Ind. Eng. Chem. Res.

1991,30,1289-1293 1289
Sahimi, M. On the Determination of Transport Properties of Dis-
ordered Systems. Chem. Eng. Commun. 1988,64,177-195.
Sahimi, M.; Gavalas, G. R.; Tsotsis, T. T. Statistical and Continuum
Models of Fluid-Solid Reactions in Porous Media. Chem. Eng.
Sci. 1990,45, 1443-1502.
Sahimi, M.; Hughes, B. D.; Scriven, L. E.; Davis, H. T. Real-Space
Renormalization and Effective-Medium Approximation to the
Percolation Conduction Problem. Phys. Reo. E 1983,28,307-311.
Schopper, J. R. A Theoretical Investigation of the Formation Fac-
tor/Permeability/PorodlityRelationship Using a Network Model.
Geophys. Prospect. 1966,14, 301-341.
Sing, K. S. W. The Use of Gas Adsorption for the Characterization
of Porous Solids. In Fundamentals of Adsorption; Proceedings
of the Third International Conference on Fundamentals of Ad-
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of Germany; Mersmann, A. B., Scholl, S. E., Ma.; Engineering
Foundation: New York, 1990.
Stauffer, D. Introduction to Percolation Theory; Taylor & Francis:
London, 1985.
Stinchcombe,R. B.; Watson, B. P. Renormalization Group Approach
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Received for reuiew May 14, 1990
Revised manuscript receioed November 19, 1990
Accepted December 2, 1990

Kinetics of the Conversion of Calcium Sulfate to Ammonium Sulfate

Using Ammonium Carbonate Aqueous Solution
Elamin M. Elkanzi* and Mohamed F.Chalabi
Department of Chemical and Petroleum Engineering, U.A.E. University, P.O.Box 17555, Al-Ain, U.A.E.

A two-step procedure is described for measuring the intrinsic rate of the slurry reaction between
calcium sulfate and ammonium carbonate. In the first step, experiments were conducted following
the shrinking core model concept to get estimates of the kinetic parameters. These estimates were
then used in a mathematical model to predict an experimental program under which the conditions
of chemical reaction control is likely. The second step is to measure the intrinsic kinetic parameters
under these favorable conditions. A simple power law model fitted to the experimental data of the
second step predicted an activation energy of 72 kJ/mol and a pseudo-first-order reaction with respect
to ammonium carbonate. The procedure may prove useful in measuring the intrinsic kinetics of
fluidaolid heterogeneous reactions and may reduce the effort put on experimental work to establish
favorable conditions for chemical reaction control.

Introduction appreciable amounts even at high conversions of calcium

Ammonium sulfate for use as a fertilizer is generally
manufactured from anhydrous ammonia and strong sul-
furic acid. An alternative process originally developed in
Germany as long ago as 1909 (Higson, 1951)is now in use.
It is based on combining ammonia and carbon dioxide to
produce ammonium carbonate, which then reacted with
gypsum or anhydrite in a three-phase slurry reactor to
sulfate when the overall reaction was carried out in a
fluidized bed reactor. These findings suggest that the first
two steps may not control the overall reaction.
The purpose of this paper is to report a kinetic study
CaS04.2H20(s)+ (NH4)&03(aq) -
for the reaction described by the equation

CaC03(s) + (NH4)2S04(aq)+ 2H20(1) (1)

yield ammonium sulfate and calcium carbonate. However,
little work is reported regarding the kinetics of the reac-
tions involved (Ganz et al., 1959; Chalabi et al., 1975). This
may be attributed to the complexity resulting from the
influence of physical processes that must take place in
order for the overall reaction to proceed. In the three-
phase gas-liquid-solid system involved here, the overall
rate of reaction at any instant of time may be controlled
by one or more of the following steps: (1) gas-liquid mass
transfer; (2) chemical reaction between ammonia solution
and carbon dioxide to form ammonium carbonate; (3)
transfer of ammonium carbonate solution through the
liquid-solid film; (4)diffusion of ammonium carbonate
solution through the calcium carbonate product layer; ( 5 )
chemical reaction at the surface of unreacted calcium
sulphate core.
As these steps take place in series, it is evident that the
slowest step would be rate controlling. Andrew (1954),in
an investigation on carbon dioxide absorption by partially
carbonated ammonia solutions, reported that the rate of
carbon dioxide absorption is controlled by the reaction
between carbon dioxide and ammonia. Chalabi et al.
(1975)reported that ammonium carbonate was present in
* Author to whom correspondence should be addressed.
0888-588519112630- 1289$02.50/ 0
A two-step procedure is to be investigated in order to
measure the intrinsic rate of the above reaction. The first
step is to establish reaction conditions under which
chemical reaction control is likely. These reaction con-
ditions, namely, calcium sulfate particle size, calcium
sulfate slurry concentration, ammonium carbonate initial
concentration, rate of mixing, and reaction temperatures,
are predicted by using a mathematical model based on the
relative importance of the resistances offered by steps 3-5
above. The kinetic parameters of the model are estimated
experimentally by using the shrinking core model concept
(Levenspiel, 1972). The second step is to measure the
intrinsic kinetics of the reaction by using an experimental
program predicted from the results of the first step.
Mathematical Model
As far as is known, the effects of mass-transfer limita-
tions on the course of reaction 1 have not yet been in-
vestigated. Previous experimental investigations (Ganz
et al., 1959; Chalabi et al., 1975) have shown that the
calcium sulfate conversion increases with decreasing size
of calcium sulfate particles and with decreasing slurry
concentrations. Therefore it seems a reasonable assump-
tion that the chemical reaction occurs mainly at the surface
of the available calcium sulfate. As the reaction proceeds,
0 1991 American Chemical Society
1290 Ind. Eng. Chem. Res., Vol. 30, No. 6, 1991
the calcium sulfate will be used up, but the particles may
become coated with solid calcium carbonate product.
Higson (1951) provides a photomicrograph of reaction
magma in which crystals of calcium sulfate and aggregates
of deposited calcium carbonate are clearly shown. This
evidence and the above-mentioned findings would suggest
that the overall reaction can be visualized to take place
via the following sequence: (a) mass transfer of aqueous
ammonium carbonate from the bulk liquid phase to the
external surface of the calcium sulfate particle; (b) diffu-
sion of aqueous ammonium carbonate through the de-
posited calcium carbonate product layer; (c) chemical re-
action at the core surface.
The relative importance of each of these steps will
change as the reaction proceeds. The model equations
describing the rates of the steps at one position in the
reactor are given as
step a: (-rb = k,ap(CAL - )
,C (2)
step b: this is modeling the shrinking core model for a
first-order reaction:
d/dr (P(dCA)/dr)= 0 rc C r C dp/2 (3a)
step c: (-rA) = upkCAc r = rc (4)
Considering the progress of reaction from fresh solid
spherical particle to acompletely converted particle in an
isothermal, irreversible fmborder reaction, the average rate
of reaction of the fluid reactant (A = (NH,),CO,) based
on unit surface area of particle may be obtained by com-
bining eqs 2-4 as follows:
(-r~)av = CAL/P/(~+
J (dp/4De) + (3/k)l (5)
Since the shrinking core model envisages the overall pro-
cess as composed of three resistances in series, the con-
centration difference of the transferring component (N-
H1)2C03over each of these steps will be inversely pro-
portional to the resistance to transfer in that step. From
eq 5 we have
ACA/CAL= [l/kn + (dp/4De)l/[l/k, + dp/4De + 3 / k ]
(6)
where ACA is the difference in concentration of (NH4)&03
between the liquid bulk (C,) and that at the gypsum core
of a particle (CAc). Reduction of the mass-transfer re-
sistances to low values allows chemical reaction to be rate
controlling. Equation 6 is used to make estimates of the
relative importance of the resistances to mass transfer,
diffusion through product layer, and chemical reaction.
Although none of these resistances could be predicted with
confidence, it was thought that the effort might lead to
a worthwhile reduction in experimental work, before
conditions were established where the reaction was truly
the rate-determining step.
Estimation of Model Parameters
The liquid-film mass-transfer coefficient may be esti-
mated in the case of a mechanically agitated reactor from
correlations reviewed by Pandit et a1 (1986):
(ha/ U ) N s $ 7 6 ( d p U p ~ / p ~ ) o 3.04
.6 (7)
when 17 C N b C 270 and 13.7 C N h C 3200, or from
k,/ U = 2.165/ (Nb)O.*(Ns,)
2/3 (8)
when N b C 17.
The effective diffusivity of (NH,),CO, solution through
ciolid CaC03 may be estimated from the molecular diffu-
riivity using a solid tortuosity factor (Satterfield, 1980;
Epstein, 1989). The value of the reaction velocity constant
has not been reported in literature. Estimates of this
parameter have to be determined experimentally. Here
the application of the Shrinking core model to the reaction
would yield an estimate of the apparent reaction rate
constant provided that the assumptions and conditions
embodied in the model are approached. With these pa-
rameters being established, eq 6 becomes a function of
calcium sulfate particle size and of speeds of mixing and
of temperature. A plot of ACA/C, versus calcium sulfate
particle size, with temperature and with speed of mixing
as parameters, would yield a family of curves from which
the conditions under which chemical reaction control is
likely may be predicted.
Experimental Section
The first set of experiments were conducted to establish
an estimate for the apparent reaction rate constant under
conditions approaching those embodied in the shrinking
core model. The reaction conditions selected were as
follows:
(1)Calcium sulfate slurry concentration was of 5% by
weight (Ganz et al., 1959; Chalabi et al., 1975).
(2) Ammonium carbonate aqueous concentration was
kept constant at ita saturation value at each temperature.
In this manner the calcium sulfate conversion would be
a function only of its slurry concentration. This would
ensure that the time for complete conversion and the ap-
parent reaction rate constant be constant for constant
temeprature, particle density, and diameter. The as-
sumption of pseudo-first-order kinetics embodied in the
shrinking core model would also be approached.
(3) Calcium sulfate particle size was kept below 50 pm.
(4) The temperature was varied between 10 and 20 "C
in steps of 5 "C. These temperatures were lower than those
used in previous work.
(5) Speed of mixing (impeller speed) was kept constant
at its maximum value of 2200 min-'.
The second set of experiments were conducted to es-
tablish the intrinsic rate expression for the reaction under
conditions predicted by the mathematical model of eq 6.
The independent parameters investigated include ammo-
nium carbonate concentration, temperature, and conver-
sion time.
Apparatus. All experiments were conducted in a l-L
three-necked round-bottom flask supplied with a stirrer,
thermocouple ports, a sampling port fitted with a micro-
filter, and suction pump. Agitation of the reactor contents
was carried out with a pitched-blade turbine having three
blades. The turbine was driven by a variable-speed motor.
The reactor temperature was maintained constant by a
constant-temperature bath provided with a thermoelectric
controller. The reactor was operated in a batch manner.
Materials. The calcium sulfate used in this study was
Analar quality microfine powder. The ammonium car-
bonate used was of the commercial type (NH4HC03+
NH2COONH4)genral reagent quality. Deionized water
was used. Other chemicals used as reagents in analysis
were all of the AnalaR type.
Procedure. For each experimental run, a weighed
amount of ammonium carbonate was charged to the re-
actor containing 500 mL of deionized water. Stirring of
the reactor content, at 36.6 revolutions/s, was then started.
When the desired temperature had been reached, calcium
sulfate already cooled to the reaction temperature was
added as required for the reaction to start. It is important
 Ind. Eng. Chem. Res., Vol. 30,No. 6,1991 1291
to charge first the ammonium carbonate because of its
highly negative heat of solution. .55 -
The course of the reaction was followed by means of
1-mL clear-liquid samples that were analyzed for ammo- 45-
nium sulfate content through the determination of the
sulfate radical. The analytical method devised was based
on measuring light absorption by a turbid suspension
caused by reacting barium chloride with the already
treated sample containing ammonium sulfate. For this
purpose a Pye Unicam Model SP8-400double-beam UV-
vis spectrophotometer was used. The analytical method D 1 :291K
is quite sensitive, and ammonium sulfate concentrations
as low as 1 X lo4 M can be detected. The accuracy of the
method depends upon the sample being dilute and
.
& T
T
.2edn
281 n

therefore the original 1-mL sample goes through a series

of dilutions. Corrections to the analytical results were 0 2 4 6 8
REACTION TI=,
IO
Minules
12 14 16

made on account of the sulfate content of dissolved calcium

sulfate, of the withdrawal of liquid by sampling, and of Figure 1. Shrinking core model.
dilution due to the generation of water by reaction.
In the first set of experiments the data were taken in
the temperature range 10-20 O C , ammonium carbonate
concentrations corresponding to the saturation value at
each temperature, and calcium sulfate concentration of -2.5-

0.05 kg/L of water.

In the second set of experiments the data were taken
under the conditions predicted by the mathematical model,
3-
namely, the temperature range and calcium sulfate particle
size. Ammonium carbonate initial concentrations ranged
-
P

-
.
from 0.1 to 0.2 M and calcium sulfate was present in exceas.
Different initial concentrations of ammonium carbonate -1.5 -
were used so as to measure the kinetic parameters over a
wider range of concentrations.
Rssults and Discussion
3.4 1.12 1.45 1.47 3 50 1.52 1.55
For the process design, it is important to obtain the 1 I 103 n"
-
kinetic expression for the reaction of eq 1. This reaction 1

is the most important and effective one occurring during
the ammonium sulfate production process. A two-step
procedure is followed in this study: (a) determination of
the conditions under which the reaction is chemically
controlled and (b) measurement of the intrinsic kinetic
parameters under the conditions determined in step (a).
Results from the kinetic analysis of each step are discussed
separately.
Reaction Conditions. The conversions for calcium
sulfate with time, at temperatures of 10,15, and 20 OC and
ammonium carbonate concentration of 1.38,1.60, and 1.85
kmol/m3 (saturation value at each temperature, respec-
tively) were obtained. These experimental data were an-
alyzed on the basis of the shrinking core model. Levenspiel
(1972) showed that when the rate is controlled by the
chemical reaction at the core surface, then for both
shrinking and constant-size particles the solid reactant
conversion is given by
t/T = 1 - (1 - x)1/3 (9)
where
T = pBdp/2bkCfi (10)
The experimental data were plotted on the basis of eq 9
for all three temperatures as illustrated in Figure 1. The
values of T were obtained from the slopes of the lines in
Figure 1. The value of k can then be calculated from eq
10. It was assumed that the size distribution of calcium
sulfate particles remains constant and an average value for
dp of 30 pm was used. The molar density of calcium sulfate
is 24.6 kmol/m3. The value of b can be obtained from eq
1. The saturation concentration of ammonium carbonate,
Figure 2. Arrheniua plot of the shrinking core model.
C, at any temperature was kept nearly constant by using
excess carbonate. Thus all the parameters in eq 10 are
constant at each temperature, and hence k would change
with temperature in approximately the same ratio as the
reciprocal of T. A plot of In 1/r against the reciprocal of
absolute temperature is illustrated in Figure 2. The slope
of the line indicates an apparent activation energy of 70
kJ/mol for the reaction of eq 1. The apparent reaction
rate constant can be represented by
k = 1.54 X (11)
Since the stirring speed was kept constant at 36.6 revolu-
tions/s, the value of k, can be estimated from eq 7. An
order of magnitude value for the effective diffusivity De
of 3 X lo-" m2/s is estimated from the molecular diffu-
sivity by using a solid tortuosity factor. Substitution of
these values in eq 6 allows the calculation of the fractional
change in concentration with the particle diameter. Figure
3 illustrates some of the results as a plot of ACA/Cfi vs
calcium sulfate particle diameter with temperature as a
parameter. As expected, the fractional change in con-
centration decreases with decreasing particle size at each
temperature. Figure 3 indicates that with particles of less
than 50 pm and with temperature of 10 OC or lower, the
mass-transfer limitations on the rate of reaction would be
less than 2%. Therefore it seemed likely that with a
stirring speed of 36.6 revolutions/s, with temperatures of
10 "C or lower, and with particle sizes below 50 pm, the
reaction of eq 1 would be effectively controlled by the
speed of the chemical reaction. Besides the effect of the
particle size on mass-transfer limitations, the effect of
1292 h d . Eng. Chem. Res., Vol. 30, No. 6, 1991

1.5-
(5) T i 293 K
1.25-

_1 20
( 4 )
5 1 -

,751
13)

(2)
o 1 i 278 K

0 20 40 60 80 1W 12C
PARTICLE DIAMETER,
r m REACTION TIME,MInulcr

Figure 3. Fractional change in concentrationsv8 particle diameter Figure 4. Continuous reaction model.
(es 6).
8 ,

Tuble I. Experimental Results for the Reaction Starting

with 0.1 ka mol/m8 (NHACO, Aqueous Solution
reaction (NH,)$O, concn, kg mol/m3 X lo2
time, min T = 273 K T = 278 K T = 283 K
0 0 0 0
10 0.5 0.8 1.2
20 0.9 1.5 2.3
30 1.3 2.1 3.3
40 1.7 2.1 4.1
60 2.4 3.8 5.4
80 3.0 4.7 6.5
100 3.1 5.4 7.3
120 4.3 6.1 1.9
140 4.8 6.1 8.4
160 5.2 1.2
180 5.6 1.6 I5 352 355 357 3 5 362 365 357 37
f I 10 '. K1

temperature level should not be overlooked. In fact, the

reaction of eq 1 is both reversible and parallel with respect
to ammonium carbonate. Nowak et al. (1989) studied the
kinetics of the decomposition of ammonium carbonate in
aqueous solutions. They found that the reaction is second
order with respect to ammonium carbonate concentration
and has an activation energy of 98.9 kJ/mol. Therefore,
low-temperature level and low concentration level would
not favor the decomposition of ammonium carbonate. To
minimize the effect of this side reaction in comparison to
the main reaction of eq 1, and to make mass-transfer lim-
itations small, the following reaction conditions may be
used for the study of the intrinsic rate of the reaction of
eq 1: (i) calcium sulfate concentration of 5 wt 90' (Ganz
et al., 1959; Chalabi et al., 1975); (ii) ammonium carbonate
aqueous concentration of 0.1-0.2 kg mol/m3; (iii) speed of
mixing of 36.6 revolutions/s; (iv) temperature range of 0-10
OC; (v) calcium sulfate particle sizes below 50 pm.
Intrinsic Rate Measurement. Several runs were made
using ammonium carbonate initial concentrations of 0.1,
0.15, and 0.2 kmol/m3. Calcium sulfate concentration was
kept constant a t 5 wt 9'O (this is in excess of its stoichio-
metric proportion of eq 1). This would allow the surface
area to remain essentially constant during the course of
the reaction and the rate to be independent of the calcium
sulfate concentration. Each run was repeated in duplicate
and repeated for a third time to check reproducibility.
Concentration vs time results were as presented in Table
I for the initial concentration of ammonium carbonate of
0.1 kg mol/m3.
Having correlated the results in the absence of mass-
transfer limitations, it was found that the kinetic equation
representing the continuous reaction model, of a firsborder
Figure 5. Arrhenius plot of the continuous reaction model.
irreversible reaction, is best satisfied. The integral form
of the kinetic equation is
In C,/CA = k,t (12)
The fitting of the above equation to the experimental
data is illustrated in Figure 4. The rate constants k, a t
different temperatures were calculated from the regression
analysis of these data.
An Arrhenius plot shown in Figure 5 gives an activation
energy of 72 kJ/mol for the reaction of eq 1. From this
plot the estimated frequency factor is 4.4 X lo9 s-l at an
ammonium carbonate concentration of 0.1 kmol/m3 and
in the temperature range 0-10 O C . At these conditions the
following equation holds:
k, = 4.4 X lo9 exp(-17234/Rl') (13)
The rate of reaction was found to be independent of the
initial concentration of ammonium carbonate in the range
0.1-0.2 kmol/m3.
Substituting the value of k, from eq 13 into eq 6 and
using a particle diameter of 50 pm and the previously
estimated values of k, and De,the percent fractional change
in concentration was less than 0.019i for the temperature
range studied. This clearly demonstrates that mass-
transfer limitations were negligible and that the rate of
conversion is controlled by the reaction step.
Conclusions
The work presented in this paper applies a general
method involving a two-step procedure for the measure-
ment of intrinsic kinetics of fluid-solid heterogeneous
 Ind. Eng. Chem. Res. 1991,30, 1293-1300 1293

reactions. The method has been applied to the measure-
ment of the intrinsic kinetics of the conversion of calcium
sulfate to ammonium sulfate using aqueous "onium
carbonate solution. In the first step the conditions for
chemical reaction control were established. In the second
step the intrinsic kinetics were measured under the con-
ditions established in the first step.
The experimental findings showed that the main ad-
vantage of this method is that it helps to predict the re-
action kinetics by establishing the conditions where the
chemical reaction is truly the rate-controlling step.
Under the experimental conditions studied here, the
kinetics of the conversion of calcium sulfate to ammonium
sulfate using ammonium carbonate aqueous solution were
tentatively represented by a pseudo-fmt-order model, and
an activation energy of 72 kJ/mol was obtained.
Nomenclature
a, = area per unit volume, m-l
b = stoichiometric coefficient (eq 10)
CA = concentration of aqueous ammonium carbonate,
kmol/m3
CAc= concentration of aqueous ammonium carbonate at the
core surface, kmol/m3
C, = concentration in bulk liquid, kmol/m3
C, = initial concentration, kmol/m3
Ck = concentration at the surface of the solid, kmol/m3
ACA = molar concentration drop of component A, kmol/m3
De = effective diffusivity of aqueous ammonium carbonate
solution through calcium carbonate ash layer, m2/s
d, = particle diameter, m
k = apparent reaction rate constant, m/s
k, = intrinsic rate constant, s-l
k, = liquid-film mass-transfer coefficient, m/s
NRe = Reynolds number, defined by N R =~ dpUeL/pL, di-
mensionless
N k = Schmidt number, dimensionless
R = gas constant, cal/mol K
r = particle radius, m
(-rA) = rate of reaction, kmol/m3 s
r, = core radius, m
T = temperature, K
t = reaction time, s
U = slip velocity, m/s
U, = relative velocity between a particle and liquid generated
because of impeller action, m/s
X = fractional conversion
Greek Letters
pL = liquid viscosity, kg/ms
pB = molar density of calcium sulfate, kmol/m3
pL = liquid density, kg/m3
7 = time required for complete conversion, s
Registry No. CaS04, 7778-18-9; (NH4)2C03, 506-87-6; (N-
H4)2S04,7783-20-2.
Literature Cited
Andrew, S. P. Carbon dioxide Absorption by Partially Carbonated
Ammonia Solutions. Chem. Eng. Sci. 1954, 3, 279.
Chalabi, M. F.; Younis, S. M. Conversion of CaS04 into (NH4)804
at Ammoniated Gypsum Slurries by Co, Gas. Presented at Chisa
International Congress on Chemical Engineering, Prague, Che-
cozlovakia, 1975.
Conversion of Gypsum or Anhydrite to Ammonium Sulfate. Nitro-
gen 1967, No. 46.
Epstein, N. On tortuosity and the tortuosity factor in flow and dif-
fusion through porous media. Chem. Eng. Sci. 1989,44,777-779.
Fertilizer Manual; No. IFDC-R-1; International Fertilizer Develop-
ment Center: AL, December 1979.
Ganz, S. N.; Leibovish, S. B.; Gorbman, S.I. Conversion of CaS04
into (NH4)2S04by Agitating a Mixture of Gypsum Slurry, NHS
and Coz in a Variable Speed Disc Mixer. Zh. A'klad. Khim. 1959,
32,975-978.
Higson, G. I. The Manufacture of Ammonium Sulfate from Anhy-
drite. Chem. Ind. 1951, Sept 8,750-754.
Levenspiel, 0. Chemical Reaction Engineering, 2nd ed.; Wiley New
York, 1972.
Nowark, P., Skrzypek, J. The Kinetics of Chemical Decomposition
of Ammonium Bicarbonate and Carbonate in Aqueous Solutions.
Chem. Eng. Sci. 1989,44, 2375-2377.
Pandit, A. B.; Joshi, J. B. Maes and Heat Transfer Characteristics
of Three Phase Sparged Reactors.
Satterfiold, C. N. Heterogeneow Catalysis in Practice; McGraw-Hilk
New York, 1980.
Received for review May 25, 1990
Accepted December 8, 1990

Heterogeneous Photocatalytic Oxidation of Phenol with Titanium

Dioxide Powders
Tsong-Yang Wei and Chi-Chao Wan*
Department of Chemical Engineering, National Tsing Hua University, Hsinchu, Taiwan, Republic of China

The photocatalytic oxidation of phenol in oxygenated solution with suspensions of titanium dioxide
powders has been investigated. The experimental results indicate that there is an optimum value
for the Ti02content. Sufficient O2supply is needed, but a too high gas flow rate induces large bubbles
that eliminate the gas residence time and the gas/liquid contact interface. The initial concentration
of phenol demonstrates a negative effect on the pseudo-first-order reaction rate constant. A
mechanism of the phenoxide ions being adsorbed on the Ti02 surface has been proposed to account
for this inverse effect. Moreover, the different pH regions affect the competitive adsorption between
the phenoxide ions and OH- ions on the Ti02 surface, which in turn influences the generation of
the hydroxyl radicals on the T i 0 2 surface.

Introduction the degradation of this compound to reach the safety level

Phenol is a major pollutant and under strict effluent in the range of 0.1-1 mPL-' is not easy. Many conven-
restriction. owingto its and solubility in water, tional methods have been proposed to treat phenol solu-
tions (Devlin and Harris, 1984; Eisenhauer, 1964, 1968;
Getoff, 1986; Hackman, 1976; Kharlamova and Tedoradze,
* To whom correspondence should be addressed. 1981; Sadana and Katzer, 1984; Sharifian and Kirk, 1986;
0888-5885/91/2630-1293$02.50/00 1991 American Chemical Society