedimentation
Equation (79) occurs
gives in a centrifugal field, on the other han
where JsedJsed
= vc
Equationsis the(82)
flux
andacross
(83)
in theeasily
are
Equation areaintegrated
(4): due to sedimentation
to produce expressionsand JdIffis
that g
The
in of
Jdlff
which x
is
v at
is equilibrium.
given
the
and for Equation (83)
d C by Equation
sedimentation Defining(22),
velocityc , and
and
and c2
c to
Jsed
is be
by
the the equilibrium
concentration at concentra
the plane.
Equations= D--
v c100
respectively,
(22) and and
(80)then
into integrating,
Equation we
(79) obtain
gives for Equation (82)HIEMENZ AN
dX Equations (82) and (83) are easily integrated to produce expressions t
Jsedwe
Finally, vc Equation
= recall of x (32), which
at equilibrium. Defining cus
permits , and
to c2
substitute k,T for
to be the equilibrium g
conce
Df,
If we vsubstitute dC
the value Equations
for the (82)
rate
respectively, and
andofthen (83) are easily
sedimentation
integrating, integrated
under
we obtain to produce
forgravity,
Equation (82)express
Equation
c =for
in which v is D-- Equation (83)
d X the sedimentation velocity and c is the concentration a
and of x at equilibrium. Defining c , and c2 to be the equilibrium
(1 - (22)
Equations ri)gand D dc
z into Equation
respectively,
c = (80) and then integrating, we obtain for Equation (82)
(79) gives
If we substitute the value for the rate of sedimentation under gravity, Equation (4
f we recalld CEquation (32), which permits us to substitute k,T for Df, giving
Finally,
(1 - r i )g c = D z
dc
c = D-- occurs in a centrifugal field, on the other hand, g must be r
If the vSedimentation
infor f
Equation (4): dX
sedimentation equilibrium under gravity and
IfIf we
the Finally,
Sedimentation occurs
we recall
substitute the in for
a centrifugal
Equation
value (32), field,
which
the rate on the
ofpermits usother hand,
to substitute
sedimentation under must
g k,T be Df
for rep
gravity
in Equation (4):
(1 - ri)gc = D z
dc
for sedimentation equilibrium under gravity and
Equations (82) and (83) are easily integrated to produce expressions that give c