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Wat. Res. Vol. 22, No. 3, pp. 279-286, 1988 0043-1354/88 $3.00+0.

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Printed in Great Britain Pergamon Press plc

ADSORPTION OF POLLUTANTS FROM WASTEWATER


ONTO ACTIVATED CARBON BASED ON EXTERNAL
MASS T R A N S F E R AND PORE D I F F U S I O N
GORDON McKAY* and M ~ J. BrNo
Department of Chemical Engineering, The Queen's University of Belfast, Belfast BT9 5DL, Northern Ireland

(Received September 1985)

Abstract--The adsorption of four pollutants in aqueous solutions onto activated carbon has been studied.
The following solutes have been investigated, phenol, p-chlorophenol, sodium dodecyl sulphate and
mercuric ions. The kinetics were studied using an agitated batch adsorber and a model was proposed,
based on external mass transfer and pore diffusion. The model presented has a rapid analytical solution
and is based on the assumption of a pseudo-irreversible (rectangular) isotherm.

Key words--adsorption, carbon, mass transport, phenol, mercuric ions, sodium dodecyl sulphate,
p-chlorophenol

NOMENCLATURE rr = Radius of concentration front (cm)


g[i = Modified theoretical Sherwood number
A Outside surface area of particle, 4nR2(cm 2)
a ~ Constant in evaluation of equation (23) Sh = Sherwood number, (krR)/Dmoj
( l - - C h / C h ) 0"33
t= Time (s)
V= Volume of effluent (dm 3)
Bi= Biot number, k/R/Dpo~
W= Weight of adsorbent (g)
B A constant, [1 -- (1/Bi)], in Spahn and Schlunder
x = Variable of integration in equation (23), (1 -~/)3
model
Y~*= Hypothetical solid phase concentration, in this
C = Concentration of solute in aqueous phase work it taken to be the saturated monolayer
(mg din- 3)
coverage (rag g-i)
Concentration of solute at equilibrium, in aque-
ous phase (rag dm -3)
Greek letters
co..= Concentration of solute at equilibrium on the
solid phase (mg dm -3) r/= Dimensionless solid phase concentration
co= Concentration of solution liquid at the outer = Dimensionless liquid phase concentration,
surface of particle (rag dm -3) (c,/co)
c,= Capacity factor in Spahn and Schlunder model, n = Geometrical constant
( YhW/Co V) p, = Bulk density of adsorbate particle, g dry ad-
Ce. co Equilibrium liquid phase concentration in batch sorbent per cm3 of bed .volume
contact when system has reached equilibrium = Dimensionless time, pore diffusion model
(mg dm -3) (D,o~tCo/A~p. r~).
C t~ Liquid phase concentration at time t (mg dm -3)
Defr = Effective diffusion coefficient (cm2 s -~)
Dm~ = Pore diffusion coefficient (cm2 s-I)
Particle diameter (cm) INTRODUCTION
f-~ Liquid phase mass transfer coefficient (cms -I)
k,= Mass transfer coefficient in the solid phase, in Activated carbon is widely used for the adsorption o f
single resistance model (cm s -I) solutes from gases and liquids (Mantell, 1968; Hass-
~'(t) Adsorption rate at time t (mgs -1)
=
ler, 1974; Perrich, 1981; Allen et al., 1967). It is
Qe = The amount of solute adsorbed per unit weight of
adsorbent in forming a complete monolayer on gaining prominence in the removal o f organics from
the surface for the Langrnuir isotherm expression drinking waters and wastewaters (Burke et al., 1980;
(mgg -l) Wu, 1978; Ramalho, 1977). Various contacting de-
Mean value of concentration of adsorbate on
vices are available for adsorption systems, such as
adsorbent (rag g-l)
Concentration of adsorbate at surface of ad- batch adsorbers and fixed bed adsorbers. The accu-
Qe. !
sorbent at equilibrium (mg g-') rate design of such systems is achieved by developing
Qe. ~o Concentration of adsorbate on adsorbent at mass transfer models which adequately describe the
infinitetime (rag g-l) kinetics and mechanisms o f the adsorption process.
Qe.t Solid phase concentration time t (mg g -~)
This paper presents a mass transfer model based on
R = Radius of particle (cm)
r = Radial distance from the centre of particle (cm) external mass transfer and pore diffusion to describe
the adsorption of various pollutants onto activated
carbon in a well agitated batch adsorber. The pollut-
*To whom all correspondence should be addressed. ants under investigation are phenol, p-chlorophenol,

279
280 GORDON McKAY and MURAD J. BINO

sodium dodecyl sulphate and mercuric ions. Ad-


sorpti0n isotherms have been determined and contact VariabLespeed
time studies undertaken to assess the effect of system
Rubber support I I~ motor

variables such as adsorbent mass and initial pollutant


concentration.
A review of two-resistance mass transfer models
prior to 1974 has been presented (Weber and Chak-
ravorti, 1974). Other two-resistance models have been
developed for liquid phase adsorption, some incor-
porated a numerical solution (Furusawa and Smith,
1974; Neretnieks, 1976) for adsorption in batch ves-
sels. A limited number of analytical techniques have
also been reported (Neretnieks, 1974; Spahn and .
/ II
,i i ,i .
Schlunder, 1975; Weber, 1978; Ditl et al., 1978; Fritz
et al., 1981), however, they involved either graphical
differentiation or the solution to a series of complex
equations. Obviously, for practical design purposes,
the more mathematically simple the model the more D
amenable it is to designers of wastewater treatment
plants. Fig. I. Agitation unit. Z = height of liquid in vessel = D;
In this investigation the adsorption rate is devel- B = baffle width = 0.075D; b = height of impeller blade =
oped as an analytical function which can be solved 0.1D; diameter of impeller blade = 0.5D; distance between
impeller blade and vessel bottom = 0.5D.
rapidly on a computer, based on the assumption of an
irreversible isotherm, that is, where the operating and
tie lines terminate on the monolayer. mass transfer in the particle,
~V = A p , k , ( Q , . , - O.o). (2)
EXPERIMENTAL
It is assumed that the concentrations at the granular
Materials
surface (C, and Qs) remain in equilibrium as de-
The solutes used, namely, phenol, p-chlorophenol, so-
dium dodecyl sulphate and mercuric chloride, were of analar scribed by the adsorption isotherm during the entire
grade as supplied by B.D.H. The carbon was Filtrasorb 400 period of adsorption. The mass transfer coefficients kr
as supplied by Chemviron. and k, are generally functions of all system param-
Analysis eters. They can be determined from batch test
Phenol and p-chlorophenol concentrations were deter- evaluations.
mined by absorption spectrophotometry at wavelengths of At time t -- 0 a prepared wetted quantity of acti-
270 and 280 nm respectively, corresponding to the maxi- vated carbon W of uniform particle size was brought
mum absorption values. Sodium dodecyl sulphate was together with a quantity of water V of initial ad-
analysed using a Beckman Model 915-B Total Organic
Carbon Analyser. Mercuric ion concentrations were meas- sorbate concentration Co in a well agitated beaker.
ured by the sodium borohydrate flameless technique on an Changes of adsorbate concentration C were meas-
atomic absorption spectrophotometer. ured with a spectrophotometer while those in the
adsorbent ~., were calculated from mass balance.
Equipment
Graphical differentiation of Ctt I gives d C / d t which
The agitated batch adsorber is shown in Fig. 1 and is proportional to the adsorption rate .N(t), since the
comprises a 1.7 dm3 vessel. The impeller agitation rate can
be carefully controlled using a Heidolph motor. For the differential mass balance is given by:
agitation runs using mercuric ions the system was entirely
glass but aluminium was used for the impeller and baffles in N(t) = - V dC W d~'c. (3)
the other experiments. The relative dimensions are shown on -~= dt
the figure.
From the adsorption rate N(t) the equilibrium con-
centrations Cs and Qc can be determined as a function
THEORY of the concentrations C, and ~.c as shown in Fig. 2,
provided the external mass transfer coefficient kr is
E x t e r n a l m a s s transfer a n d pore diffusion m o d e l f o r
known.
batch adsorbers
At time t = 0 all the mass transfer resistance is
It is assumed that the adsorption rate is controlled restricted to the external layer on the particle.
by an external and internal mass transfer resistance.
This linked transport mechanism may be described
v (dC
kr = - ACo" \ ' ~ - } t - o ' (4)
using mass transfer coefficients defined as follows:
Hence the external mass transfer coefficient can be
mass transfer in the external layer,
readily determined (Spahn and Schlunder, 1975; Fur-
N = X k r ( C ' - C,); (1) usawa and Smith, 1973; McKay and Allen, 1980).
Adsorption of pollutants 281

C]c Reacted r* Ct
"N / -
O,

/ / Tie
.....Un,~ ~ i \ o0.~-.... . . . . .

/ \
Co Co Unreocted / "~ i
anectiolL between
Fig. 2. Connection be:ween bulk and
mql surf; "e cox
surface concentration porhcl, e ~ ' ~ Cen¢~ntration front
during the adsorption in batch tests,

Once k r is known, the equations (1) and (3) can be Fig. 3. Concentration profile in particle.
used to determine the concentration of the adsorbate
in the liquid phase C~ at the granular surface. This Each Cao was plotted on the isotherm and the
gives the value of the concentration Q~0 in the solid corresponding equilibrium value Q~0 was obtained.
phase which is assumed to be in equilibrium with C~¢o. The operating line for the above process was also
These equilibria are described for both high and low drawn by plotting the Cto, Q,~o values, determined
adsorbate concentrations in water by the equilibrium from the batch contact experiment, and C,.~ and
isotherms. Q,. ~ values were determined by extending the oper-
The adsorbent particle is regarded as a porous ating line to cut the isotherm (Fig. 2). Knowing the
solid. The subsequent description of the adsorption concentrations Ct0, Q~0, C, and Q, at any time, the
rate will therefore be based on the following assump- time dependent internal mass transfer coeffÉcient, k,
tions: values, were calculated by utilizing equations (1) and
(2) in the form,
(i) The adsorbate is transferred within the pores of
the adsorbate solely by means of molecular kf ( C , - C,)
k, = (6)
diffusion. p,(Q,,,-O,)
(ii) Adsorption equilibrium according to the iso-
The rate of adsorption on a carbon particle can be
therm is presumed between the pore water and
determined as follows:
the adsorbent throughout adsorption process.
In other words, the deposition rate of the (i) Mass transfer from the external water phase:
adsorbate molecules in the pore water on the
adsorbent surface is taken to be much higher = 4rrR 2kr(C, - C,). (7)
than their rate of diffusion. (ii) Diffusion in the pore water according to Fick's
(iii) The adsorbate concentration in the carbon is law:
independent of that in the water, i.e. the ad-
47rDeer C
sorption is irreversible. = ~ ~,~ (8)
(iv) The quantity of absorbate in the poore water
is much lower than that on the adsorbent per \rr R]
unit volume and can therefore be neglected. where D,fr is the effective diffusion coefficient in
Because of the external mass transfer resistance, the pore water.
the concentration of adsorbate in the water drops (iii) The velocity of the concentration-front is ob-
from value C0~ in the bulk to the equilibrium value tained from the mass balance on a spherical
C~tl at the surface. The concentration of adsorbate in element:
the pore water, therefore, decreases from C~0 to zero
at rt. The adsorbate in the pores is adsorbed in a N= -4nr~Y~p,(drr~. (9)
\at)
well-defined concentration front, moving with vary-
ing velocity from the particle surface inwards. A (iv) The average concentration in the particle is
concentration curve in the particle is shown in Fig. 3. given by:
The equilibrium concentrations C, and Q, were
determined as a function of the concentration Cto and
~ by substituting the value of kf from equation (4)
and the adsorption rate .~'(t) at different times in: Introducing dimensionless parameters:
+Z.(dq Co D,~t
C~t) = C,) Akr\ dt ]" (5) P, Yg' R2 (11)
W,R.2.2/3.--B
282 GORDON McKAv and MuaAo J. BINO

layer coverage the system can be treated with a


r/ = y-~ (12)
"pseudo-irreversible" isotherm approximation, so
that,
__Ce (13)
Co Q, - Oe = Y~' - Oe. (20)

Bi = kfR. (14) This assumption allows an analytical solution of


Ddr equation (18) in the following manner. Let,
The adsorption rate for a single particle follows 1
B = 1 --- (21)
from equations (7), (8), (9) and (10): Bi
dr/ ~ 3(1 - q),/3 and
-- = (15)
dt 1 -- [1 -- (1/Bi)](l -- q)1/3" x = (1 - 17)0.33. (22)
This equation is of the type,
Substituting equations (21) and (22) and rearranging,
dr/ equation (18) becomes,
d-z = ~f (r/ )Bi. (16)
x ( l - Bx)
The adsorption rate to the individual particle is dz = [1 - Ch(1 -- x3)] dx (23)
thus a function of adsorbate concentrations in the
and if
water phase ~, in the carbon phase r/and of the Biot
number. a __fl-
The coefficients kstt) determined experimentally \ Ch ,] " (24)
were compared in the form of a modified Sherwood
Thus
number. This Sh-number is proportional to the ad-
sorption rate, which follows from equations (2) and 1
(3). dr =--~h\ x3 + a3 j dx (25)

S---h= _ _ 1 dr/ (17) and this can be integrated using partial fractions
3(1 - r / ) dr according to the following form,
with the adsorption rate dr//d~ from the batch tests . +,oF(x .
one obtains the experimental values of Sh while from L\ 1 + a)aJJ
the rearranged equation (15)
I f I-(2- a)-I
dr/ 3(1 - Chr/)(1 -- r/)~/3 + ~larctan L ~ j
d--~= 1 -- [1 -- (l/Bi)](1 - r/)u3 (18)
the theoretical values Sh can be predicted. Thereby (26)
the concentration ¢ in equation (15) was replaced by
(1 - Chr/) which follows from the total mass balance The limits of integration in equation (26) are r = 0,
for the vessel. Here C h = WY~/LCo is the capacity r/=0, atx=l andr=z,r/=qandx=x
factor for the individual test. The value of the
effective diffusivity in the pores D ~ has been adopted r =~-~.~h{ln[(x3+aS)(2B--!)]+ln[(x + a)~]}
to give the best fit between experimental and theor-
etical data. 1 f [-(2 - a ) - ]
From adsorption tests presented in this paper it + ~larctanL a--~-~J
follows that the experimental and theoretical values
of any given system can be fitted with sufficient
accuracy introducing a constant diffusion coefficient
ar,tao[ ll (27)

Den for mass transfer inside the porous carbon


particle. Therefore, by converting dimensionless time, r,
into real time it is possible to compare experimental
and theoretical concentration decay curves.
Comparison of experimental and theoretical results
based on the assumption of a pseudo-irreversible iso-
therm
DISCUSSION
The coefficients k,(t) obtained from batch tests are
now compared in the form of a modified Sherwood •Adsorption isotherms were determined to assess
number, Sh. This Sh is proportional to the ' the capacity of activated carbon for the four pollut-
ants. The monolayer adsorption capacities are 206,
=
l t'dr/ (19) 410, 335 and 130 mg g - l for phenol, p-chlorophenol,
sodium dodecyl sulphate and mercuric ions re-
provided the operating line terminates at the mono- spectively. F o r the kinetic model to be applicable the
Adsorption of pollutants 283

Ci,t ,QI,t 1.0

--" 200-- ~

08 .

0.6
v 100 -
~;

0.,~ I I
20 40 60
Time (rain)

Fig. 5. Concentration decay curves showing the effect of


0 100 200 300 400 500
adsorbent mass for the adsorption of phenol on carbon. $ ,
Co (mg dm -~) wt = 0.85 g; &, wt = 1.7 g; C), wt = 2.66 g; - - - , theoretical.

Fig. 4. Equilibrium relation showing operating line and tie


lines for phenol. line approaches the curved region of the isotherm the
agreement is not as accurate.
tic lines and operating lines must terminate at the The effect of varying the mass of adsorbent is
saturation capacity monolayer line. Figure 4 shows shown in Fig. 6 for the adsorption of phenol. The
various tie lines and an operating line for the ad- model gives good prediction of experimental results
sorption of phenol onto carbon using an initial using a constant effective pore diffusivity and a single
concentration of 500 mg dm -3. constant external mass transfer coefficient. The effect
The operating line is constructed from a point on of initial concentration on the adsorption of p-
the C¢ axis of the equilibrium curve, having coordi- chlorophenol onto carbon is shown in Fig. 6. Cor-
nates C= = Co and Q¢= 0. The operating fine is d.rawn relation between experimental and theoretical results
from this point, having a slope-solution volume/ is achieved for only 10-20 min, after this period the
adsorbent mass, to the equilibrium curve thus pre- theoretical equation decreases at a greater rate than
dicting the final liquid phase concentration and solid the experimental results. The deviation from the
loading. The tie or time lines must fall between the theory is probably due to a change in the effective
operating line and the equilibrium curve. The lower pore diffusivity. A branched pore theory was pro-
point is located by the experimentally measured Ct posed (Peel et al., 1981) which involves a change in
value and the particle surface concentration is calcu- Dar with varying extents of adsorption. This extent of
lated from equation (5). adsorption is a function of pore size distribution
In a previous model it was assumed that the solute within the particle and the relative size of the solute
concentration in the pariiele is independent of that in molecule. A detailed description of the branched pore
the water, that is, the adsorption is completely irre- model is given by Peel et al. (1981). Figures 7 and 8
versible. Consequently, the equilibrium concen-
tration, Qe.= can be replaced by a hypothetical 500
equilibrium constant, Y~' = constant. It was found
that this hypothetical equilibrium constant did not
give the best fit between experimental and theoretical
data. In fact, in certain cases Spahn and Schlunder 400
(1975) were unable to use Y* to fit experimental and
theoretical data and selected a value of Y* =0.5.
In the present work this model was tested exten-
sively for the adsorption of phenol onto carbon and
it was found to give a very good correlation between
IE
"D
=" 3C;0
E
\,
experimental and theoretical data. It was also tested
for p-chlorophenol, SDS and Hg 2+ adsorption onto
carbon. The value of Y* adopted in these cases was
200
that of the saturation monolayer coverage of the
relevant isotherm. The variables studied were: (a)
initial concentration and (b) mass of carbon.
The effect of varying the initial concentration is
I I I I I
shown in Fig. 5 for phenol. It can be seen that for IGOC) 5 10 15 20 25
steep operating lines terminating at the adsorption Time (rain)
i.
isotherm monolayer the agreement between theor- Fig. 6. Concentration decay curves showing the effect of
etical andexperimental data is very good and extends initial concentration for the adsorption of p-chlorophenol
for up to 50 rain of contact time, but as the operating on carbon. , Theoretical,
284 GORDON McKAY and Mu~D J. BINO

1.0 (dCt/dt) can be calculated. Figure 9 shows this


Co• 200 mg drn -3 process for a phenol--carbon system. Once /~'(t) is
wt • 1.0g
d~:• 605 pm known at fixed values of Ct, equations (4), (5) and (6)
o~ - - TheoreticoL
can be used to determine ks.,.
~ 0.8
Since k r is extracted from the slope of concen-
tration decay curve at t = 0. From the appropriate
value of Ct. Qt can be read from the relevant iso-
therm, and also Qe can be located on the isotherm
0.6 I I I
since it exists in equilibrium with Cs.
100 200 300 If ks., is calculated under the assumption of
Time (min) diffusion in a homogeneous particle the following
Fig. 7. Concentration decay curve for the adsorption o f SDS equation is valid for the boundary conditions of
on carbon. constant particle surface concentration Q ....
(Dpore 7~2"~ ( 4 R2 ~ (29)
for SDS and Hg 2+ adsorption show a trend consistent
k s ' t = \ R 3]+\nDpo~tJ"
with the pore diffusion mass transfer process being
rate controlling. The values of kr and Dcfr are shown If this diffusion process occurs with the boundary
in Table 1 for all the runs. condition of constant surface particle concentration,
then a plot of (ks.t)2 vs (I/t) should have a straight
Estimation of experimental k, values relationship. Figures 10 and 11 show the plot of log k,
Equation (28) describes the rate of mass transport vs log t for SDS and phenol systems respectively. As
in terms of a rate of change of a solute in the liquid was suggested by Spahn and Schlunder (1975) the
or the solid phase for the system as a whole. ~ / t - law is indeed obeyed.
A comparison of experimental and theoretical par-
dxt
N(t) = -- V---~--= WddQe (28/ ticle internal mass transfer mass transfer coefficients
are shown in Table 2. Five values of k,., are presented
by carrying out graphical differentiation (dx/dt) or for the two systems at the following time values; 10,
25, 36, 49 and 64 min. It is observed that these values
do not compare particularly well in the case of phenol
1.o but are well within the range of accuracy expected for
the experimental calculation in the case of SDS. It is
0.8 ~ Theoreticat noticed that when the concentration decay curves are
steep at the initial few minutes of contact time,
experimental and theoretical values do not match.
~, 06 But for systems such as SDS the concentration decay
curves are much less steep than those of phenol
systems at similar experimental conditions.
0.4 The following observations can be made from the
results.
I I I I I
o 20 40 60 an loo (i) Experimental and theoretical values of a given
Time (rain) system can be fitted with sufficient accuracy by
Fig. 8. Concentration decay curve for the adsorption of introducing a constant diffusion coefficient D,~r
Hg2+ on carbon. for mass transfer inside porous particles.

Table I. Film mass transfer and effectivepore diffusion coefficientsfor the adsorption of different
pollutants
Co W dp kr D~ Yt
Run Pollutant (mgdm -3 ) (g) (m) Ch (10 -4 ) (10 -~) (mgg -I )
I Phenol 200 0.85 428 0.515 1.0 2.0 206
2 Phenol 300 0.85 428 0.343 1.0 2.0 206
3 Phenol 400 0.85 428 0.257 1.0 2.0 206
4 Phenol 200 1.70 428 0.941 I.O 2.0 206
5 Phenol 300 1.70 428 0.687 1.0 2.0 206
6 Phenol 400 1.70 428 0.515 1.0 2.0 206
7 Phenol 500 1.70 428 0.495 1.0 2.0 206
8 Phenol 600 1.70 428 0.343 1.0 2.0 206
9 Phenol 300 1.70 605 0.625 1.0 2.0 200
10 Phenol 500 3.40 ' 605 0.786 1.0 2.0 200
II Phenol 326 1.70 303 0.644 1.0 2.0 210
12 Phenol 509 3.40 303 0.825 1.0 2.0 210
13 p-Chlorophenol 500 1.00 428 0.482 1.20 10.0 410
14 p-Chlorophenol 400 1.00 428 0.603 1.20 10.0 410
15 p-Chlorophenol 300 1.00 428 0.804 1.20 10.0 410
Adsorption of pollutants 285

500 -

Phenot.
450
CO = 5 0 0 mg dm - 3
~'~ wt : 1.79 g
E dp = 4 2 8 F m
'1o

E 400.

350

I I
o 50 loo 15o 200 2.50
Time (rain)

Fig. 9. Graphical differentiation of concentration-time curve.

(ii) The diffusivity value may be either smaller or Table 2. Comparison of experimental and theoretical
larger than molecular diffusion coefficients in particle mass transfer coefficients for SDS and phenol
systems
the water phase.
Experimental Theoretical
(iii) The porosity has no recognizable effect on the Pollutant k,, t (m s- i) k,,~(m s-J)
transfer mechanism. Phenol 1.5 x 10-s I.I x 10-s
(iv) The adsorption rate (dn/dT) can be predicted 0.88 x I0 -5 0.88 x I0 -5
with a constant diffusion coefficient, Dc~, which 0.40 x 10-5 0.63 x 10-5
0.28 x 10 -5 0.35 x I0 -5
depends solely on the test system and can be 0.12 x 10 -5 0.23 x 10 -5
determined in a straightforward batch tests.
SDS 7.69 x I0 -7 9.00 x I0 -7
(v) The equilibrium isotherm is very important 5.00 x 10 -7 6.92 x 10 -7
and a constant value of a monolayer coverage, 4.1 x 10-7 5.69 x 10-7
3.31 x 10-7 4.82 x 10-7
Y*, can be used to fit experimental and 2.75 x 10-7 4.10 x 10-7
theoretical results.

CONCLUSION
-6.1

-6.2 A two-resistance mass transfer model has been


¢n
developed for the adsorption of pollutants onto
-6.3
carbon. Theoretical concentration decay curves were
-6.4 generated using an external mass transfer coefficient
-6.5 and a pore diffusion coefficient and these were cor-
I related, using a best fit technique, against the experi-
2.3 2.4 2.5 2.6 2.7 2.8 mental curves. It was possible to correlate all the
Log t i m e
experimental curves, with reasonable accuracy using
Fig. 10. Log particle mass transfer vs log time for SDS. a single constant external mass transfer coefficient
and a single constant pore diffusion coefficient for
each solute/carbon system. A rapid analytical solu-
-4
tion has been developed for adsorption systems in
which the operating fines and tie lines terminate on
the saturation monolayer of the isotherm.

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