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Is It Really So Simple?

In teaching an
introductory, graduate-level
course in diffusional operations over the past several
years, I have been struck by the lack of a dci ivation
of the complete difli ential equation dosci-ibing dlSportion olicts in beds and othei multiple-phase systems. Most authors simply give a simpli find equation applicable to some special case, with no dei ivtion and with only a briefly-stated mentlon of the
equation folliiwing fFGm a water ial balance on a
component in the fluid phase in question, oi- with a
statement i efei i-ing to the comparable equation for- a

singlephase fluid.
For example, Sherwood, Pigfoi-d, and
Wilko II ]

As expected, this equation is cci-rect for the

simplified case to which it applies, but unless care is
exercised, there is g'rciit dangci- ct or i-oi- when aclclitional terms are added to include the effcts of chemical reaction or a sour-cc (such its the inti oduction of a tiacoi- material ). In addition, two Standar d for ins of
the dispei-sion-model equation ai'e commonly found
in the liter-ature whet c the terms fi ore one of these
equations ate ft equently used inconsistently in the
othei- standai d form. Finally, thCfC hlIS been considerable confusion in applying the solutions ft-ore massand heat-ti ansfoi ches in unpacked conduits
similar cases in packed 1ods.
For those i-oasons, in my classes I have liiund lt
necessary to pi-esent a simple derivation of the applicable differential equation. The dei-ivation will be
given in this paper , and then the two Standar d forms
of the differential oijuation will be stated, the i elationship between thom will he developed, and some
of the potential on ore in writing the equations v ill

be dlscussed. Flnally, an example of using a solution

of the comparable di ffoi cntial equation ft-ore heat
conduction to provide a solution to a dispci-sion pi oblean in a packed bed will be presented to illusti ate
the need for car o in using such solutions.
Dot i ving the appl icablo differ-ential
equation for desci i bing the concenti-ation ot
some component A in fluid phase i as a
function of location and time for a packed or
fluldized bed, in both phases for a gas-sparged
llquid, and for all phases in othei simi- lar
systems, may be done simply by const dering a
water-ial balance on a dlffei-on tial volume of
the sys- tem using the well -knovi n, shellbalance techniQue f2J i olcri ing to an element
of II uid phase i. In such a treatment, each fluid
phase may be consider cd sepa- rately. The
equation for fluid phase i is, in svoi-d hmm,
Iiite o i /n /i r//s :i.s/ii / + {liiic oj i in I
ect/on /


The dispoi 81GF1 ter ins in Equation 2 i-eprcsont

the combined effects of diffusion and dispel-sion duo
to convoctivo stir-i-i ng caused by the relative flows of

fluid phase i and the packing or othei phase or by

William 1. Rice is a pro/essor o/ c/cervical engineer
/ng af Al//anova L/niversfj'. w/ere he has been snce

i 957. /-ie received his BS an:/ /\IS mom I\/orces/er

Polytechnic Institute and his PhD from Princeton
University, all degrees being in chemical engineering. He teaches thermodynamics. separation processes, dilfusional operations. and Ia0oraiory. His
published research has been on Iluidized beds. solar
energy. and fluid mechanics

velocity gradients. For convenience, these

combined effects
using a dispersion coefficient
which relates a mass flux to a concentration
gradient in the same form in one dimension as the
well-known Fick's first law: Flux = - (D)x
concentration gradient). In this use, the dispersion
coefficients are used in place of the
diffusion coefficient, D, giving: Flux = - (E)x (concentration gradient). The dispersion coefficient, E, is
frequently different in different directions, whereas
diffusion coefficients are the same in all directions.
To simplify the remainder of the derivation, let
us assume that the system consists of a cylindrical
conduit with the concentration of component A in
fluid phase i symmetric about the z-axis and with
the net flow only in the axial direction. Then, for
very small r and z, the various terms in Equation
2 expressed for a chosen ring element of volume =
2iirArAz are
d CA



(2ii c rArAz)


= local fraction of the total volume

occupied by fluid phase i, taken as a
continuous function of space and time
(i.e. , fluid phase i is treated as a continuum fluid with
properties in space and timed.
Cq = local concentration of A in fluid phase i
E,, E, = local effective axial and radial
dispersion coeffi- cients, respectively
U, = actual local velocity in the z-direction of
fluid phase i (e.g., if fluid phase i is the
fluid phase in a packed bed, then U, is the
local velocity in the z-direction of fluid
phase i in the interstices between the
bed particles)
R = local net rate of production of A by
chemical reac- tion in fluid phase i per
unit volume of that phase
SA = local rate of introduction of A into fluid

phase i from a point, line, or area source

within fluid phase
i per unit volume of that
= local net rate of introduction ofA into
fluid phase i from another phase or
region outside fluid phase i
per unit volume of fluid phase i (e.g., this
term al- lows for mass transfer being

Each term in Equation 3 also has the

units of (moles ofA)/(time). Equation 3 can
now be simplified by dividing all terms by
2irArAz to obtain
E,c(r + Ar)


where each term has the units of Creoles ofA)

[(volume of entire system)ttime)].
Now, Ar and Az in Equation 4 are
allowed to approach zero as a limit, and
Equation 4 becomes
where each term still has the units of
Creoles of A)(length)/[(volume of entire
As additional simplifications, which are
nearly always made, E,, E,, and c are

considered constant in space and time,

and U, is replaced by U; , the average
axial velocity of fluid in fluid phase i. This
allows Equation 5 to be written for a fluid
phase i of constant density as
considered from an- other phase into fluid
phase i)
r, z = radial and axial distances,
respectively t = time

Fall 1990


+c R + c SA '

A '0


where each term now has the units of (moles of

A)/ [(volume of entire system I time)J. The above
deriva- tion is an independently derived extension of
the equation for an adsorption column given by
Holland and Liapis [3].
Equation 6 can be obtained by dividing by
c to obtain

where each term has the units of Creoles of A)/[(volume of phase i)ttime J.
Equations 6 and 7 represent two different
forms Of th8 complete differential equation

for the speci- fied simplifying conditions.

They are the basis for the two standard
forms of these equations
in the
literature. Various forms of these with certain
terms omitted are the usual starting