,
0
b. ,
.. . . ansP,()ftnc_. eDOinena;
4.A Basic Concepts and Mechanisms
4.A.l Contaminant Flux
4.A;2 Advection
'4.A.3 Molecular DiffusiOn
4.A.4 Dispersion
4.B Particle Motion
4.B.l Drag on Particles
4.B.2 Gravitational Settling
4.B.3 Brownian Diffusion
4.C Mass Transfer at Fluid
4.C.l MassTransfer Coefficient
4.C.2 TransPort across the AirWater Interface
4.D Transport in PorqusMedia.
4.D.l Fluid Flow through Porous Media
4.D.2 Contaminant TransPort in Porous Media
. References
Problems
Transport phenomena are encountered in almost every aspect of environmental engi
neering science. In assessing the environmental impacts of waste discharges, we seek
to predict the impact of emissions on contaminant concentrations in nearby air and
water. Contaminant transport must be understood to evaluate the effect of wastewater
discharge to a river on downstream w,ater qualiry or the cff""'t cf an incinerator on
downwfild air pollutant levels. In waste treatment co11taminant transport
within the control device influences the overall efficiency. In many. instruments used
to measure environmental contamination, performance depends on the effective trans
port of contaniitiants from the sampling point to the detector.
The physical scales of concern for contaminant transpOrt spaii ari enormous
range. At the low end, we are interested in phenomena that occur over molecular di
mensions, such as the transport of a contaminant into the pore of an adsorbent. At the
upper extreme, we consider the transport of air and waterborne contaminants
159
l
t :;
I
1:
t
I
!
I
!
I
! .
I
!
l
I
!
l
i.<.
...__ .'
,,,(_
}
.; ; .Transport Phenomena
) ',. \ ''tiobal distances. This range of linear dimensions encompasses approximately 15
magnitude. Not some phenomena importantat one
of the spectrum are irrelevant atthe other. "
:: , ; Transport phenomena also are important in other fields of study; notably chemical
and mechanical engineering. In these fields, the subject is often subdivided fluid
mechanics, heat transfer, and mass transfer. In environmental.engineering, where the
focus is on the movement of contaminants in air 'and water, elements ofall three of
these branches are conSidered. The essential ingredients fot understanding contami
nant transport processes are knowledge of the basic physical phenomena coupled with
the analytical tools of engineering mathematics.
Because of the importance of both molecular and particulate impurities in envi
ronmental fluids, the dominant transport processes of both molecules and particles
will be discussed in this chapter. We consider both the movement of impurities with
fluids and their movement relative to fluids. In Chapter 5, we will explore how the
transformation mechanisms studied in Chapter 3 and the transport mechanisms ex
plored in this chapter are combined to predict system behavior using mathematical
models.
4.A BASIC CONCEPTS AND MECHANISMS
4.A.l Contaminant Flux
Transport of both molecules and particles is commonly quantified in terms of flu.x
density, or simply flux. Flux is a vector quantity, comprising both a magnitude and a
direction. The flux vector points in the direction of net contaminant motion, and the
magnitude indicates the rate at which the contaminant is moving.
For example, think of an environmental fluid as depicted in Figure 4.A.l. Imagine
a small square frame suspended in this fluid and centered at a point of interest. The
frame is oriented so that the transport of contaminants through it is maximized. Then
the vector points in a direction normal to the frame, aligned with the direction of
contaminant transport. The magnitude of the flux vector is the net rate of contaminant
transport per unit area of the frame. Since the flux can vary from one position to an
other, the flux at a point represents the net transport through the frame per area in the
limit of the frame becoming infinitesimally small. The common units of flux are mass
or moles per area per time. We will use the symbol J to represent flux. An arrow is
written above J when we wish to emphasize its vector character. Contributions to flux
=a
 .. J . '
., , .: .. "t;;<
(x,y,z)
+
Figure 4.A.l Flux, 'J , is a vector quantity whose value varies with
position (x, y, z). The contaminant flux vector points in the direction
of transport, and its magnitude is the quantity transported (usually
mass or moles) per area per time.
= species concentrati
diffusivity, es =
= inertial drift velocit:
Electrostatic drift applit
may be cau
to explore t.
Advection
Advection i
. material is
eluding bot!
Figure
flowing thn
formconce1
slice of fluit
leading edg
the lower P'
The ad'
the same di1
xis obtaine
crosssectio
of contamir
volume of t1
thickness of
vective flux
urities in envi
s and particles
impurities with
\plore how the
techanisms ex
mathematical
1 terms of flux
agnitude and a
and the
lXimized. Then
the direction of
of conttarnltnaJBt
position to an'"'
per area in
,f flux are mass
tx. An arrow is
ibutions to flux
: . ..
TranSport induced
t;5 Ig = Cv,
dispersion
media)
Elec:trostatl'c driftd
m, p Transport by random
.thermatmotion.  _
m,p ..
m,p
m,p
p
Transport caused by apparently random
fluid velocityfluctuations in turbulent flow
Transport caused by nonuniform flq.id
flow with position
Transport caused by nonuniform flow
through porous material
Movement of charged species
in an electric field
Transport associated with acceleration
of a fluid
J = _
0
dC.
4
 dx
dC
J =c
t r dx
1
=cdC
s sdx
dC
Jh = .ehdx
: Je = Cve
""' species concentration, U = fluid velocity, v, = settling velocity, D =molecular or Brownian diffusivity, e, =
diffusivity, es =shearflow dispersivity, eh = dispersion coefficient, ve =electrostatic drift velocity,
= inertial drift velocity, J = flux.
diffusion and Brownian motion apply to and particles, respectively; both occur from the same
may be caused by several mechanisms (Table 4.A.l ). A major thrust of this chapter is
to explore the basic physical mechanisms that cause contaminant flux.
Advection
Advection is the transport of material caused by the net flow of the fluid in which that
material is suspended. Whenever a fluid is in motion, all contaminants in the fluid, in
cluding both molecules and particles, are. advected along with the fluid.
Figure 4.A.2 shows' how an advective flux can be evaluated. Consider a fluid
flowing through a tube with a uniform velocity. Assume that the fluid contains a uni
form concentration, C, of some contaminant. Focus on the amount of contaminant in a
slice of fluid of thickness A.L. As shown in the upper part of the diagram, at time t, the
leading edge of the slice has just reached position x. At some later time,.t +At (see
the lower part of the diagram), the trailing edge of the slice passes position x.
The advective flux vector for_ this. contaminant points along the axis of the tube, in
the same direction as the velocity vector. The magnitude of the flux vector at position
x is obtained by dividing the. amount of contaminant that pa8ses position ,x by the
crosssectional area of the tube (A) and by the time interval required (At).; The amount
of contaminant that passes position x is the contaminant concentration. (C) times the
volume of the depicted slice (AL X A). Note that the time interval (At) is equal to the
thickness of the slice divided by the fluid velocity (AL/U). So, for this case, the ad
vective flux magnitude,. la, is the quantity of contaminant passing position x per area
\ 
t+ IlL
u
Figure 4.A.2 Advective flux of contaminant through a tube.
The two pictures represent the same tube at two points in
t and t + At, where At = ALl U.
per time:
J =CXA.LXA=CU
a A(A.LIU)
In general, the threedimensional advective flux :vector is the product of the con:
taminant concentration and the fluid velocity:
+
la (x, y, z) = C{x, y, z) X U (x, y, z)
Molecular Diffusion
The molecules in air and wate.r are constantly moving. If it could be viewed at a
lecular sca1e, this movement would appear random and chaotic. Molecular movemef!!
in gases is particularly frenzied. In air at ordinary environmental conditions, a
'molecule, moving at a speed of 400 m s
1
, collides with other molecules on the order
of 10 billion times per second. Each collision involves an exchange of momentum
tween the participants, causing them to change direction and speed. Every cubic centl
meter of air has a phenomenally large number of molecules ( 25 million trillion at
T = 298 K and P = 1 atm) participating in this dance. In water, where the molecules
are packed a thousand times more densely, molecular motion is less fi:enetic,b,ut still
extremely energetic.
Although the molecularscale motion seems hopelessly disordered, the
scopic effects are well underst'Ood and predictable. Qumitativdy, the random motion
of fluid molecules causes a net movement of species from regions of high concentra
tio.n to regions of low concentration .. This phenomenon is known as molecular dijfu
. sion:, The rate of movement depends' on the 'concentration difference, with
differences leading to higher rates of transport .. The rate also varies according to
. far the species must travel from high to low concentration: The longer the distance,
the lower the flux. The rate of transport varies according to the molecular properties
the species, particularly size and mass, with larger size and larger mass resulting in.,
transport. The properties of the fluid itself play a key role: Molecular diffusion
"';
lfis;much slo
nidter.molecul
catalowmc
... , .. ::_vifonnienta
dif
Cussler, 19}
Law
To better UI
such as the
a moderate
The bulb is
cules evapo
bulb equal t
ylbenzene n
After a sho
through the
liquid ethyll
in inverse p
tube, and in
teristics can
where Jd is
time), ll.C h
and llx is tht
the diffusive
By intn
to an equati(
The constan
diffusing sp
x=L
T
:'is muchslOWei' ia watet than in
termolecwes .. .:
,._OUr discUSsio& is restricted __,,_
at a low mole fraction (<l),
vironmental engineering coricen
... trations, diffusioo can cause
Cussler, 1984).
Pick's Law
.,.
To better understand diffusion, it is useful to think about a specific physical system,
such as the one depicted in Figure 4.A.3. A glass bulb at 25 oc contains a liquid with
a moderate vapor pressure, such as ethylbenzene (1280 Pa at 25 C; see Table 3.B.l).
The bulb is open to the air through a thin cylindrical glass tube. Ethylbenzene mole
cules evaporate from the liquid, maintaining a partial pressure in the gas phase of the
bulb equal to the saturation vapor pressure. Because of their random motion, the eth
ylbenzene molecules gradually migrate through the tube and escape into the open air.
After a short transient period, the net rate of transport of ethylbenzene molecules
through the tube will reach a steady value that will be maintained as long as is
liquid ethylbenzene in the bulb. The escape rate of ethylbenzene from the tube varies
in inverse proportiOn to tube length, in proportion to the crosssectional area of the
tube, and in proportion to the partial pressure of the species in the bulb. These charac
teristics can be expressed quantitatively by the relationship
]doc _AC
llx
(4.A.3)
where Jd is the diffusive flux density (moles per crosssectional area of the tube per
time), A.C is the change in concentration of ethylbenzene molecules across the tube,
and Ax is the tube length. The minus sign appears in this relationship to remind us that
the diffusive flux proceeds in the direction of decreasing concentration.
By introducing the proportionality constant, D, this be converted
to an equation:
ac:
Jd= D
Iu
(4.A.4)
The constant, D't is called the diffusion coefficient, or diffusivity. _It is a property of the
diffusing species (ethylbenzene in this case), the fluid through which it is diffusing
x=L
Tube
.BUlb
Psat
la=D RTL
C= 0
I C= Psat
RT
Volatile liquid
maintained at
temperature T
Figure 4.A.3 Apparatus for producing a
controlled diffusive flux of a volatile species.
P sat is the saturation vapor pressure of
species at temperature T. Provided that the time
scale for evaporation and condensation is much
more rapid than the time scale for diffusion
through the a molar concentration P salRT
will be attained throughout the bulb. The vapor
molecules will diffuse through the tube with a
net diffusive flux J d
. <I
I
l
1
,:".'"'
1'.'"'..
sucltf:.S?:temperature
. . has. dimension,s of length squared pc;r time; typically,dl;is,Teported ill
. tube reaches a
to the partial derivative of concentration in that coordinate and the ,<.,:; .. .,. um.e is obtained by
tionality constant is D for each direction. So diffusive flux occurs in the direction op
posite to the concentration gradient at a rate that is proportional to its magnitude.
Equations 4.A.5 and 4.A.6 are known as Pick's first law of diffusion, or simply Fick's
law. See Exhibit 4_A.l for more details about the system depicted in Figure 4.A.3.
Significance of Diffusion
Diffusion is a slow transport process. Albert Einstein showed that the characteristic
distance a molecule (or a particle) will travel by diffusion in time t is given by
x)2Dt
' So a gas molecule with a diffusivity of 0.1 cm
2
s
1
can be expected to move a charac
teristic distance of 5 mm in a second, 3 em in a minute, 30 em in an hour, and 1 m in a
day. Molecules in water, with diffusivities lower by a factor of 1 Q4, will travel only 1
_percent as far on these time scales.
Another perspective is gained by comparing the simple form of Pick's law
tion 4.A.4) with the simple advective flux expression (equation 4.A.1). If a species
concentration diminishes from C to zero over some distance Ax, then diffusion causes ..
itransport afa rate equivalent to advection at a velocity D/Ax. Given the small.values of
D for air and especially for water, we see that the effective diffusive velocity is very
small except when the concentration changes by a large fractional amount over a very
small distance.
'Tdf
:],_tenstiC time require(
profile th
c; fpr typical values in
5 em and D  0.1 cr
/ With co.nditions hel
0+
0
Although molecular diffusion is a slow process, it plays a very important role
contaminant transport and fate. Diffusion is particularly important at interfaces, for
example between two fluids such as air and water, or at solidfluid interfaces. There ,,,n:\;)'ii\"'
r
can be no fluid advection at an interface in the direction normal to the surface. So im
purities cannot be transported by advection all the way to an Instead, some
other transport mechanism must convey the species through a small distance, known.
as a boundary layer, to the interface. For uncharged molecular impurities, diffusion is
the dominant mechanism of transport through boundary layers. For ions and particles,
diffusion always contributes, although other mechanisms such as electrostatic drift
and gravitational settling may also play a role. These details are important because
impurities may be removed from a fluid by deposition or other transformation pr<}
Diffusivity
Predictions
ficient, D.
Table4.A.2
nary enviro
there are
""re:)The ....
,:reported in.
1 rl 1 '
s t. t n wa"er,
j;
tor is proportional
n, and the propor
n the direction op
to its magnitude. ,
1, or simply Fick's
1 Figure 4.A.3.
t the characteristic
is given by
1 to move a charac
1 hour, and 1m ina
4
, will travel only''r.
)f Pick's law (equ.
.f.A.1). If a speci
1en diffusion
l the small values
;ive velocity is
amount over a
ry important role
mt at interfaces,
tid interfaces. The
l the surface. So
Instead,
1all distance,
1purities, di
or ions and part'""'""!ii:
as electrostatic
e important because
transformation
4.A
. .
ceSSes that OCCUf 00 sfoVehlStl
removal :::....: ... ,._, ___ , __ '""
Appliei#i of
further explore the behavior of the system ' that will be::iJWntaiJied as long as liquid remains
in Figure 4.A.3. Devices like this are , in the
to release a volatile substance at a constant The characteristic for the to
By diluting the emissions from the top of the pletely evaporate is obtained as the number of
with a known flow rate of contaminantfree . moles of liquid in the bulb divided by the molar
one generates an air stream with a constant,
concentration of the volatile Substance.
air stream can be used for instrutilent calibra
among other purposes.
When liquid is first placed into the bulb, some
must elapse before the diffusive flux leaving
tube reaches a steady value. An estimate of this
is obtained by rearranging equation 4.A_.7
for t and L for x):
L2
'T dffusion  2D
(4.A.8)
expression yields an estimate of the time
uired for a molecule to diffuse through some
distance L. It is a good estimate for the
teristic time required to establish a steady con
centration profile throughout the tube length.
Jpr typical values in a device of this sort, L 
,S em and D 0.1 cm
2
s
1
, so rdiffusioa 2 min.
conditions held steady for a time t >>
irdiffusion the flux win approach a steady value
Psat dC Psat
RT RTL
rate of by diffusion:
'T 
evaporation J dA
(4.A.9)
where pis the liquid density, Vis the liquid volume,
MW is the molecUlar weight of the diffusing spe
cies, and A is the crosssectional area of the tube.
For the case of ethylbenzene, we can estimate an
evaporation T . tion  4 X 10
7
s  d.
We have assumed values for the input
data: pV = 1 MW = 106 g mor
1
, Jd = 7.2 X
10
9
mol cm
2
s
1
(D = 0.07 cm
2
s
1
, P sat = 1280
Pa, R = 8.31 X 10
6
cm
3
Pa K
1
mol
1
, T = 298 K,
and L = 5 em), and A = 0.031 cm
2
(0.2 em inner
tube diameter). For times t that satisfy r diffusion <<
t << ,.evaporation' the diffusive flux from the tube
into the air will be constant During this time inter
val, the concentration profile within the tube will
also be constant, varying linearly with position x, as
shown in Figure 4.A.4.
Figure 4.A.4 Steady concentration profile
within the tube shown in Figure 4.A3, valid for
times t that satisfy 'Tdiffusion << t << 'Tevaporation
'o
Distance along x
L
Diffusivity of Molecules in Air
Predictions of diffusive flux depend on the selection of an appropriate diffusion coef
ficient, D. Measured diffusion coefficients for selected species in air are presented in
Table 4.A.2. This table emphasizes species of environmental interest, with air at ordi
nary environmental temperatures and pressures as the background fluid. Note that
there are discrepancies in the data reported from different sources (e.g., ammonia).
\'
f
',f
r
ti.
;I
NH
".
3
;:t_:273 .
298:2""'1 0.096't CU8sler;;l984
Carbon dioxide
co :;
2.
.. i.
McCabe. et 1993:
'\317.2
Etlulnot <;H
5
0H :: :273 0.102 ;
McCabe et al.,l993;Cussler, 1984
313 ''0.147 et at, 1987 (pressure = 1 bar)
Helium
Hydrogen
Methane
Methyl alcohol
nOctane
Naphthalene
He
H2
c;H4
CH
3
0H
CsHts
c;oHs
276.2
273
273
273
.273
273
0.624 Cussler, 1984
0.611 1984; MCCabe et al., 1993
Cussler, 1984
0.133 McCabe et: 1993
0.051 McCabe et al., 1993
0.051 McCabe et al., 1993
303 0.087 Reid et 1987
Oxygen
Toluene
02
<;Hs
273
273
0.178
Cussler, 1984; McCabe.et al., 1993
0.071 McCabe et al., 1993
299.1 0.086 Cussler, 1984
Water H
2
0 273 0.219 Bretsznajder, 1971; McCabe et al., 1
289.1 0.282 Cussler, 1984
298.2 0..260 Cussler, 1984
"312.6 0.277 Cussler, 1984
313 0.292 Reid et al., 1987
two sources disagree by less than s percent, onlY one value is listed.
The data in Table 4.A.2 show that the diffusivity of gases in air varies over
an order of magnitude from about 0.05 cm
2
s
1
for large organic molecules
. and naphthalene) to about 0.6 cm
2
s:'
1
for helium and hydrogen. Diffusivities
with increasing temperature because of the higher kinetic energy of the molecules.
. Diffuswities of Molecular Species in W(ller
Experimental data for selected species in water are presented in Table 4.A.3.
data exhibit a range of about a factor of 5.
4.A.4 .Dispersion
Our everyday experience tells us that impurities released into open air .or water do
confined at high concentration in a sniall volume for very, long. _Cookin
odors, incense, and cigarette smoke detectable throughout an indoor
within minutes of their release. The visible smoke plume from a fire can be seen
spread significantly as it travels downwind. The rate of contaminant spreading is
substantial interest in environmental engineering. And although fundamentally it
curs as a result of advection and diffusion, the rate of spreading is.much more
than might be inferred from the discussion so
Benzene
Hydrogen
Air
Methane
Carbon dioxi
Methanol
Ethanol
Ethylbenzene
Oxygen
Vinyl chloridt
8
Wben two sou
Uniform
that molecul
1984 ). Imag
coast of the 1
of5 m s
1
to
much spread
travel? The ti
km + 5 m s
sivity in air o
be the charac
equation 4.A.
tirely cont.rat:
distance of 5G
concepts we h
Our error
property ofm(
constant nor t
1
in the fluid te1
spreading of c
damentally dis
vection and in
Figure 4.1
analysis of en\
vated stack an
weak dispersic
centrations rer
spread rapidly
within the plm
ground rimch I
*We will use the t(
f':]' . , '
Cussler, 1984
)SUre = 1 bar)
beet al., 1993
.beet al., 1993
n air or water do not
very _long.
hout an indoor
a fire can be seen
inant spreading is
fundamentally it
much more
.. . . . 8SIC . an . ............. ':, . F .
4.A B .
Species . . . Fonnula. T (K)" <I D (em s ) . .,,., r I
18ble 4.A.3. for Species in,Water,"t<:.t<.L_,;... .
' ' ' . ' : ' ' ' .. ' ' 2 1 ' ' ' . ' . . , '
. . . . . M . . '" "
Hydrogen H
2
298 3.36 x los Bretsznajdej:,J971 ,:)
 _, __ :;._ 298 4.50 x to
5
CuSsler, 1984': _ if
Air
298
Methane
CH4
275
2.00 X 1 o
5
1984
0.85 x to
5
Reid et al., 1987 
Carbon dioxide C0
2
298 2.00 X I o
5
Reid et al., 1987
Methanol CH
3
0H 288 1.26 x Io
5
Reid etal., 1987
298 0.84 X 1 o
5
Cussler, 1984
Ethanol C
2
H
5
0if 288 1.00 x to
5
Reid et al., 1987
298 0.84 x 10
5
Cussler;l984
Ethylbenzene
CsHio
293 0.81 X 10
5
Reid et al., 1987
Oxygen
02
298 2.60 X Io
5
Bretsznajder, 1971
Vinyl chloride C
2
H
3
Cl 298 1.34 x Io
5
Reid et at, 1987
8
When two sources disagree by less than 5 only one value is listed.
Uniform, steady advection does not cause pollutant spreading, and we have seen
that molecular diffusion is a slow process. Consider the following situation (Cussler,
1984). Imagine that a thin stream of smoke particles is released aiong the western
coast of the United States and is steadily advected at a constant, uniform wind speed
of 5 m s
1
to the coast. Assl.lme particles have a diameter of 0.1 IJ.ID. How.
much spreading of the plume will occur by diffusion during this
travel? The time required for the wind to travel that distance is 10
6
s or 12 d (5000
km + 5 m s
1
). In Example 4.B.3 it will be shown that a 0.1 f.Lm particle has a diffu
sivity in air of7 xto6 cm
2
s
1
The plume spread caused by diffusion is estimated to
be the characteristic distance traveled due to Brownian motion, which, according to
equation 4.A.7, is roughly 4 em. Clearly, this is not an accurate description! It is en
tirely contrary to our experience to think 'that we could even detect a smoke plume at a
distance of 5000 km from its source. Yet this example accurately applies tht? tools and
concepts we have introduced. What went wrong?
Our error was made in assuming that the wind speed is uniform and steady. It is a
property of most fluid flows, including winds and ocean currents, that they are neither
constant nor uniform. When fluid velocity varies with time or position, contaminants
in the fluid tend to be transported from high concentration to low concentration. The
spreading of contaminants by nonuniform flows is called dispersion.* It is not a fun
damentally distinct transport process, Instead, dispersion is caused by nonuniform ad
vection and influenced by diffusion.
Figure 4.A.5 illustrates why it is importai;lt to incorporate dispersion into the
analysis of environmental transport. Poiiui.auts are shown being released from an ele
vated stack and blowing downwind. The lefthand figures show that in the case of
weak dispersion, the plume slowly. Downwind of the source, the peak con
centrations remain verj high near the plume centerline and the pollutants do not
spread rapidly to the ground. On the right, dispersion is strong. The concentrations
within the plume are diminished rapidly by dispersion, but the plume reaches the
ground much nearer to the s9urce. This tradeoff is characteristic of the effect that
*We will use the term dispersion to include both shearflow dispersion and turbulent diffusion.
. :168 tilhaftta.O'A "* 1'r . na.;:;._..; ,t_ ;,_
_.::
)
\
,
Side
view
Top
view
\if!_
. .
;,.. (
.. L
Peak concentration high,
but impact area low
Peak concentration low,
but impact area high
Figure 4.A.S Effect of dispersion on pollutant concentrations
downwind of a localized source. If the relea$e rate of pollutants and
mean wind speed are the same in the left and righthand frames,
then the total flow of pollutants is the same in the two cases. Rapid
dispersion leads to smaller peak concentrations but a larger impact
area.
dispersion has in all environmental settings: High dispersion rates reduce average
concentrations at the expense of increasing the area or duration of impact. A common
challenge in environmental transport modeling predict concentrations in the 11 .
gion downwind or downstream of a pollution source. To make these predictions in
face of dispersion phenomena, we must solve two problems. First, we must have
model that describe's pollutant concentration fields in the presence of dispersion.
ond, we must be able to determine how the rate of dispersion varies with environmen
tal conditions.
In complex flow fields, it is impossible (or at least impractical) to describe
veiocity exactly as a function of space and time. Without this information, dispersio
cannot be accurately described in terms of the fundamental mechanisms of advecti"
and molecular diffusion. As an alternative, dispersion can be treated as a random
cess, analogous to molecular diffusion, by applying Pick's first law of diffusion
the molecular diffusion coefficient replaced by a dispersion coefficient .. So in one
, mens ion, we would write
dC
J dispersion =  e dx
where e is a dispersion coefficient, obtained through a combination of empirical
and theoretical equations.
Alt..h.ough equation 4.A.l0 has the same form as Fick's first law, it is important
bear in mind the great distinction between diffusion and dispersion. Diffusivities
properties of the contaminant and the depending weakly on environmental
.:ditions (such as temperature) but not at all on fluid flows. Dispersion
the other hand, are primarily a function of the fluid flow field. Environmental
are_ highly variable and very complex. Dispersion in environmental flows is far
well understood than molecular diffusion. One should not expect a high degree of
curacy froin any models that must account for dispersion, especially when applied
environmental transport.
waste man<
Seven
In
turbulent a
ShearFlo
In a shear 1
to the fluic
tion of flo'
from regio1
Shear,
contaminar
large, such
Let's consi
laminar flo
fluid flow i
taminant is
so that its c
as it is adv
shows the L
L/U
0
At th
L, but it hru
centerline o
same time,
the cer.
ward veloci
pulse along
velocity. Tb
rate of dispt
Position: x = 0
I
I
E
I
.I
I
"'Ir
r
I
Figure 4.A.6
effects of she'
tes reduce
impact. A cotn.mcM
;ntrations in the
;e predictions in
st, we must have
of dispersion.
s with environmen'
rmation, dispers
misms of adveciliii
!d as a random
w of diffusion
.w, it is important
Jn. Diffusivities
environmental
)ion
':nvironmental
ttal flows is far
a high degree
tlly when applied .
4.A 169
: . ' .: ', ,:.. .
't"'
:DiSpersiOn ,phenomena aiise in i all; .tm.ee i>ianches::of:enviionmentil engineering
diseussed in this ;text illusfrates;:one :.of in air
qualicy: engineering.; In .water qitality, the impact:of WllsteWater 'discliargesoncontami
.'.nantcoilcentration8 in:rivers;flakes, .or'oceaJisdepetldon dispersion. IIihazardous
waste management, dispersion controls the movement of contamiriants in groundwater.
Several types of dispersion phenomena are encountered in environmental engi
neering. In this section, two are introduced: shearflow dispersion and
turbulent diffusion.
ShearFlow Dispersion
In a shear the fluid speed varies with position in a dirCctjon that is perpendicular
to the fluid velocity. If contaminant concentrations in a shear flow vary in the direc
tion of flow, then dispersion will occur, leading to a net transport of contaminants
from regions of high concentration to areas of low concentration.
Shearflow dispersion is generally important when there is a shortterm release of
contaminants, such as a spill, in environments in which the velocity gradients are
large, such as a river, an estuary influenced by tides, or the nearground atmosphere.
Let's consider a relatively simple example: shearflow dispersion in fully developed
laminar flow through a circular tube or pipe (Figure 4.A.6). The velocity profile of the
fluid flow is parabolic because of wall friction. At .timet= 0, some mass, M, of con
taminant is injected into the tube at position x = 0 and instantaneously mixed laterally
so that its concentration is uniform across the tube. We then observe the contaminant
as it is advected past some position, L, downstream. The upper frame in the figure
sh9ws the initial condition. The lower frame shows the tube at a subsequent time, t =
L/U
0
At the later time, the contaminant pulse is centered on downstream position x =
L, but it has been substantially stretched because those molecules that lie close the
centerline of the tube are advected at a higher velocity than those near the wall. At tlle
same time, contaminant molecules positioned near the leading edge of the pulse and
,pear the center of the tube tend to diffuse toward the walls. reducing their average for
ward velocity. Conversely, contaminant molecules located near the trailing edge of the
pulse along the tube walls tend to diffuse toward the center, increasing their forward
velocity. Therefore, surprisingly, the net effect of molecular diffusion is to slow the
rate of dispersion, in this case.
Position: x = 0

x=L
L___ , Time
I
; I
r
I t=O
I
L
t= Uo
Figure 4.A.6 Schematic of a model problem illustrating the
_effects of shearflow dispersion.
'
'
I
.
h
it;
HI
F:
;.,
_,A
"
;l t
H
i
Hi
t.
;
;
l'l,O;
) . . . . For the sifuatiOirdepicted in FigUre 4.A.6; direcfi91
' :1!> :: :s;.flow.:can be described as the
ne.the overallipulsetthrougll the tube. and
7
)
d Re P
p
112
v
1
= 11.4Cd
Now,,
werepeat
change fro
10.4, 10.4
figures is a
Figt
a function
locity
diameter, a
considered.
in air and s
for
The pa;
flux
The vector1
where C(x, .
downward, J
illustration <
mental ques
Studies have
of its area is
the same reh
initially clea
containing It
cles are sphe.
The pc:
ble4.B.l):
v
1
=
18 I
The number c
by the mass p
C=
;!:.
)2
o3
104
2.5 g
water
>m the
,r of
1from
Regime
tameter of 1 mm and a
lies in the intermediate
1 1 p 4 B'
g em s . 1gure . . ..
m s
1
With these values,
.5 em s
1
X 1 g
ediate regime.
tVe approach. Equations
,own parameters for
ese expressions): ,
. 4.B/ r Particle qJion 79.
Ptll1kle Settling Velocity for Intermediate Drag Regime (continued)
Now, we evaluate these equations in series, initially assuming v, = 15 em s
1
and
calculating ReP' then using that result to calculate and then using Cd to calculate v,.
We repeat this process until the numbers converge to a stable solution that doesn't
change from one cycle to the next. The intermediate results are v
1
= 11.3, 10.6, 10.4,
10.4, 10.4 em s
1
With a reasonable initial guess, a stable answer to three significant
figures is achieved after three iterations.
Figure 4.B.4 shows the terminal settlingvelocity for spherical particles in air as
a fur.:tion of size, according to equation 4.B.l4. Figure 4.B.5 the settling ve
locity for particles in water and the rise velocity of bubbles in water as a function of
diameter, according to equations 4.B.l4 and 4.B.l5. Note that for the particle sizes
considered, the settling velocity spans an enormous range: seven orders of magnitude
in air and six orders of magnitude in water. As a general rule, settling is unimportant
for particles smaller than about l p,m in diameter.
The particle flux caused by gravitational settling is analogous to the contaminant
flux by advection (equations 4.A.12) .. The magnitude is given by
Jg = Cv
1
The vector form of this relationship is
1
8
(x, y, z) = C(x, y, z)v
1
(4.B.l6)
(4.B.l7)
where C(x, y, z) is the concentration of particles at the point (x, y, z). The vector points
downward, parallel to the gravitational settling velocity, vr Example 4.B.2 presents an
illustration of how the prediction of particle flux can be applied to a practical environ
mental question.
4Jl.2 Soiling Due to Particle Deposition
Studies have shown that a white surface becomes noticeably soiled when 0.2 percent
of its area is covered by black particles soot) (Hancock et al., 1976). Assume that
the same relationship applies for soil dust particles. Estimate the time required for an
initially clean, horizontal surface to appear soiled if it is exposed to an atmosphere
containing 10 llg m
3
of soildust particles of diameter 5 JLm. Assume that the parti
cles are spherical and have a density of 2.5 g cm
3
SOLUTION The particle settling velocity is determined by the Stokes's law expression (Ta
ble 4.B.1):
v = [Ccgd:(p Pt)] = [1.03 X 980 X (5 X 104)
2
( 2.5 )] = O.l
9
ems 1
1
18 p., 18 1.8 X 104
The number concentration of particles is obtained by dividing the mass concentration
by the mass per particle:
10 10
6 . 3 ( 102 1)3
C
X g m X m em 0 061 rt. 1 3
= =.
2.5g cm
3
x ( 11'/6) X (5 X 104 cm)
3
!I
i
!
180 Chapter 4 '"Transport Phenomena
Soiling :e to PilrtiCie DepiJsiiion (
The isgiven by ". .
. , , . :. , ; 1; , . . : :i , :. . . r: . . .
J
8
=: Cv, = 0.061 x 0.19 par:ticles cm:
2
s
1
Each particle a xp, equal to that of a of diameter 5 &J.ffi.
The fractional rateR, at which the surface is coveredis the of AP and 1
8
:
R = id;J
8
= x 104 cm)
2
x o.oi2 cm
2
s
1
= 2!3 x I0
9
s
1
The time required to cover 0.2 percent of the surface is obtained directly as
t =
0
002
= 9 X 10
5
s = 10 days
R
Note that this is similar to the time scale over which household surfaces become per
ceptibly dusty.
4.8.3 Brownian Diffusion
In 4.A.3 we discussed molecular diffusion, a transport mechanism caused by the ran
dom motion of fluid molecules. An analogous phenomenon applies to particles sus
pended in a fluid. This transport mechanism is known as Brownian diffusion (or
Brownian in recognition of the botanist Robert Brown, who in 1827 reported
observing, through a microscope, the wiggling motion of pollen grains suspended in
water. Brownian diffusion results from the random collisions of particles suspended in_
a fluid with surrounding molecules. The overall effect in a fluid with a population of
suspended particles is to cause net transport from high concentration to low concen
tration. The rate of Brownian diffusion is much slower than the rate of molecular dif
fusion because particles are much larger and much more massive than molecules.
Fick's law effectively describes the flux of particles caused by Brownian diffusion
(see equations 4.A.56). A key issue in applying Fick's law for particles is the evalua
tion of the diffusion coefficient, D.
Diffusivity of Particles in Air and Water
The Brownian diffusivity of particles is detemrined by an equation known as the
StokesEinstein relation,
D=kT
f
(4.B.l8)
where k is Boltzmann's constant {1.38 X 10
16
erg K
1
, where the erg is an energy unit
equivalent to 1 g cm
2
s
2
), T is temperature (K), and f is the friction coefficient com
puted according to Stokes's law
066
(2.51 + 0.80 (O.SS X O.l)]= 2.89
c 0.1 exp 0.066
So the diffusivity of this particle in air is
Dair = 1.38 xlo
16
x 293 x 2.89 =
6
_
9
x
cm2 s1
31T(l.8 X 104 X 0.1 X
In water, the slip correction factor doesn't apply. The diffusivity is
D = 1.38 X 1016 X 293 = 4 3 X 108 cm2 s1
water 317'(0.01 X 0.1 X 104) .
Comparing Particle Transport by Settling and Diffusion
It is interesting to compare travel distances for gravitational settling with those for
Brownian diffusion. Figure 4.B.7 makes this comparison for particles in air and wa
ter. Typical settling and diffusion distances are comparable for particle diameters of
n
'l .
L
I
181 ChaPter 4 Transport Phenomena
...
(==
,
,
,
,
,
,
,
,
........ 0
.............. ,
.,.. ................... ...
, 
,
,
,
,
,
,
,
,
,
,
,
Figure 4.B.7 Distance traveled in 10 s by particles in air or water
because of gravitational settling and Brownian diffusion. Particle
settling velocities were determined from Stokes's law_(Table 4.8.1)
with T = 293 K and P = l atm. Diffusion distances were estimated
from expression 4.A.7, u8ing the StokesEinstein relation to compute
diffusivity (equation 4.B.l8). Particle density is 2.5 g cm
3
0.2 tJ.ffi for air and 0.7 ILm for water. (The exact crossing point depends on the as
sumptions about particle density and travel time.) For particles with a diameter of
1 tJ.ffi or larger, diffusion is a relatively unimportant transport mechanism in com
parison with gravitational settling (and other processes that depend on particle mass
or inertia). For particles with a diameter of 0.1 ILm or less, the role of gravitational
settling as a transport mechanism is negligible compared with Brownian diffusion.
4.C MASS TRANSFER AT FLUID BOUNDARIES
Several important phenomena occur at the boundaries of fluids. The rate of contami
nant transport to and from these boundaries may have a strong influence on contami
nant . concentration. This influence occurs in both natural and engineered systems.
Contaminants can enter or leave a fluid at a boundary, and they may also undergo
chemical transformations there. The boundaries of interest include airwater interfaces
as well as boundaries between either air or :water and (a) soil, (b) other solid surfaces,
or (c) nonaqueous liquids such as fuels and solvents.
There is a close relationship between the transport phenomena explored in this
section and the transformation processes involving phase change discussed in 3.B. In
fact, the distinction between transport and transformation is somewhat blurred here.
The kinetics of phase change processes depend, in general, both on the rate of trans
port to or from the fluid boundary and the kinetics of the transformation processes.
Transport and transformation processes occur serially, so the slower process governs
the overall
Transport across airwater interfaces is of particular interest in environmental engi
neering. Several treatment technologies involve transferring pollutants from one phase
,!(,
(
.  ;.: '('
(
c
c
1:
1
p
a
y
0
e
b
$1
a:
fl
k
K
ii
tl
4.C.l M
T
tt
H
is
th
c
th
be
cil
dil
Vo

 'i"'""
!
on the as
ameter of
n in com
dele mass
.vitational
iffusion.
: contami
l contami
i systems.
o undergo
interfaces
1 surfaces,
red in this
in 3.B. In
ured here.
e of trans
processes.
ss governs
ental engi
one phase
'', ,,._ ..
4.C 183
to the other. For example, scrubbers remove acid gases such as sulfur dioxide and hy
drochloric acid from waste air..streams by transferring them to. water, where they can
easily be Air strippers remove volatile organic compounds from water.
Once the organic molecules. are transfened to the gas phase,::they can be more easily
captured by sorption or destroyed by oxidation processes. In nature, airwater ex
changes are also important. The transfer of oxygen from air to water supports aquatic
life. The ultimate fate of many air pollutants involves transfer to cloud or rainwater fol
lowed by deposition to the earth's surface. The uptake of carbon dioxide by the oceans
plays a key role in moderating the impact of fossil fuel combustion on climate.
Transport to a fluid boundary may occur by a Variety of mechanisms. Diffusion is
always present and often is the ratelimiting process because, at rigid boundaries, flow
velocities diminish to zero. Advection usually plays a role in controllillg the thickness
of the layer through which diffusion must occur. For particles, gravitational settling,
electrostatic drift, inertial drift, and other mechanisms may dominate transport near
boundaries.
For engineering analysis of transport processes at fluid boundaries, we seek a de
scription that captures the overall that does not violate central principles such
as mass conservation, and that is practical to apply. We will employ models that link
flux to concentrations .. and may include an empirical parameter. In the case of turbu
lent diffusion, we used an equation inspired by Fick' s law of diffusion, and the empir
ical parameter was turbulent diffusivity. For mas& transfer at boundaries, similarly
inspired flux equations will be written that in,corporate a masstransfer coefficient as
the empirical parameter.
4.C.l Coefficient
The net rate of mass flux between a fluid and its boundary is commonly expressed in
this form:
Jb = km(C C;)
(4.C.l)
Here Jb is the net flux to the boundary (amount of species per area per time). When Jb
is greater than zero, the flux direction is from the fluid to the boundary; when J b is less
than zero, the flux is directed from the boundary to the fluid. The concentration terms
C and C;, respectively, represent the species concentration in the bulk fluid far from
the boundary and the species concentration in the fluid immediately adjacent to the
boundary. The other in this equation, km, is known as a masstransfer coeffi
cient. The masstransfer coefficient commonly has units of velocity (length per time).
Figure 4.C.l shows a simple system for which a masstransfer coefficient can be
directly derived. A glass cylinder is partly filled with a pure volatile liquid (with a sat
Stagnant air
t
t::
.,g
;;
&.
Flux
Volatile liquid C C;
Concentration
Figure 4.C.l A simple system in which a
masstransfer coefficient can be directly
determined.
t
I
I
I
I
I
I
i
i
!
I
;,,
~
l'
'I
184 Chapter 4 Transport Phenomena
uration vapor pressure 1 atnt). 'Ibe remainder of the cylinder'contains stagnant air.
Molecules of the liquid evaporate, diffuse through the cylinder, and escape Jrom the
open top into the free air. Provided that diffusion is not too rapickthe :gu:..phase con
centration of the diffusing species at the liquidgas interface will be detenmned di
rectly asP sa/(RT), whereP sat is the equilibrium vapor pressure of the liquid. Assume
that the concentration at the top of the cylinder is maintained at some value,c, deter
mined by processes occurring in the open air. After an initial transient period, during
which the gasphase concentration profiles may change, a steadystate linear profile
will be established, as depicted in Figure 4.C.l. The diffusive flux through the tube,
Jd, is given by Pick's law as
Jd =Dei c
L
(4.C.2)
The net transport rate from the air to the liquid is equal to the negative of the diffusive
flux, Jd. Comparing equation 4.C.2 with equation 4.C.l, we see that the masstransfer
coefficient for this system is
k =D
m 
L
(4.C.3)
This is a general result. provided that the concentration profile is steady: For pure dif
fusion through a stagnant layer, the masstransfer coefficient is given by the diffusivity
divided by the thickness of the layer.
A second case is illustrated in Figure 4.C.2. Particles are suspended in a fluid
above a horizontal boundary. The fluid is motionless, the particle concentration is uni
form, and the particles migrate only because of gravitational settling. All particles are
assumed to have the same settling velocity, v,. The concentration of particles in the
fluid at the interface is taken to be zero. This may seem peculiar, since the particles
accumulate on the bottom boundary. H.owever, provided resuspension does not occur
(as it will not in a stagnant fluid), once the particles strike the boundary, they are no
longer suspended in the fluid, and so it is reasonable to assign Ci = 0. The gravita
tional flux to the surface, 1
8
, is then given by
0 0
0
0
0
0
0
0
goo
cg
0
0
~
Jg = v
1
C
0
0
0
0
0 0
0
0
0
t V
1
0
0
0
o'b
0
0
Figure 4.C.2 In a uniform suspension of monodisperse
particles settling through a stagnant fluid onto a horizontal
surface, the masstransfer coefficient is equal to the settling
velocity.
(4.C.4)
. .... . \
~
:
I
.... :i, ..
c
c ~
T
S{
tt
e'
S<
P
e;
lr'
Ct
is
V<
dt
ic
in
b(
\\
rn
at.
rn
th
rn
pl
he
b3
te1
an
(fl
m
Fe
us
lat
sy
lal
Fi.
Th
Ac
f u ~
to
co
'
'stagnant air.
tpe from the
.;phase con
termined di
Assume
C, deter
during
inear profile
gh the tube,
(4.C.2)
the diffusive
nasstransfer
(4.C.3)
For pure dif
te diffusivity
in a fluid
ration is uni
particles are
rticles in the
the particles
>es not occur
',they are no
The gravita
(4.C.4)
,. ...,,'.!: ..
iii
I
_c_;.,L_
4.C Boundaries 185
Comparing this result with equation 4.C.t, we see that for this.case the masstransfer
coefficient is equal to the particle settling velocity:
km = V
1
(4.C.5)
This too is a general result. Whenever contaminant. transport to a surlace occurs
solely because of a net migration velocity, the masstransfer coefficient is equal to
that velocity.
These examples yield exact expressions for the masstransfer coefficient. How
ever, in most applications, the use of a masstransfer coefficient is a simplified de
scription of what is a very complicated set of processes. a high degree :of
precision should not be expected in problems involving mass transfer at boundaries.
Applyitig equation 4.C.l wisely requires a sound understanding of the meaning of
each of the four variables. First, let's consider the concentration at the interface, C;. In
many cases, C; can be taken to be zero. This is appropriate when a transformation pro
cess that is fast and irreversible occurs at the boundary. Particle deposition by settling
is one example where C; is zero: When a particle strikes a surface with a low incident
velocity, it adheres essentially immediately. Chemical transfofmations can also pro
duce an interface concentration of zero if transport, rather than surfacereaction kinet
ics, is the ratelimiting step. In some cases, such as that shown in Figure 4.C.l, the
interface concentration can be determined by assuming local equilibrium at the
boundary ..
An important issue arises concerning species concentration in bulk fluid, C:
Where should it be determined? The issue is easily resolved when the fluid is well
mixed outside of a thin boundary layer (see Figure 4.C.3). Then C is the concentration
anywhere outside the boundary layer. some circumstances arise in environ
mental engineering in which species concentrations v.ary strongly with position
throughout the fluid. In such cases, the use of a masstransfer coefficient may yield no
more than a rough approximation of the masstransfer rate at surfaces.
A arises when the fluid boundary occurs at a surface that has a com
plex texture. Iflb represents the quantity of contaminant transferred per area per time,
how do we define the area? Typically, the flux to rough surfaces is determined on the
basis of a superficial or apparent area. fu other rather than determining the in
terface area and the masstransfer coefficient separately, their product is determined
and the masstransfer equation is rewritten in terms of total net transfer of species
(flux times area) rather than in tenns of flux.
The final issue to address is how an appropriate masstransfer coefficient is deter
mined for a given situation. There are two main approaches, and both are widely used.
For systems with fairly. regular geometries, the masstransfer coefficient is calculated
using existing correlations based on theory or experimental data. Some of these corre
lations are presented below. A second approach, commonly used for more complex
systems, is to calculate masstransfer coefficients based on experiments conducted in
laboratory or field settings.
Film Theory
The simplest model system that includes fluid flow divides the fluid into two layers.
Adjacent to the surface is a stagnant layer, or film, through which species must dif
fuse. The concentration profile within the film is assumed to.be linear, corresponding
to steady diffusive flux. In the second layer, the. fluid is well mixed and the species
concentration is uniform
'
y;
186 Chapter 4 Transport PhenOmena
C;
Concentratioa
Flux
c
Wellmixed
Stagnant fluid film
Figure 4.C3 Schematic of mass transfer to a
surface according to film theory.
Mass transfer from the fluid to a surface, according to film theory, is depicted in
Figure 4.C.3. This situation is almost identical to that depicted in Figure and so,
in analogy with equation 4.C.3, it should be clear that the masstransfer coefficient for
this case is
D
k =
m L
'f
(4.C.6)
where L
1
is the film thickness. Film theory suggests that for given flow conditions, the
masstransfer coefficient should scale in direct proportion to species diffusivity (km oc
D). Experiments consistently demonstrate that, in systems with fluid flow, the mass
transfer coefficient flow increases in proportion to Da._, with a < 1. The key weakness
of film theory is its dependence on a specific value of the film thickness, 4 In most
circumstances, there is no practical way to determine L
1
that is independent of a mea
surement of mass transfer (or heat transfer) to a surface. Furthennore, the effective
thickness of the fiim through which species must diffuse varies with species diffusiv
ity: A higher diffusion coefficient results in a larger film thickness. Still', although not
entirely accurate, film theory provides a helpful conceptual picture of interfacial mass
transfer. ,
Penetration Theory
Recall (equation 4.A.8} that the characteristic time required for a steadystate concen
tration profile to be established by diffusion is given by L
2
(2Dt
1
where L is the dis
tance over which diffusion occurs. In film theory, the boundary must be in contact
with the fluid for a minimum time ofT L}(2D)
1
for the concentration profile to ap
proach the constantslope condition depicted in Figure 4.C.3. In some circumstances,
the contact time between a boundary and a fluid is not long enough for film theory to
apply. A second conceptual model, known as penetration theory, has been developed
to address this case.
The model is based on transient diffusion in one dimension. At timet= 0, the
concentration in the fluid is assumed to be uniform everywhere except at the position
of ,the boundary, where it is Then diffusion to the surface begins and a boundary
layer begins to grow (Figure 4.C.4). Fluid motion affects the contact time between the
fluid and the boundary.
Analysis of time""dependent diffusion to a flat surface yields the following expres
sion for the masstransfer coefficient:
km(t} =
instantaneous
(4.C.7)
..... J
.g
!
11
th
th
cc
Fr
ef
cc
is
at
ne
di
fu
Bt
Tr
dil
in.
de
co
ef
fa<.
thf
ris
u
s transfer to a
s depicted in
and so,
oefficient for
(4.C.6)
mditions, the
. usivity (km ex
,w, the mass
;.ey weakness
s, Lf In most
ent of a mea
the effective
:cies diffusiv
although not
mass
state concen
! L is the dis
be in contact
1 profile to ap
ircumstances,
film theory to
.!en developed
ime t = 0, the
at the position
nd a boundary
1e between the
lowing expres
(4.C.7)
\
t
d
.g I ' < '2 < t3
4.c :Massn:anst at Fluid Bound&rii;s 187
 
.Fluid
Boundary
Figure 4.C.4 Schematic of mass
transfer to a surface according to
penetratio1.1 theory.
This is the instantaneous masstransfer coefficient at time t. Because the distance
throughwhich species must diffuse increases with time, k, decreases as t increases. If
the contact period is maintained for some interval t*, the timeaveraged masstransfer
coefficient is obtained by integration:
t
km = km(t) dt = 2[_Q_]
112
0 1rt*
average (4.C.8)
From equation 4.C.8, we see that penetration theory predicts that the masstransfer co
efficient should increase in proportion to the square root of species diffusivity. By
contrast, we have just seen that film theory predicts that the masstransfer coefficient
is proportional to diffusivity .. The reason for the difference lies in the assumptions
about the distance through which species must diffuse. In film theory, the film thick
ness is assumed to be constant and so is independent of D. In penetration theory, the
diffusion distance increases with time, and the rate of growth depends on species dif
fusivity.
BoundaryLayer Theory: Laminar Flow along a Flat Surface
Transport from moving fluids to boundaries is caused by simultaneous advection and
diffusion, with advection being stronger far from the boundary and diffusion dominat
ing adjacent to the boundary. Film and penetration theories simplify the analysis by
decoupling advection from diffusion. Boundarylayer theory can predict masstransfer
coefficients for simple flows and geometries while simultaneously accounting for the
effects of both transport mechanisms.
Let's consider the case of laminar fluid flow at velocity U, parallel to a flat sur
face (see Figure 4.C.5). The species concentration is Ci at the surface and is C far from
the surface. Within the boundary layer there is a concentration gradient, which gives
rise to diffusion toward the surface. There are also advective velocity components in
u
l
x
ci
, I<""': I < . I L<_
c
Figure 4.C.S Schematic of
mass transfer to a surface
according to boundarylayer
theory for the case of a flat
surface parallel to a uniform,
laminar fluid flow.
_r
188 Chapter 4 Transport Phenomena
', ..the xdirection (relatively strong} and the zdirection (relatively weak} that affect the
concentration profile. The characteristic thickness of the boundary layer for a contam
inant species is the distance from the surface 'over which the concentration increases
to approximately C. As shown in Figure 4.C.5, the boundarylayer thickness grows
withincreasing distance downstream of the leading edge. The thickness of this bound
ary layer at any xposition is a function of species diffusivity, with higher diffusivity
causing a thicker boundaly layer. For any given species, a thicker boundary layer
means slower mass transfer to the surface. Because of species loss at the surface, the
boundarylayer thickness grows with downstream distance and the rate of mass trans
fer correspondingly decreases.
This problem is analyzed using equations that describe the conservation of fluid
mass, momentum, and species in the boundary layer {Cussler; 1984; Bejan, 1984).
The result is a masstransfer coefficient calculated at a specific position x downstream
of the leading edge of the surface:
(
u)u2
km(x) = 0.323 :; v116D213 local
(4.C.9)
where v is the kinematic fluid viscosity. (Recall that v = p/p, where p.. is the dynamic
fluid viscosity and pis the fluid density.) The overall masstransfer coefficient to the
surface is obtained by averaging over the length of the smface:
L
km = i: L km(x) dx = 0,646(f
2
v116D213
average
(4.C.10)
Equation 4.C.l 0 gives the average masstransfer coefficient for this flow system for a
surface from the leading edge to a distance L downstream. Note that the masstransfer
coefficient, km, varies with the diffusion coefficient raised to the 2/3 power. It is gener
ally true that when advection and diffusion are combined, the masstransfer coeffi.:.
cient increases with diffusivity raised to some power between 0.5 (penetration theory)
and 1 (film theory).
4.C.2 Transport across the AirWater Interface
. In en:vironmental engineering the rate of transport of a molecular species
across an airwater Interface is described by an expression similar to equation 4.C.l:
Jgl = kgl( Cs C)
(4.C.ll)
where Jg
1
is the net flux of a species from the gas phase to the liquid phase (mass per
interfacial area per time), kg
1
is a masstransfer coefficient (length per time C is the
concentration of the species in the bulk liquid phase, and Cs is the saturation (or equi
librium) concentration of the species in the liquid phase that corresponds to t.he given
partial pressure of the species in the gas phase. 1Jpically, Cs is obtained from
law (see 3.B.2). When Cs exceeds the current aqueous concentration, Jg
1
> 0 and net
transfer occurs from the gas to the liquid. when the water is supersatu
rated with respect to the gas phase, C > Cs, so Jgt < 0, and equation 4.C.ll predicts
a net rate of volatilization.
Ill general, the masstransfer coefficient kg
1
depends on fluid flow near the inter
face and on species diffusivity in both air and water. The film model introduced in the
previous section can be extended to. a twofilm model, as depicted in Figure 4.C.6,
with the airwater interface as the boundary. In this model, stagnant film layers exist
1
1"
'
'
0
u
a(
e<.
fi
li
e<
w
fi
w
w
te
ar
w
us
e0
he,
wl
an
that affect the
for a contam
tion increases
ckness grows
Jf this bound
er diffusivity
>nndary layer
e surface, the
lf mass trans
ation of fluid
Bejan, 1984).
r downstream
(4.C.9)
; the dynamic
fficient to the
(4.C.l0)
1 system for a
masstransfer
er. It is gener
ansfer coeffi.:.
ration theory)
!cular species
,ation 4.C.l:
(4.C.ll)
.ase (mass per
ime), Cis the
1tion (or equi
ls to the given
from Henry's
:I > 0 and net
: is supersatu
.C.ll predicts
near the inter
roduced in the
Figure 4.C.6,
m layers exist
J
Air
L_
4.C Mass TrariSferat:Fluid BOundaries 189
Pi P Partial pressure.
Turbulently
mixed zone
..
E
 8
s '
 ___
c::
.9
Water
c ci
Turbulently
mixed zone
Concentration
Figure 4.C.6 Schematic of the
twofilm model for estimating mass
transport across an airwater
interface.
on either side of t..lte boundary through which species transport occurs only by molec
ular diffusion. Outside of its stagnant film layer, each fluid is well mixed. Immediately
adjacent to the interface, the partial pressure in the gas phase, Pi .. is assumed to be in
equilibrium with the aqueous concentration, C;, as described by Henry's law. As in the
film model, the concentration profiles in the stagnant film layers are assumed to be
linear. Also, because of mass conservation, the flux through the air layer must be
equal to the flux through the water layer.
Applying Fick's law, we can write the gasside flux (from air to the interface) as
_ . (P P;)IRT
Jgl Da (4.C.12)
T.
a
where D a is the species diffusivity through air and La is the thickness of the stagnant
film layer in the air. Likewise, the liquidside flux (from the interface into the water) is
c.c
J gl = D w_.;..
1

Lw
(4.C.l3)
where D w is the species diffusivity in water and Lw is the filmlayer thickness in the
. water. Since we don know either P; or C;, we would like to eliminate these parame
ters from the expressions. So far, we have two equations but three unknowns (Jg
1
, C;,
andPJ
The third equation comes from the equilibrium relationship at the interface:
ci = K
8
P; (4.C.l4)
where KH is the Henry's law constant for the species (see Table 3.B.2). Now, we can
use algebra to derive an expression for flux that is in the form of equation 4.C.ll. Use
equation 4.C.l4 to replace Pi with CJKHin equation 4.C.l2. Then equate the right
hand sides of equations 4.C.12 and 4.C.13 and solve for Ci to obtain
C.= aCs + C
' 1 +a
(4.C.15)
where
DaLw
a = "'"'
DwLaK8RT
(4.C.16)
and
. cs = KHP
(4.C.l7)
,,
lfransport Phenomena
Next substitute for C
1
from equation,4.C.l5 into equation 4.C.l3. After some alge
,braic manipulation, one arrives at equation 4.C.ll, where
. ' .. ,( . . . .. ,
... , , kg
1
= Dw(__!C) ::;
1
(4.C.l8)
Lw 1 +a L.,., La
+KHRT
Dw Da
The film thicknesses, L_.. and La, cannot be measured. So for practical application,
we rewrite equation 4.C.18 in this form:
l 1 KHRT
=+
kg/ kl kg
(4.C.l9)
where k
1
and k
8
are the respective masstransfer coefficients through the liquid and gas
boundary layers near the interface, each corresponding to the diffusivity divided by
the film thickness (Dw/ Lw and D
0
/L
0
, respectively), as in equation 4.C.6. The factor
KH appears with kg in this expression because kg
1
is used with the aqueous concentra
tions to determine flux (equation 4.C.ll) The factor RT is needed to convert partial
pressure to molar concentration, since we write Henry's law in a way that relates
aqueous molar concentration to gaseous partial pressure.
Equations 4.C.ll and 4.C.l9 are together sometimes called the tworesistance
model for interfacial mass transfer. Since species must be transported through fluid
on both sides of the interfaCe, the total resistance (kJ) is the sum of the resistance in
the liquid side of the interface (k[
1
) plus the on the gas side (KHRTk;
1
).
From equation 4.C.l9 we see that the relative sizes of the gas and liquid resis
tances vary according to the Henry's law constant, KH. The diffusion coefficients, D,
of molecular species in a given fluid vary byabout one order of magnitude (4.A.3).
The film resistance tenns k
1
and kg are expected to vary by no more than D to the frrst
power (4.C.l ). The Henry's law constant, on the other hand, varies by at least eight
orders of magnitude among species of interest in environmental engineering (see Ta
ble 3.B.2). Therefore, even for fixed flow conditions, the interfacial masstransfer co
efficient, kgb may vary greatly from one species to another according to the value of
the Henry's law constant. This.point is illustrated in Figure 4.C.7.
Liss and Slater (1974) reviewed available information on the mass transfer of
species between the oceans and the atmosphere and concluded that liquidside and
gasside masstransfer coefficients of k
1
= 0.2 m
and kg = 30 m h
1
apply for
average meteorological and ocean current conditions. These coefficients are sug
gested to be approximately correct for species with molecular weights between 15 and
65 g/mol. Figure 4.C. 7 shows how the overall masstransfer coefficient varies with
the Henry's law constant for molecular species exchange between the atmosphere
and the seas. For sparingly soluble gases such as oxygen (KH = 0.0014 M atm
1
), the
resistance lies entirely on the liquid side and an overall average masstransfer coeffi
cient of approximately kg
1
= 0.2 1nlh applies. On the other hand, the resistance for a
highly soluble species such as formaldehyde (K
8
= 6300 M atm
1
) lies entirely on
gas side.
The liquidside and gasside masstransfer coefficients can be combined with values
of species diffusivities to estimate effective film thicknesses: La  D ak;
1
 2 mm and
Lw  D wk )/  20 J.Lm. We see from these estimates that diffusive transport over very
small length scales controls the overall rate of interfacial mass transfer. The time scales
required for steadystate concentration profiles to be achieved in gas and liquid films of
this size are approximately Tg L:(2Da)
1
 0.1 s and T
1
 L!C2Dw)
1
 0.2 s.
'===
,.
'f:}
'
f;
t;:r
t,c
!
......_
Fi
th
w;
kg
ga
sp
ef
Fe
Fo
In
SUl
me
mJ
ten
COl
the
tra1
some alge
(4.C.l8)
tpplication,
(4.C.l9)
uid and gas
divided by
The factor
concentra
tVert partial
that relates
rough fluid
!sistance in
HRTk;
1
).
iquid resis
D,
le (4.A.3).
>to the first
t least eight
ing (see
transfer co
.he value of
transfer of
idside and
1
apply for
tts are sug
veen 15 and
varies with
atmosphere
{ atm
1
), the
asfer coeffi
stance for a
entirely on
l with values
2 mm and
'rt over very
:! time scales
1uid films of
0.2 s.
4.C 191
Sparingly soluble:
Liquid film resistance
dominates
Highly soluble:
Gas film resistance
dominates
Figure 4.C.7 Dependence of the overall masstransfer coefficient on
the Henry's law constant for average conditions in large bodies of
water. The curve traces equation 4.C.l9 with k
1
= 0.2 m h
1
,
kg = 30m h
1
, and T = 293 K (Liss and Slater, 1974). '
For natural bodies of water, the following expressions can be applied to estimate
gasside and liquidside masstransfer coefficients in relation to environmental and
species conditions (Schwarzenbach et al., 1993). For the gasphase masstransfer co
efficient,
D ]213
kg = a
2
_
1
(7 U
10
+ 11)
.26 ems
(4.C.20)
For oceans, lakes, and other slowly flowing waters,
kl = [ Dw ]0.57
2.6 X I(Y
5
cm2 s1 (0.0014Uio + 0.014)
(4.C.21)
For rivers,
[
D ]o.s1(U )112
kl = 0.18 w
2.6 X 10
5
cm
2
s
1
dw
(4.C.22)
In these expressions, U
10
is the mean wind speed measured at 10m above the water
surface (units are rn!s). The term Uw is the mean water velocity in the river (rnls). The
mean stream depth is dw (m). The equations are written so that k
8
and k
1
have units of
mlh. Example 4.C.l illustrates how these equations are used.
In general, for interfacial transfer of molecular species in any airwater flow sys
tem, the overall masstransfer coefficient for any species can be determined by mak
ing measurements of k
81
for a minimum of two species with known Henry's law
constants, provided one is sparingly soluble and the other is highly soluble. From
these measurements, one can determine the values of k
1
and Then the overall mass
transfer coefficient for any other species can be estimated using equation 4.C.l9.
r :191 lChapter 4 H !fnirispott Phenomena
!1
,MassTransfer Coef!ieieittJO,.iJi:Yfeli.in;tiRwer: ..... ,
. ' . l . '. _ .. .. : . .. . . . ... ,:
In Nebraska, the Missouri River has 'in andfiows at a ntean veloc
ity of 1. 7 5 mls (Fischer et al., that the wind speed at l 0 m iS 4 m/s. Es
timate the overall masstransfer coefficient for .. (0
2
) from the atmosphere to
the river.  
SOLUTION The (diffusion coefficient of 0
2
in water is Dw = 2.6 X 10
5
cm
2
s:
1
(Table
4.A.3). From equation 4.C.22, the liquidside masstransfer coefficient is estimated to
be k
1
= 0.14 mlh. The diffusion coefficient for 0
2
in air is D a = 0.178 cm
2
s
1
(Table
4.A.2). From equation 4.C.20, the gasside coefficient is estimated to be
kg= 30 mlh. The Henry's law constant for oxygen is KH = 0.0014 M atm
1
(Table
3.B.2). With R = 0.0821 atm K
1
M
1
and T = 293 K, we predict from equation
4.C.l9 that kg
1
= 0.14 mlh. As expected for a sparingly soluble gas such as oxygen,
mass transfer through water adjacent to the interfacial boundary controls the overall
rate of the process.
4.D 1RANSPORT IN POROUS MEDIA
Porous materials are solids that contain distributed void spaces. Permeable porous ma
terials contain an interconnected network of voids or pores that permit bulk flow of
fluid through the material. Soil is a common example of a permeable porous material.
Usually, the pores are highly variable in shape and size, resulting in complex flow
channels. :
Environmental engineers study the movement of fluids and contaminants through
porous media for several reasons. Many treatment technologies for removing pollut
ants from water and air entail passing the fluid through a porous materiaL In munici
pal treatment plants. for drinking water is passed through sand filters to
remove small, suspended particles. Drinking water is also sometimes treated by pass
ing it through a column of granular activated carbon to remove dissolved organic mol
ecules that are harmful or that may cause taste and odor problems. Air used in
industrial processes is often passed through fabric filters to remove suspended parti
cles. Filters of granular activated carbon are also used to remove volatile organic com
pounds from gas streams. Many hazardous waste treatment technologies also involve
passing a fluid through a porous material. Much attention in hazardoUE waste manage
ment focuses on characterizing contaminant migration in subsurface soils, either to
predict the threat to water quality or to evaluate a treatment strategy.
The aim of this section is to provide an introduction to transport in porous media,
emphasizing . the movement of water and air and the contaminants dissolved or sus
pended within these fluids. The behavior of nonaqueousphase liquids in subsurface
environments is also important in environmental engineering, but the complexities
that must be addressed render it beyond the scope of this book. Application of the
ideas introduced here filtering contaminants from water are discussed in Chapter
6. 'around water contamination is addressed in Chapter 8.
Before proceeding, we must define some . basic terms and concepts that arise
when dealing with through porous materials. One quantitative descriptor of a
porous material is its porosity, here given the symbol f> and defined as
<P = pore volume
total volume
(4.D.l)
4.D.l
Th
ai1
4.I
sp<
mt'
A
po
fib
Th
gn
po
wi
SOl
int
na'
re1
bu
I at
Th
po
de
uh
rO\
Cf{
ter
of
me.
pi'
sis
ite
of
of
Flu
Du
intr
ter
Wi
mean veloc
is"4 rnls. Es
mosphere to
1
2
s
1
(Table
estimated to
n
2
s
1
(Table
jmated to be
atm
1
(Table
Jm equation
:1 as oxygen,
's the overall
e porous rna
bulk flow of
ous material.
omplex flow
1ants through
oving pollut
tl. In munici
and filters to
ated by pass
organic mol
Air used in
pended parti
organic corn
also involve
'aste manage
oils, either to
media,
;olved or sus
in subsurface
complexities
ication of the
ed in Chapter
!pts that arise
:iescriptor of a
(4.D.l)
I
I
L
,AD Transport in Porous Media 193
The pores may contain both air and water (and, in general, other fluids). We define the
airfilled porosity, .tz' and the waterfilled porosity, .p.,, in analogy with equation
4.D.l, but with the numerator replaced by the pore volumefilled with air or water, re
spectively. If the air and water are the only fluids contained in the pores, the porosities
must satisfy this relationship:
cf> = cf>w + cf>a
(4.D.2)
A porous material is saturated with a particular fluid if that fluid entirely fills the
pores. So, for example, a medium is saturated with water if t:f>w = q,.
Most porous materials encountered in environmental engineering are granular or
fibrous. Granular materials, such as soils, typically have porosities in the range 0.3
0.7. The porosities of fibrous materials are usually higher, sometimes as high as 0.99.
These materials may have two distinct classes of pores, those that are external to the
grains or fibers and those that are internal. Bulk fluid flow occurs only in the external
pores, but contaminants can migrate by diffusion into the internal pores and interact
with the solid surfaces there. This is especially important for porous
sorbents, such as activated carbon, which have large internal porosities and enormous
internal surface areas. However, in this section, we will emphasize fluid and contami
nant behavior in the pores that are external to grains and fibers.
Two densities are commonly defined for a porous solid The solids Ps'
represents the mass of solid per volume of solid (often including internal pores). The
bulk density, ph, represents the mass of solid per total volume. These measures are re
lated by the total porosity:
Pb = Ps( 1  4>)
(4.D.3)
The solids density of soil grains is fairly constant at 2.65 g cm
3
Given a range of
porosities of 0.30.7, the bulk density would be in the range 0.81.9 g cm
3
Soil bulk
density varies with grain size, but the dependence is not strong. In soil, as in any gran
ular material, porosity tends to be higher when grain sizes are distributed over a nar
row range. With a broad distribution of grain sizes, smaller grains can fill the pores
created by larger reducing overall porosity.
Porosity is an area characteristic as well as a volume characteristic of granular ma
terials. Imagine a plane slicing through a porous material. The area porosity is the ratio
of the area of the plane that intersects pores to the total area that intersects the porous
material. Conveniently, if pores are randomly distributed and the number of pores in a
plane is large, then the area porosity is equal to the porosity measured on a volume ba
sis. This conclusion is reached by considering a porous material as a collection of infin
itesimally thin slices. The volume porosity of the whole is the average of the porosities
of the individual slices. If these slices include a random distribution of a large number
of pores, then the porosity of each slice will be close to the mean for all slices.
4.D.l Fluid Flow through Porous Media
During the middle of the nineteenth century, Henri Darcy, a French engineer who was
interested in the development of groundwater resources, studied the hydraulics of wa
ter flow through a sand column using an apparatus like that shown in Figure 4.D.l.
With experiments conducted under steady flow c'onditions, he found that the follow
ing relationship described his results:
Q = KA!:ih
L
(4.D.4)
J
, 194 Chapter 4  Phenomena
'\,
area=A
1
Q
llh
l
Figure 4.D.l Apparatus similar to
that used by Darcy to study the
hydraulics of water flow through
where Q is the volumetric flow rate (m
3
s
1
), llh is the change in fluid head from the
inlet to the outlet of the column (m), A is the crosssectional area of the column (m
2
),
and L is the length of the column (m). The parameter K, which has units of velocity,
was constant for a given sand but varied from one sand sample to another, increasing
with increasing grain size.
This relationship has been generalized and is oow commonly known as Darcy's
law. For water flow in one dimension through a watersaturated material, Darcy's law
can be written as l
U = Kdh
dl
(4.D.5)
where U is called the Darcy velocity, filtration velocity, or superficial flow velocity, K
is called the hydraulic conductivity; and dhldl is the rate of change of pressure head
with distance. In relation to Darcy's experiment, U represents QIA, and the hydraulic
gradient, dhldl, replaces .1.h/L. The filtration velocity (U) should not be confused with
the local velocity of water through the pores. Rather, it represents the average volu
metric flow of water per unit total crosssectional area of the porous material. Since
solids occupy some area, and since water can flow only through pores, the average lo
cal velocity of water in the pores must be higher than the filtration velocity. The minus
sign in Darcy's law, like the minus sign in Pick's law, reminds us that water flows
from high to low pressure head, just as molecules diffuse from high to low concentra
tion. Since head has units of length, dh/dl is dimensionless, and so the hydraulic con
ductivity must have the same units as U, velocity.
Another form of Darcy's law applies to porous media saturated with any fluid:
U= _!dP
p. dl
(4.D.6)
where k is called the intrinsic permeability, or simply permeability, of the porous ma
terial; p., is the viscosity of the fluid; and dP/dl is the derivative of dynamic pressure
with respect to distance. This fonn of Darcy's law assumes that the fluid is incom
pressible, which, for air, would mean that the pressure drop across the medium must
be much. smaller than the inlet pressure.
The hydraulic conductivity in Darcy's law (equation 4.D.5) depends primarily on
two properties of the system: the viscosity of the fluid and the size of the pores. Fluids
thr
flo
Th
pel
ve'
me
ffiL
pn
lll<
fie
cie
in!
ac'
pe:
wl
H<
da
4.1
th<
r
to
r
10
_L
Cl
gr.
tus similar to
study the
>wthrough
head from the
column (m
2
),
,ts of velocity,
1er, increasing
.vn as Darcy's
J, Darcy's law
(4.0.5)
ow velocity, K
pressure head
l the hydraulic
confused with
average volu
naterial. Since
he average lo
ity. The minus
at water flows
concentra
hydraulic con
h any fluid:
(4.D.6)
porous ma
1amic pressure
luid is incom
; medium must
is primarily on
te pores. Fluids
L._
, 4D Trimsport in Porous Media 195
that are more viscous flow more slowly, and materials with smaller pores pennit less
flow. The second form of Darcy's law (equation 4.0.6) separates these two properties.
The intrinsic permeability is a function only.of the porous material and does not de
pend on the fluid properties.
Given the units of viscosity (e.g., kg m
1
s
1
), pressure derivative (kg m
2
s
2
), and
velocity (m s
1
), we see that permeability has units of length squared. For a porous
medium made up of uniform spherical grains, the permeability increases approxi
mately in proportion to the square of the grain diameter.
The dynamic pressure (P) in equation 4.0.6 is the difference between the total
pressure and the hydrostatic pressure. In the absence of motion, fluid pressure must
increase with depth to support the mass of the fluid suspended above it against the ac
celeration of gravity. This hydrostatic change in pressure with height does not induce
flow.
The difference between the two forms of Darcy's law lies primarily in the coeffi
cients K and k. By noting that head loss corresponds to dynamic pressure drop accord
ing to = where Pw is the density of water and g is gravitational
acceleration, we can show that the hydraulic conductivity is related to the intrinsic
permeability by
K= kpwg
ILw
where ILw is the dynamic viscosity of water.
(4.D.7)
Intrinsic permeability, k, may be expressed in ordinary area units such as m
2
However, the permeabilities of ordinary materials are so low that a special unit, the
darcy, has been defined for permeability, with 1 darcy = 0.987 X 1 o
12
m
2
Figure
4.D.2 shows representative permeabilities and hydraulic conductivities of soils. Note
the enormous range of values between homogeneous clays and coarse sand or gravel.
o
s::
C!l
<I)
<I)
...
<1l
0
u
e
...
.8
a
;:l
t

ws w9
,
104
l02
"0
s::
C!l
<I) "0 "0
E Q >
.E
"Or>4>0>
v ...
e E eg ]e
=
13 a
;:J u ::::: Ui::>
>.
n
>. 0
"0 >.
s:: 4J
<1l :::::
en en
0
t + + + tt + t +
lQ11 to13
10
1s
102 lQ2
l04 l06 to
8
0.6mm 60J.Lm 6p.m 0.6 p.m
Permeability (m2)
Permeability ( darcy)
Hydraulic
conductivity (mls)
Characteristic
grain diameter
Clean Clean sands, Very fine sands, Homogeneous
gravel clean sand and organic and clays
gravel mixtures inorganic silts,
mixtures of sands,
silt and clay, etc.
Figure 4.D.2 Permeability
and hydraulic conductivity
scales, indicating represen
tative values for soils and
gravel (Terzaghi and Peck,
1967; Tuma and Abdel
Hady, 1973). Characteristic
grain diameters are com
puted from the Carman
Kozeny equation (4.D.8),
assuming cp = 0.5.
196 Chapter 4 'Transport Phenomena
Area=A
v
R
..
Darcy's law Ohm's law
Q K 1
;r=TAh I=RV
Flow per area (QIA) Current(/)
Head loss (M) Potential (V)
Column length to Figure 4.D.3 The analogy between
hydraulic conductivity (UK) Resistance (R) law and law.
Fluid flow through a sand column is analogous to electrical current flow through
a resistor. Figure 4.0.3 makes the showing that the ratio of the column
length to hydraulic conductivity acts like a to fluid flow driven by a loss in
pressure head.
A widely used expression that relates permeability to grain size is known as the
CarmanKozeny equation. It was derived by analyzing flow through porous media in
analogy to flow through a bundle of small but with varying size and
tation (Dullien, 1979), giving
<P3d2
k= g
180(1  </1)
2
(4.D.8)
where is the grain diameter. For grains that are not spherical, dg is replaced by t/1 deq
where t/1 is known as the sphericity of the grain and deq is the equivalent diameter. The
sphericity is the ratio of the surface area of a sphere with the same volume as the grain
to the (external) surface area of the grain. Sphericities of materials used in granular
bed filters typically range from 0.45 to 0.8 (Cleasby, 1990). The equivalent diameter is
that which produces a sphere with the same volume as the grain. Example 4.D.l
shows how the CarmanKozeny relationship is used.
, EXAMPLE 4.D.1 Hydraulics for a Granular Activated Carbon Filter
A filter of granular activated carbon is used for treating drinking water. It has the fol
lowing characteristics, which are typical for municipal water treatment (Cleasby,
1990; Snoeyink, 1990). Estimate the permeability and the head loss.
d = lmm
eq
t/1 = 0.75
4> = 0.5
L = lm
U=3mh
1
Equivalent grain diameter
Sphericity
Porosity
. Bed depth
Filtration velocity
SOLUTION Substitution into equation 4.0.8 yields an estimate of the permeability:
k = 0.5\0.75 X 1 X 10
3
m)
2
= 1.
6
X
10
9m2
180(1  0.5)
2
' .. "0:....,
,, i<:
J
4.D.2
Fro
Tht
Tht
Cor
Al1
COl
the
am
grz
na1
tw<
tex
sur
rou
COl
the
not
tiOI
siti
DiJ
Mc
soi
10,
nol
flu.
fus
cla
fus
, /. ) '
between
flow through
f the column
1 by a loss in
as the
ous media in
ze and orien:.
(4.0.8)
aced by tjJ deq
The
e as the grain
l in granular
lt diameter is
ample 4.0.1
[t has the fol
(Cleasby,
lility:
I
I
t_
,4D. : ,Trimspot;t in Porous Media 197
' , . / . . ' ' ., '
Hydraulics for a Granular Activated Carbon 'Filter (continued)
 . '
From equation 4.0.7, the hydraulic is
K = 1.6 x 10
9
m
2
X 1000 kg m
3
X 9.8 m s
72
=
0
.
015
m s1
0.001 kg m
1
s
1
The head loss is determined from equation 4.D.5:
Ah =Ldh = LU
di "K
= 1m X
3
m h
1
1 h
0.015 m sl X 3600 s = 0.06 m
The head loss in this case is about 6
4.0.2 Contaminant Transport in Porous Media
All of the mechanisms that cause contaminant transport in bulk fluids also act on
contaminants suspended in fluids in porous media. Contaminants are advected with
the fluid flow. Molecules diffuse within the fluid through the pores. Particles settle
and undergo Brownian motion. Contaminants sorb onto and within porous media
grains. Chemical or biological reactions may cause generation or decay of contami
nants. If both air and water are present in the pores, contaminants can partition be
tween the two fluids. and migrate within both. Additional transport mechanisms
arise, such as surface diffusion, but discussion of these is beyond the scope of this
text.
Because of the large surface area of solids in contact with the fluid, contaminant
surface interactions may assume a particularly important role in transport through po
rous media. Particles may contact and adhere to the solid grains or fibers. Molecular
contaminants may sorb onto the solid surface and may undergo chemical reactions
there. Our attention in this section is focused mainly on transport mechanisms that do
not involve pollutantsurface interactions. The modeling of sorption and transforma
tion reactions in porous media is discussed in 5.B, and applications of particle depo
sition in porous filters are described in 6.<;.2 and 7 .C.l.
Diffusion
Molecular diffusion through porous materials affects the migration of gases through
soils. In groundwater, diffusion is slow (recall that molecular diffusivities in water are
iO,OOO times smaHer than in air) and therefore of little importance. In treatment tech
nologies, transport is generally dominated by advection because of the need to treat
fluids quickly.
In this discussion, we will emphasize gasphase diffusion. Pick's law relates dif
fusive flux through a porous medium to the concentration gradient, but requires some
clarification and adjustment because of the presence of the solids. For molecular dif
fusion through a porous solid! Pick's law is written in one dimension as
Jd= D dC
edx
(4.0.9)
'"
l
198 Chapter 4 Phenomena
. "'For transpOrt applications, Fick's bewtitteiiitfveetorform:
1
t = D (ac ac ac)
d ox' oy' dZ
(4.0.10}
Here J d representing diffusive flux through the porous medium, gives the quantity of
contaminant transported per total area (not just pore area) per time. The parameter De
is an effective diffusion coefficient, and Cis the species concentr3:tion in the pores
(per pore volume, not per total volume). These equations have the same form as Fick's
law for bulk fluids (equations 4.A.56), but each of the parameters has an altered
meaning.
The effective diffusion coefficient through a porous material is smaller than the
corresP,onding ordinary diffusion coefficient for the given contaminant/fluid combina
tion. For gas molecules in a granular material, such as soil, ilie following expression is
widely used to estimate the effective diffusivity (Millington, 1959):
<P 1013
D =Da
e </>2
(4.0.11)
In vadosezone soils (i.e . above the groundwater table), typical values of airfilled and
total porosity are cf>a = 0.2 and <f> = 0.4. According to equation 4.D.ll, the effective
diffusivity would be reduced to 0.03D in this case. For airsaturated pores, equation
4.0.11 reduces to
D =
e 't'a
</>a = cp
{4.0.12)
So with a typical value for dry soil of 4>a = 0.4, De= 0.3D.
An alternative expression, applied in the case of water or airsaturated pores, uses
an empirical correction factor, the tortuosity, T, which accounts for (a) the reduced
area through which diffusion can occur and (b) the longer average path a molecule
must travel to move a certain distance through the pores. The effective diffusivity is
related to the tortuosity by
D =D
e 
T
(4.0.13)
Typical values of tortuosity are in the range 2 to 6 1984), yielding effec
tive diffusivities that are approximately consistent with predictions based on 4.0.12.
Hydrodynamic Dispersion
Hydrodynamic dispersion in porous media is similar to the shearflow dispersion that
occurs in pipes and rivers, as discussed in 4.A.4. The dispersion of a nonreactive
groundwater contaminant, or conserved tracer, is depicted in Figure 4.D.4. At some
time .t
1
, contamination occurs in the groundwater, as shown in th; lefthand porilun
of the figure. The groundwater flows with a uniform filtration velocity, U, in the +x
direction. At some later time, t
2
, the center of mass of contamination has been trans
ported downstream to position x
2
, given by
Xz = x
1
+ (t
2
 t
1
)U
(4.0.14)
In words, the center of mass of contamination moves at the same speed as the fluid.
However, the areal extent of contaminated groundwater increases, and typically this
increase is much greater than can be explained by molecular diffusion alone. Because
J
Fif
no;
Sht
tin
is;
ve
1
to
tra
tht
tra
m(
m<
an
ch
nu
cu
fie
tht
ch
av
w
tht
tht
in
sh
wl
thL
Ht:
lei
Sc
fir
an
dh
th<
(4.0.10)
quantity of
U"ameter De
n the pores
mas Pick's
. an altered
ler than the
d combina
{pression is
(4.D.ll)
rfilled and
1e effective
s, equation
(4.D.l2)
pores, uses
he reduced
a molecule
iffusivity is
(4.D.l3)
ding effec
n4.D.12.
Jersion that
1onreactive
4. At some
md portion
, in the +x
been trans
(4.0.14)
:s the fluid.
pically this
te. Because
4D. Tmnsport in Porous Media 199
y
Xt
u
..
x3
Figure 4.D.4 Transport and dispersion of a fixed quantity of a
nonreactive groundwater contaminant. The figure schematically
shows the areal extent of contamination at three instants in
time, with t
3
> t
2
> t
1
The center of mass of contamination
is advected in the xdirection at a rate given by the mean
velocity, U. Hydrodynamic dispersion causes the contamination
to spread more rapidly in the direction of flow than in the
transverse direction.
the local velocity through the soil pores is not some of the contamination
travels at an average speed greater than while other contaminant molecules travel
more slowly than U. There is also some spreading in the ydirection, even though the
mean velocity in that direction is zero. Since the contaminant is conserved, the greater
areal extent of contamination is offset by a lower average concentration. The same
characteristics prevail in the interval from t
2
to t
3
This spreading is not caused by turbulence; it occurs even if the grain Reynolds
number is much less than 1, so that the flow is stable and laminar. It is observed to oc
cur in uniform sand columns in the laboratory, although it can be much stronger in the
field if the soil contains zones of higher and lower permeability than the average.
this spreading is caused by the variation of fluid velocities within
the pores. At the grain surfaces, the velocities diminish to zero. In the center of a
channel between two grains, the local velocity may be much higher than the volume
average. Individual contaminant molecules experience independent velocity histories.
When averaged over all contaminant molecules, the. rate of advection matches that of
the fluid, but some individual molecules may travel significantly faster or slower than
the mean, causing plume dispersion.
The contaminant flux in the direction of flow caused by hydrodynamic dispersion
in porous media is described by an expression analogous to law in one dimen
sion:
ac
lh = ehiJx
(4.0.15)
where e h is the dispersion coefficient and x is the direction of flow. In this expression,
the dispersion coefficient includes molecular diffusion as a limiting condition:
e, =De+ eU (4.0.16)
Here e is a characteristic of the porous medium called the dispersivity (units of
length). As defined above, U is the filtration velocity and De is the effective diffusivity.
So, the flux Jh represents the sum of transport due to molecular diffusion and due to
dispersion caused by nonuniform fluid flow. As with molecular diffusion alone, this
flux represents the net rate of contaminant movement per unit total crosssectional
area. Similar expressions could be written for the flux components in the transverse
direction, but these would require different dispersion coefficients, since it is observed
that transverse dispersion is weaker than longitudinal dispersion.
r
I .
.lrW l.lUlpter ,4 : :;I'ransport Phenomena
, REFERENCES .
BEIAN, A. 1984. Convection Mat transfer. Wiley. New York.
BrRo, R.B., STEWART, W.E., & E.N. 1960. Transport phenomena. Wlley, New York
BRETSZNAJDER, S., 1971. Prediction of transport and other physical properties of fluids. Pergamon Press,
Elmsford, NY, Chapter 7.
CLEASBY, J.L. 1990. Filtration. In F.W. Pontius, ed., Water quality and treatment: A handbook of commu
nity water supplies. 4th McGrawHill, New York, Chapter 8.
CussLER, E.L. 1984. Diffusion: Mass transfer in fluid systems. Cambridge University Press, Cambridge.
DULLIEN, F.A.L. 1979. Porous media: Fluid transport and pore structure. Academic Press, New York.
FiscHER, H.B., LIST, EJ., Koo, R.C.Y., IMBERGER,J., & BROOKS, N.H. 1979. Mixing in inland and coastal
waters. Academic Press,. New York.
GEtsuNG, K.L., TASHIMA, M.IC, GIRMAN, J.R., MIKSOI, R.R., & RAPPAPORT, S.M. 1982. A passive sampling
device for determining formaldehyde in indoor air. Environment International, 8, 153l.SS.
HANCOCK, R.P., EsMEN, N.A., & FuRBER, C.P. 1976. VISual response to dustiness. Joumal of 1M Air Pollu
tion Control Association, 26,5457.
HtNDS, W.C. 1982. Aerosol technology: Properties, behavior, and measurement of airborne particles.
Wiley, New York.
LAPPLE. C.E., & SHEPHERD, C.B. 1940. Calculation of particle trajectories. Industrial and Engineering
Chemistry, 32,605617.
Ltss, P.S., & SLATER, P.G. 1974: Flux of gases across the airsea interface. Nature, 247, 181184.
McCABE, W.L., SMITH, J.C., & HARRIOT, P. 1993. Unit operations of chemical engineering. 5th ed.
McGrawHili, New York.
MILLINGTON, R.J. I 959. Gas diffusion in porous media. Science, 130, 100102.
PERRY R.H., & GREEN, D.W. (eds.). 1984. Perry's chemkal engineers' handbook. 6th ed. McGrawHill,
New York.
REID, R.C., PRAUSNtTZ, J.M., & PoLING, B.E. 1987. The properties of gases and liquids. 4th ed. McGraw
Hill, New York.
ScHWARZENBACH, R.P., GscHWEND, P.M., & IMBODEN, D.M. 1993. Environmental organic chemistry. Wlley,
New York, Chapter 10.
SNOEYINK, V.L. 1990. Adsorption of organic compounds. In F.W. Pontius, ed., Water quality and treatment:
A handbook of community water supplies. 4th ed. McGrawHill, New York, Chapter 13.
ThRZAGHI, K., & PEcK, R.B. 1967. Soil mechanics in engineering practice. 2nd ed. Wiley, New York.
TtrMA, J.J., & ABDELHADY, M. 1973. Engineering soil mechanics. PrenticeHall, Englewood Cliffs, NJ.
PROBLEMS
4.1 Environmental transport: Concepts and exercises
(a) If the concentration of a species is measured in mass per volume, what units are
. associated with the following parameters?
(i) Concentration gradient
(ii) Flux
(b) What is the difference between the intrinsic permeability of a sand column and its
hydraulic conductivity? ,
(c) Typical molecular diffusivities are 0.1 cm
2
s
1
in air and 1()
5
cm
2
s
1
in water. Ex
plain why the diffusion coefficient Is so much smaller in water than in air.
(d) !.. 1olecular diffusion results from the random motion of molecules in a fluid. Pro
vide an analogous explanation for turbulent diffusion.
(e} We write the twofilm model asJ = kgt_Cs C). The masstransfer coefficient,
can vary markedly from one species to another. What is the dominant species property
that controls kg
1
?
4.2 More on environmental transport processes
(a) Gaseous pollutants are emitted at a constant rate from an industrial as de
picted in the figure. the xcoordinate be parallel to the wind and the zcoordinate
l
'\
. po
the
(b;
pu
CO;
as
(c)
pru
en<
de
as
pru
is (
(d)
the
fra
4.3
(a)
tha
York.
Pergamon Press,
ibook of commu
;s, Cambridge.
'New York.
land and coastal
passive sampling
i3158.
of the Air PoUu
rbome panicles.
and Engineering
:1184.
neering. 5th eel.
d. McGrawHill,
+th ed. McGraw
:hemistry. Wiley,
ty and treatment:
.: 13.
New York.
)Od Cliffs, NJ.
units are
and its
: in water. Ex
ir.
n a fluid. Pro
oefficient, kgb
ecies property
l stack, as de
! zcoordinate
.I
1
.n'''i''"'lH s Problems
. . " ... \ . .,,. ... ... .
pomt Name the dommant transport flux m each of
the x, y, and tcOordinate directions within the plume.:li h ;':
... .._J ...
u
1 ... _,.,_._,_
(b) Consider the case of welldeveloped water flow through a pipe. A shortterm
pulse of a nonreactive contaminant is injected into the water at the inlet. Sketch the
concentration profile, C(t), as a function of time at the outlet, providing as much detail
as possible.
Welldeveloped velocity
profile with mean speed = U
0
I
Contaminant pulse
injected at inlet at
timet =0
Tube length= L
)
+
Monitor concentration
w.. time, C(t), at outlet
(c) A container is filled with water containing monodisperse particles. Initially the.
particle concentration is uniform. The fluid is motionless. The particles are large
enough so that Brownian motion may be neglected. Sketch the total number of parti
cles in the vessel as a function of time. Label your axes with as much detail
as possible. The vessel dimensions are L = length X W = width X H = height, the
particle diameter is dP' the settling velocity is v P and the initial particle concentration
is C
0
(d) The following figure shows the idealized concentration profiles for a species near
the airwater interface, according to the tworesistance model. Assume that the mole
fraction in air is fixed. Sketch the concentration profile at equilibrium.
Air
Water
4.3 Magnitude estimates for diffusion
(a) If a fluid flow has a turbulent diffusivity of e, what is the characteristic distance
that a species may be transported by turbulent diffusion in time t?
r
7/t':': .., L',"'* ., 7 cueuomena
,
0
b"'y};(b) uA cubicalvessel. em 'on a is filled with water. A: drop of food coloring is
carefully dispensed into the center of the vessel. Assume the water is still (no advec
tion). Estimate the time required for the color to disperse by molecular diffusion
throughout the vessel. You may assume that the dye in food coloring is anionic
molecule.
(c) Odorous gas molecules are relea5ed into a cubical room that measures3 mona
side. Assuming the air is. estimate the . time required for the odor mole
cules to diffuse throughout the room volume.
4.4 Comparing transport and reaction time scales
A species diffuses (diffusivity =D) through a stagnant;air layer of thickness L. The
species also undergoes firstorder decay with rate constant k (k ::. 0). Write an expres
sion that, if satisfied, would permit decay to be neglected when analyzing transport
through the stagnant air layer.
4.5 Contaminant flux
(a) Contaminant flux is a vector. What is the precise meaning (physical significance)
of the magnitude of contaminant flux?
(b) What is the meaning (physical significance) of the direction of the flux vector?
(c) Write an equation that expresses the dependence of advective flux on concentra
tion. Define the variables.
(d)' A contaminant is present at a unifonn concentration of 5 g m
3
in water that is
flowing at uniform velocity of 2 m s
1
\Vhat is the magnitude of contaminant flux due
to advection?
(e) A contaminant is present at a concentration that varies in the xcoordinate direc
tion as shown in the following figure. The contaminant concentration is uniform in the
y and .directions. The diffusion coefficient is 0.9 m
2
day
1
What is the
flux due to diffusion? Include both magnitude and direction.
4.6 Estimating plume spread
(a) Commonly, air pollutants generated by largescale processes are emitted from an
elevated stack so that objects on the ground (i.e., people) near the source are protected
from exposure to extreme concentrations. Consider air pollutants released from a
stack 100 m above the ground. The wind speed is 3 rn/s. The turbulent diffusivity. in
the vertical direction is 0.5 m
2
s
1
Given these data, make a magnitude estimate of the
distance downwind where the plume contacts the ground.
(b
str
wi
do
ac
4.7 D
Tl
(a
gi
(b
(c
bt
p1
4.8 F:
(2
d<
n<
pl
(i
(i;
(t
Sl
til
4.9 A
Ir
tl
tt,
d
(I
a'
tb
p;
(f
(I
aJ
1
(<
aJ
"d coloring is
II (no
lar diffusion
.s
res 3m on a
mole
L. The
te an expres
, ng transport
'iignificance)
IX vector?
n concentra
water that is
1ant flux due
dinate direc
liform in the
What is the
itted from an
are protected
:ased from a
diffusivity. in
;timate of the
..... "" ...... .. ... .,
(b) Consider the situation depicted below, in which pollutants ;are: emitted from a
stack and the plume spreads downwind. The height of the stack is H = 50 m. The
wind speed is U = 3 in s
1
The plume first contacts the ground at a distance L = 2 km
downwind. Estimate the vertical turbulent diffusiyity,. e,t, plume char
acteristics.
L
4. 7 Drag on a sphere
This problem is concerned with the drag on a spherical particle immersed in a fluid.
(a) The drag force is sometimes expressed by Stokes's law: Fd = 31TpdP V. Define and
give appropriate units for the three parameters on the righthand side of the expression.
(b) As the parameter dP or V increases past some law begins to fail.
What condition must be satis&ed for to hold?
(c) Again consider that parameter dP or V increases past a limit such that Stokes's law
begins to fail. Is the drag as predicted by Stokes's law too low or too high? Briefly ex
plain.
4.8 Factors influencing particle settling
(a) Drag on a particle is caused by two intrinsic properties of a fluid: viscosity and
density. The particle Reynolds number defines which of these properties is the domi
nant cause of drag. For each of the two cases state which fluid property (or
properties) contributes significantly to particle drag.
(i) 0 Re :::; 0.3
(ii) 0.3 Re 100
(b) When analyzing particle settling in environmental engineering, we generally as
sume that the forces acting on a particle are in balance: drag + buoyancy = gravita
tional force. Why is this a reasonable approximation?
4.9 Acceleration to the terminal settling velocity
In analyzing particle settling, it is argued that a particle rapidly attains its terminal set
tling velocity, and therefore particle acceleration need not be considered. Demonstrate
the conditions under which this is true. Consider a spherical particle of diameter d and
density Pp that is initially held at rest in a stagnant fluid of viscosity IL and density Pt
(Fluid density is less than particle density.) At time t = 0 the particle is released and
accelerates downward because of gravity (gravitational acceleration =g). Assume
that drag is described by Stokes's law, Fd = 31ifL where Vis the velocity of the
particle relative to the fluid.
(a) Derive an expression for the timedependent settling velocity of the particle.
(b) What condition must be satisfied for the terminal settling velocity to be a valid
approximation of the particle's settling velocity?
(c) What is the characteristic time required for a of dP = 10 J.Lffi (= 10
3
em)
and p = 2.5 g cm
3
to approach its terminal (stec,ldy) settling velocity in water?