oooS2509/93 $6.00 + o.

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0 1993 Pergamon Pres Ltd

THE KINETICS OF UNCATALYZED SODIUM SULFITE

OXIDATION

PETER M. WILKINSON, BERT DOLDERSUM and PETER H. M. R. CRAMERS

Department of Chemical Engineering, University of Groningen, 9747 AG Groningen,
The Netherlands

and

LAURENT L. VAN DIERENDONCK

DSM Research, P.O. Box 18, 6160 MD Geleen, The Netherlands

(First received 24 June 1991; accepted for publication in revised form 3 June 1992)

Abstract-The influence of pH, oxygen partial pressure, and sulfite conversion on the reaction rate of
uncatalyzed sodium sulfite oxidation is determined experimentally at a temperature of 20°C. In addition to
these experiments, the change in composition of the sulfite solutions during the reaction was estimated on
the basis of equilibrium and activity constants. A comparison between the outcome of these calculations
and the experimental results shows that the sulfite oxidation mechanism depends on the bisulfite concentra-
tion. Furthermore, it is argued that uncatalyzed sulfite oxidation is to bc recommended as a model reaction
for mass transfer studies as an alternative to cobalt-catalyzed sulfite oxidation at low cobalt catalyst
concentrations.

INTRODUffION vessel. The reactor that was made of glass contained

Catalyzed oxidation of sodium sulfite to sodium sul-
fate is a reaction that is often used for the determina-
tion of the interfacial area or the volumetric mass
transfer constant in different gas-liquid contactors.
The advantage of this catalyzed sulfite reaction sys-
tem is that the oxidation rate constant can be varied
substantially with the catalyst concentration and type
[copper or cobalt catalyst, e.g. Linek and Vacek
(1981)]. The influence of different catalysts on the
oxidation rate has been investigated for over 50 years.
In spite of this, however, there is still much disagree-
ment in the published kinetic data, and the reaction is
not well understood. Large differences between the
oxidation rates in the literature occur for apparently
same reaction conditions, which are usually
attributed to the fact that the oxidation rate is very
sensitive to impurities.
The oxidation of sodium sulfite without catalyst
has been investigated much less than catalyzed oxida-
tion, and while the catalyzed sulfite reaction is used
often for the study of mass transfer, the uncatalyzed
reaction has, at present, been used only by van
Dierendonck (1970) and van Dierendonck et al.
(1988). It is the aim of this paper to determine the
influence of the oxygen concentration, the sodium
sulfite concentration and pH on the reaction rate.
Finally, it is also discussed as to what extent un-
catalyzed sodium sulfite oxidation can be used for the
evaluation of mass transfer data as an alternative to
catalyzed sodium sulfite oxidation.
EXPERIMENTAL PROCEDURE
The oxidation rate of sodium sulfite was deter-
mined with the aid of a standard flat interface stirred
four baffles and an impeller. The stirrer speed could be
varied between 0 and 1.5 s-l, without causing dis-
turbances at the liquid interface. At the start of each
experiment, the reactor was filled with one liter of
a solution of sodium sulfite (Baker CAS No. 7757-
83-7 p.a.) in deionized water. The initial pH (measured
with a Knick portamess 654) of this solution was
adjusted by adding sulfuric acid (Merck, No. 754 p.a.,
Appendix C). During the initial period of the experi-
ment, the oxidation of the sodium sulfite solution by
oxygen and the absorption of carbon dioxide was
prevented by purging the reactor with nitrogen. When
the solution had reached a constant temperature of
2O”C, the reaction was started by feeding the reactor
with air or pure oxygen (presaturated with water
vapor at the temperature of absorption, at atmo-
spheric pressure). The rate of sulfite oxidation was
determined by analyzing samples taken from the solu-
tion at regular time intervals. These sulfite samples
were analyzed with a standard iodometric titration
procedure. In addition to determining the rate of
sulfite oxidation as a function of the pH, the pH
change during the reaction was also measured. The
range of conditions for which these experiments have
been done are:
c Na2soa:0.4 or 0.8 kmol/m3
initial pH: 6.3-9.0
yo* : 0.2-l
N at,rrsr:o-1.5 s-l.
Furthermore, the influence of sulfite conversion on
the reaction rate was also studied in a number of
experiments, by letting the sulfite oxidation proceed

CEI 44:5-w 933

934 PETER M. WILKINSON et al.

for several days until high sulfite conversions
reached.
ABSORPTION THEORY
The experimentally determined oxygen absorption
rate in the sulfite solution is interpreted on the basis of
the penetration theory. On the basis of this theory, it
can be shown (Westerterp et al., 1984) that the absorp-
tion of a gas into a liquid followed by a fast pseudo
nth-order irreversible reaction can be described by
= A k(~,)“(Cb,)” -’ Do,(G).
were The results of the experiments and the calculated
reaction rates are first discussed and then interpreted
on a theoretical basis.
SULFITE OXIDATION RESULTS FROM ABSORPTION
EXPERIMENTS
Influence of oxygen on reaction rate
The reaction order, IV, of oxygen was determined
using two different oxygen partial pressures (air and
pure oxygen). The result of these experiments was that
the absorption rate is proportional to the oxygen
partial pressure. Consequently, the reaction is first-
(1) order (N = 1) in the oxygen concentration.

This equation holds provided Influence of pH and conversion on reaction rate

2 i Ha 4 EAeoo As a consequence of the fact that sodium sulfite (a
base) reacts to the much less basic sodium sul-
with fate, the pH of the solution decreased during the
reaction. From the experiments it appeared, however,
Ha = d-/k, (2) that the reaction rate is not influenced by this pH
change during the first part of the reaction until the
and pH decreases below a value between 5.7 and 5.9. For
higher conversions and, thus, lower pH values, the
E ,,,=1+=. (3) reaction rate decreased abruptly (Figs 1 and 2). Fur-
02 02 thermore, it appeared that the sulfite conversion (X*)
at which the reaction rate decreases depends on the
Whether these conditions are fulfilled or not can be
checked by varying the stirrer speed (Ihaveri and initial sulfuric acid concentration, A,,, and initial so-
dium sulfite concentration, S,; Fig. 3.
Sharma, 1968). For the present experiments it was
observed that the stirrer speed (between 0 and 1.5 s- ‘)
has no influence on the absorption rate, thus justifying
the use of eq. (1) for the evaluation of the reaction rate
constant [k(C,)“]. Furthermore, for the present ex-
periments the value of the Hatta number [eq. (2)] is
higher than two, when estimated from literature k,
values (van Dierendonck, 1970) obtained in a similar
flat-interface stirred vessel. In order to solve eq. (I),
the oxygen solubility is calculated (Appendix A) with
an equation of Schumpe et al. (1978) and the diffusion
constant was taken from data of Linek and a.aL-.-...--.-...............’
0 100 *oo 300 ‘00 so0 .,:

Mayrhoferova (1970) (Table 1). The pseudo first-order time/l 000 03)
reaction rate (K,) was then calculated fom the experi-
mental absorption data by rewriting eq. (1): Fig. 1. Sulfite conversion and pH vs time (initial sulfite
concentration = 0.77 mol/l, initial sulfuric acid concentra-
2
tion = 0.059 mol/l and T = 20°C).
K, = & k(C,)M (C&J- 1= i d%-
Do, [ A(&) 1
1
1 0.5Rml 2
=-
Do* [ z5 .
8, PH

(molll)

Table 1. Physical properties of the sodium sulfite

sohnion

GWO. 10-3q 10 9Do,

boliV (Pa s) (m’/d

0.00 1.002 2.27

0.25 1.17 1.95
0.50 20 1.35 1.75 Fig. 2. Sulfite conversion and pH vs time (initial sulfite
0.80 20 1.45 1.60 concentration = 0.79 molfl, initial sulfuric acid concentra-
tion = 0.25 mol/l and T = 2O’C).
 Kinetics of uncatalyzed sodium sulfite oxidation 935
dix A]. Consequently, it can be concluded that the
infIuence of the amount of added sulfuric acid, Au, on
the reaction rate is not a result of catalytic impurities
X’ in the sulfuric acid.

THEORY FOR SULFITE OXILBATION AS A FUNCTION OF

0.4 REmoN OF
CONST*M CONVERSION AND pI4
0.1 REAFTlON RATE From the above-mentioned experimental results it
_._ appears that the oxidation rate of the uncatalyxed
0.00 o.,o 0.10
sodium sulfite reaction is a function of the initial
OIO a.0 0.10

WS. amount of sulfuric acid added to the solution (Fig. 4),

Fig. 3. Total sulfite conversion, X,,, below which the reac-
tion rate remains constant vs A,,/&.
Influence of initial sulfuric acid addition on reaction
rate
In order to adjust the initial pH of a sodium sulfite
solution, an exactly determined amount of (96%) sul-
furic acid was added at the beginning of the reaction
for each experiment (Appendix C). From these experi-
ments it appeared that the (pseudo first-order) reac-
tion rate constant (K,) increased with the amount of
sulfuric acid added (Fig. 4). (The value was calculated
from cq. (4) and the initial slope of the sulfite vs time
curve.) At sulfuric acid concentrations below
0.11 mol/l, the reaction rate can be approximated by
K, = 12.5(A0)0.5
while the pH decrease during the reaction has no
influence on the reaction rate down to a pH between
5.1 and 5.9. It was also found that the reaction rate is
no longer constant but decreases (Figs 1 and 2) for
higher sulfite conversions and, thus, lower pH values.
In order to explain the pH and sulfuric acid influence
on the reaction rate and the pH change during reac-
tion, it is necessary to determine the relation between
pH and the composition of the solution. This can be
done by taking into account that at every stage of the
reaction there are two constraints on the composition
of the solution: it is electrically neutral, and the total
amount of sulfur is constant; furthermore, it is as-
sumed that there are four acid-base equilibriums in-
volved:
(5) ~SO;Z~O+ mso:-m5t,0+
(7)
K_i =

mHs0;
while for sulfuric acid concentrations above 0.11 mol/l 3

a different relationship holds: k0i YH,O+ %SOi mH,O+

GO, = (8)
K, = 350(.4,)2. YQ *,a
(6)
Furthermore, it was found that this relationship be- _ _ _ x30:- hsO+ k:- mH,O+
K *-- (9)
tween the initial sulfuric acid concentration, A*, and VHSOi mHSOi
the reaction rate, K,, is not caused by trace (catalytic) K v = YOW- YH,o+ ~OH- mn,o+la,. (10)
impurities in the added sulfuric acid, because repeat-
ing the experiments with sulfuric acid from a different Charge neutrality:
firm (AKZO Chemicals) and with sodium sulfite solu- musc+musc~+2mso- + 2mso- +mou-
tions from a different firm (Merck, art. No. 6657 p.a.)
leads to the same results. In addition to these experi- = %,O+ + mN.+ (11)
ments it was also determined that the addition of Total sulfur is constant, C:
sulfuric acid neutralized with sodium hydroxide had
no influence on the reaction rate Cprovided a correc- 2mH,; + 2m-; + 2mso:- + 2msof- + 2mso,
tion was made or the decrease in oxygen solubility = mu,+ + [2ms&- It-0 = C. (12)
using the method of Schumpe et al. (1978), see Appen-
Sulfite conversion, X, is:

x=l_Cmso:- +m-;+W0,1, =-SO-S,

so so
10 (13)
K I (s-‘) with initial amount of sulfite

SO = Cmsoj- + ms.0; + m0,1,=0. (14)

I
The above set of equations determine the composition
of the sulfite-sulfuric-acid solution throughout the
0.t
I . . . . . . .
reaction (provided reaction intermediates are neg-
m.a, 0.1
lected). The main problem in solving these equations
m.00,

A* (molll)
is that the activity coefficients will not be equal to one
Fig. 4. First-order reaction rate constant vs the initial for the concentration range involved in our experi-
amount of added sulfuric acid, A,. mental study. Furthermore, the exact value of the
936 PETER M. WILKINSON et al.

activity constant cannot be determined easily. The

L
concentration level (and ionic strength) of the solution lh model

is much too high for an accurate estimation of activity - m

___ -;
coefficients by the Debye-Hlckel equation. Other -- so:-
(semiempirical) equations for estimating the activity - *n_
coefficients at. higher concentrations and ionic
strengths have been deveioped [e.g_ Pitter and
Mayorga (1973) and Bromley (1973)]. For the present
calculation the equations of Pitzer and Mayorga
(1973) (Appendix B) were used to estimate the activity 0.0 0.i 0.4 0.0 *.I Ii
constants, y, and the water activity, aw. By solving the convercion (Xb

equations for the activity constants together with eqs

(7)-(14) and the equilibrium constants (Table 2), the
pH and the composition of the sulfite solution were
calculated as a function of the sulfite conversion, X.
The sulfite and sulfate equilibrium constants neces-
sary for the evaluations of eqs (7)-(10) were taken
from literature sources. The value of these constants
at 20°C are given in Table 2.
RESULTS OF MODEL CALCULATIONS
In Figs 5 and 6 the calculated pH, the suhite con-
centration, the bisulfite concentration and the sulfur
dioxide concentration are shown as a function of
sulfite conversion, together with the experimentally
determined pH change. From these figures it appears
that the experimental pH is predicted reasonably well
Fig. 6. Calculated bisuhite concentration, sulfite eoncentra-
tion and pH vs conversion, together with the experimentally
determined pH change (for the same conditions as ia Fig. 2)
drawn from the solution to the gas phase, which may
account for the underestimation of the predicted pH.
From Figs 5 and 6 it can also be seen that the
AND DISCUS!3ION (calculated) bisulfite concentration remains virtually
constant during the reaction until the pH decreases
considerably. The reason for this can be understood
by combining eqs (11) and (12) into
m-:-= 2(mso-)rze - mnsoi - 2Qo,
- mH,0+ + ~OH- (19

by the calculated pH. It does, however, demonstrate the total initial amount of acid being
that the pH is systematically underestimated at low
pH values. A possible explanation for this observation c%o-]1=0 = Ao. (16)
is that the partial pressure of sulfur dioxide becomes This equation can be further simplified by compar-
only relatively high at low pH values (and thus high ing the values of the terms on the right-hand side of
conversions). Consequently, especially at low pH, the equation. The value of the first term on the right-
some sulfur dioxide (a strong acid) is constantly with-
hand side is twice the amount of initially added sul-
furic acid, Aa. Its value was determined experi-
mentally (Fig. 7). The values in Fig. 7 indicate that
Table 2. Equilibrium constants at 20°C
A0 9 m&o+ (17)
Equilibrium
constant Value Reference A0 p man- (18)
provided that the initial pH of the solution is less than
5.448 x 10-s Zemaitis et aI. (1986)
0.0195 Zemaitis et aI. (1986) 11 and the pH is higher than three. The order of
0.012 Robinson and Stokes magnitude of mso, and mnso; can be estimated by
(1970)

- PM
--- M6oj
PH -- SO:-
- SUL

0.0 0.) 0. 0.. 0.0 2.0

aonvarsion (Xl Sulfuric 6oid (molll)

Fig. 5. Calculated bisulfite eoneantration, sulfite eoneantra- Fig. 7. Experimental pH of sulfite solution vs sulfuric acid
tion and pH vs conversion, together with the experimentally concentration for various sodium sulfite eoneentrations (at
determined pH change. (for the same conditions as in Fig. 1). 20°C).
 Kinetics of uncatalyzedsodium sulfiteoxidation
rearranging eqs (8) and (9):
YSO:- YH,O+%a, - mHsO+
m HSO; =
K HSO; .
YHSO;
Both sulfur dioxide and bisulfate are strong acids
(I&,, and Kaso; are relatively large, Table 2) and,
therefore, their concentration will be high only at low
pH values (pH 4 6). Consequently, on the basis of eqs
(17)-(20), it can be concluded that the right-hand side
of eq. (15) contains only one nonnegligible term for
pH values above x 4-5:
m HSOi x 2Ao.
In other words the bisulfite concentration remains
constant during the initial period of the reaction and
its concentration can be calculated from eq. (21). Fur-
thermore, Figs 5 and 6 show that the pH drops signi-
ficantly when the conversion is such that virtually all
the sulfite (not bisulEte) has reacted. This can be
understood from the fact that sulfite (SO:-) is a base
that reacts to form a more neutral component
(sulfate). The most important result of the present
calculations is, however, obtained by comparing Fig.
1 with Fig. 5, and Fig. 2 with Fig. 6. From both these
comparisons it appears that both the reaction rate
and the sodium bisulfite concentration remain con-
stant during reaction down to a pH of six, while they
both decrease at higher sulfite conversions and, thus,
lower pH values. Obviously, this is an indication that
the reaction depends on the bisulfite concentration. In
other words, uncatalyzed sulfite oxidation appears to
proceed through a teaction mechanism that depends
on the bisul~te (mHao,) concentration:
K, = k(m,so,)M.
This assumption can also be used to explain the fact
that the initial amount of the sulfuric acid, Ao, deter-
mines the value of the reaction rate K,, as was shown
in Fig 4. Furthermore, by substituting eq. (21)
(maso,-= 2Ao) in eqs (5) and (6), two new equations for
the rate constant are obtained:
K, = 8.8(mHros)‘-’ for m-, -c 0.22 mol/l
and
K, = 87.5(musoj)2 for mnsoi z=-0.22 mol/l.
SULFITE OXIDATION AT LOW pH AND HIGH
CONVERSION
So far, it has been argued that the initial concentra-
tion of bisulfite remains constant during the reaction,
provided the pII remains above 5.9, and it was argued
that the reaction rate depends on the bisul$te concen-
tration. Furthermore, on the basis of experiments it
was shown (Fig. 3) that the reaction rate remains
constant provided
2.2A.
x*31---.
SO
937
In what follows, the change in reaction rate at higher
conversions and, thus, lower pH values will be dis-
cussed with arguments similar to the above.
In the preceding section it was argued that the
bisulfite concentration remains constant during the
(20) initial stage of the reaction. It was also calculated
(Figs 5 and 6) that when the conversion is such that
virtually all the sulfite in the form of SO:- has
reacted, then the remaining sulfite is mainly present in
the form of HSO; (bisulfite) and still almost equal to
the initial bisulEte concentration. Obviously, for still
higher conversions the bisulfite can no longer remain
constant but will decrease. In other words, the bisul-
fite concentration will certainly decrease when
(21) 5, < mHSOi c= 2&v eq. (2111
Combining with eq. (13) leads to the conclusion that
for conversions above
the bisulEte has to decrease (and, in addition, the pH
drops significantly). A comparison of this equation
with eq. (25) shows that these two equations are very
similar but not same. This difference (although small)
seems to indicate that the reaction rate starts to
decrease just before the bisulEte concentration
decreases, which indicates that the reaction rate is
controlled not just by the bisuhite concentration. To
study this aspect of the reaction further, some addi-
tional calculations were made. In order to establish
whether the reaction orders and (thus, the reaction
mechanism) remain the same for high conversions
(and, thus, low pH values), the model eqs (7)(14) were
combined with the reaction rate eqs (23) and (24).
With the aid of these equations the change in sulfite
(22) concentration as a function of time was calculated and
compared with the experimentally determined con-
centration decrease. These calculations were done
both for low sulfuric acid concentrations (for which
M = 0.5, Fig. 8) as well as for high sulfuric acid
concentrations (for which M = 2, Fig. 9). The results
of this comparison clearly show that the experimental
conversion at which the reaction rate decreases is
(23)
(24)
Fig. 8. Experimental and calculated (with M = 0.5) sulfite
concentration, SJS,,. vs time (for the same conditions as in
(25)
Fig. 1).
938 PETER M. WILKINSON et al.
PH
Ikw - For the evaluation of mass transfer in gas-liquid
I---z%*
I: mPmImMt
Py
time/ 1000 (al
Fig. 9. Experimental and calculated (with A4 - 2) sulfite
concentration, &/So, vs time (for the same conditions as in
Fig. 2).
indeed slightly lower than is calculated, but what is
even more noticeable is that the experimental de-
crease in the reaction rate in Fig. 8 is much more
abrupt than is calculated. The main problem in ex-
plaining these differences is caused by the fact that the
reaction mechanism of sulfite (or bisulfite) oxidation is
not known. One speculative explanation is that the
reaction rate depends not only on the oxygen and
bisulfite concentrations but also that it changes from
zero order in the sulfite concentration to first order at
very low sulfite concentrations. If the sulfite concen-
tration then becomes very low, as is the case for sulfite
conversions that approach X* [eq. (25) or eq. (26)],
then a marked decrease in the reaction rate would
occur. However, at present no conclusive statements
can be made as to the exact reaction mechanism, and
although the present experiments and calculations
have shown that bisulfite is certainly involved in the
reaction mechanism, more research will be necessary
to determine the precise reaction mechanism.
COMPARJSON WITH LITRRATURE DATA
In the previous section it was argued that un-
catalyzed sulfite oxidation proceeds through a reac-
tion mechanism that depends on the bisulfite concen-
tration, and it was established that the reaction is
first-order in oxygen. A comparison with literature
data on the oxidation of sodium sulfite in the presence
of a cobalt catalyst reveals that this catalyzed reaction
must proceed through a very different mechanism.
First of all, the catalyzed reaction rate decreases with
a decrease of the initial pH (which is opposite to the
uncatalyzed reaction); as a result, the catalyzed reac-
tion rate decreases during the reaction as the pH
decreases (Linek and Tvrdik, 1971), which also differs
from the uncatalyzed reaction (Figs 1 and 2). Finally,
it also appears that the reaction order in oxygen is not
the same. According to Linek and Vacek (1981), the
reaction order in oxygen is two for the air-cobalt-
catalyzed sulfite system (at atmospheric pressure),
while it is one for the uncatalyzed oxidation.
DETERMINATION OF MASS TRANSFER WiTH
UNCATALYZED OR CATALYZED SULFITE OXIDATION
AS A MODEL REAC~~ON
reactors such as bubble columns and stirred reactors,
various model reactions have been proposed
(Gianetto and Silveston, 1986) as an alternative to
cobalt-catalyqed sulfite oxidation. In spite of this, sul-
fite oxidatibn is probably s&l1 the most frequently
used modei ,re&tion. The main advantage of the sul-
fite system is that the reaction rate can be varied
substantially by a change in catalyst concentration.
From the present investigation it appears, however,
that the use of this catalyzed sulfite oxidation at very
low catalyst concentrations should be used with cau-
tion. For extremely low catalyst concentrations it is to
he expected that the reaction mechanism and reaction
orders will change and ultimately become equal to the
kinetics of the uncatalyzed sulfite oxidation described
in the present paper. An example of this phenomenon
can be found in the work of Sawicki and Barron
(1973). They observed a change in the reaction order
of oxygen as a function of the cobalt concentration_
For low cobalt concentrations the reaction appeared
to be first-order in oxygen (which is in agreement with
the uncatalyzed oxidation) while for higher cobalt
concentrations the reaction was second order in oxy-
gen (which is in agreement with the catalyzed oxida-
tion).
As a consequence of this uncertainty in applying the
catalyzed sodium sulfite reaction at very low cobalt
concentrations, it is to be recommended that the un-
catalyzed sodium sulfite reaction be used as a model
system for the study of mass transfer when a low
reaction rate is required. A particular advantage of
uncatalyzed sulfite oxidation in determining mass
transfer is that the reaction rate remains constant
until relatively high conversions (depending on the
initial sulfuric acid and sodium sulfite concentration,
Fig. 3). An example of the use of this reaction for
determining the volumetric. mass transfer rate in
a bubble column (Wilkinson, 1991) and a loop venturi
reactor will be the subject of a subsequent paper.
CONCLUSIONS
The main conclusions that can be drawn from the
present research on uncatalyzed sodium sulfite oxida-
tion are:
-Model calculations involving activity constants
and equilibrium data can be used to predict
accurately the change of pH as a function of
sodium sulfite oxidation to sodium sulfate.
-In addition, these calculations were also used to
explain the kinetic results from uncatalyzed so-
dium sulfite oxidation in terms of a bisulfite-
dependent reaction mechanism.
-It is demonstrated that cobalt-catalyzed sulfite
oxidation and uncatalyzed sodium sulfite oxida-
tion differ considerably.
 Kinetics of uncatalyzed sodium sulfite oxidation
- Furthermore, it is argued that uncatalyzed sulfite
oxidation is to be recommended as a (slow)
model reaction for mass transfer studies.
NOTATION
activity, mol/kg
aA+ Debye-Hiickel constant, (ks/mol)“.5
A flat-interface surface area of stirred cell, m2
initial amount of added sulfuric acid, molfl
A0
b constant in Pitzer equation (B3), dimension-
less
B interaction terms defined by Pitzer equa-
tions (B4) and (B5), kg/mol
Pitzer interaction coefficient, (kg/mol)2
concentration of component A, mol/l
molecular diffusion coefficient of species b,
m’/s
enhancement factor for an infinitely fast re-
action (3), dimensionless
f’ interaction term defined by Pitzer equation
(B3), dimensionless
interaction term defined by Pitzer equation
f4
(B lo), dimensionless
Hi,j salting-out coefficient in eq. (Al) l/mol
Ha Hatta number defined in eq. (2), dimension-
less
k reaction rate constant defined in eq. (I),
m3’N+M-l~/mo~‘N+M-” s
kt mass transfer coefficient, m/s
K, pseudo-first-order rate constant, s- 1
K equilibrium constant defined in eqs (7)-(10)
mA molality of component A, mol/kg
N stirrer speed, rev/s
P pressure, Pa
R rate of conversion, mol/s
initial amount of sodium sulfite, mol/l
SO
S-r sum of the S02, HSO; and SOj- concen-
trations, mol/l
T temperature, K
X sulfite conversion, dimensionless
oxygen mole fraction in gas phase, dimen-
yol
sionless
Zi ionic valence of species i, dimensionless
Greek symbols
constant in Pitzer equation, (kglmol)“.5
; Pitzer interaction coefficient, kg/m01
YA activity coefficient of component A, dimen-
sionless
f viscosity, Pas
yb stoichiometric constant of species b, dimen-
sionless
osmotic coefficient, dimensionless
oxygen absorption rate, mol/s
Subscripts/superscripts
a anion
C cation
i interface
i ions
939
N reaction order
M reaction order
t time
W water
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APPENDIX A: OXYGEN SOLUBILITY
Due to the high concentration of ions in the sodium sulfite
solution, the solubility of oxygen will be lower than in pure
water. The extent to which the solubility is lowered is cat-
culated with an equation proposed by Schumpe et al. (1978):
log (H./Ho) = x&I, (Al)
Co, = Ho/K CCo,li. purew.,er . 642)
H,, is the salting-out coefficient for interactions between
ion i and gas j, and Ii is the ionic strength of ion
i (= 0.5m,Z:). The necessary salting-out coefficients were
940 PETER M. WILKINSON er al.

Table A 1. Oxygen solubility of air in a 0.8 M sodium sulfite solution at various pH values,
calculated by the method of Schumpe et a[. (1975) and with eq. (A3)

Schumpe et al. Linek

PH GSo, CL;- C.+ (mol/m3) C0,@Wm3)

6.5 0.398 0.402 0.199 0.152 0.153

7.0 0.190 0.610 0.0952 0.153 0.153
7.5 0.0719 0.728 0.0360 0.153 0.153
8.0 0.0242 0.776 0.0121 0.154 0.153
8.5 0.0078 0.792 0.0039 0.154 0.153
9.0 0.0025 0.798 0.0012 0.154 0.153

‘This composition is calculated on the basis of eq. (21).

taken from Schumpe et al. (1978) with the assumption that Bw = Bib + 2/G/(a’l)(l - (1 + al”.5) exp (- aJ”.5))
the solubility in sodium sulfite is equal to the solubility in (B4)
sodium sulfate [the error due to this assumption is less than
2%, Yasunishi (1977)]. The calculated results from this B6 = 2f%*l(a02 [ - 1 + (1 + a10-5 + a’1/2)
equation for a 0.8 M sodium sulfite solution with different x”xp(-a1”.5)] (B5)
concentrations of sulfuric acid are shown in Table Al. The
conclusion that can be drawn from this calculation is that the
cc, = - c,?
influence on the oxygen solubility of the additional sulfuric
acid is relatively small. For comparison the oxygen solubility
&5F.?
in sodium sulfite solutions was also calculated with an em- and the ionic strength is
pirical equation of Linek and Vacek (1981):
I = 0.5 Cm,z;. W’l
1602.1
Co, = 5.909 x 10-6Po, exp ---f- The values of the constants are: b = 1.2, A, = 0.392 (at 20°C)
and a = 2. Apart from these constants, the component-speci-

1 (mol/l)
0.9407(7,3 - fic interaction parameters (fl”, /3’ and C#) were taken from
- (A3) the literature (Rosenblatf 1981; Zemaitis et al., 1986), except
1 + o.1933csoo3- for the interaction parameter for Na+-HSO; and
for0 < c+- -= 1 M and 288 < T -z 308 K with PO, in atm. Na*-SOS- interactions. These constants were estimated
With this equation, it is not possible to estimate the by regression analysis of the experimental activity data
potential influences of the addition of sulfuric acid on the (Morgan, 1960) with the Pitzer equation (Fig. Bl, Table BI).
oxygen solubility. T’he agreement with the results of the In addition to the ion activities, the water activity, a,, was
equation of Schumpe et al. (1978) is, however, good also calculated with the equation of Pi&r:
(Table Al).
Ina,=*& 038)
APPENDIX Bz ACTIVITY COEFFICIENT CALCULATION
In order to calculate the activity constants for high ionic
strengths and high molalities (as high as 6 M) the equations
of Pitzer and Mayorga (1973) for a multicomponent solution
can be used. The main disadvantage of this equation, how-
ever, is that it requires the knowledge of five component-
specific interaction parameters for each ion combination
(and, regretfully, all these are not known for the sodium
sulfite-sulfate, sulfuric acid mixture). However, it has also
been demonstrated that the value of the calculated activity
constant is mainly determined by only three of these inter-
action parameters (PO, /J’ and C*) and that the higher-order
terms in the equations of Pitzer and Mayorga (1973) can
safely be neglected (Zemaitis et al., 1986; Rosenblatt, 1981).
After neglecting these higher-order interaction terms, the . ..I
0 1 s I
remaining set of equations (for 1-l and 1-2 electrolytes)
become lonia strength (mol/kg)

Fig. Bl. Activity coefficients for sodium sulfite and sodium

bisulfite from the data of Morgan (1960) compared with the
best fit from Pitter equation.

Table Bl. Pitzer interaction parameters de-

termined by regression analysis from the ex-
perimental activity data of Morgan (1960)

Parameter Na,SO, NaHSO,

0.127 0.0119
with 0.522 - 0.657
- 0.0354 0.0
fy = - A+(1°.5/(l + bP5) + 2/bin (1 + bI”-5)) (B3)
 Kinetics of uncatalyzed sodium sulfite oxidation 941

$ is the osmotic coefficient that can be calculated by ments it was also noticed that the amount of sulfuric acid
necessary to set a (0.8 M) sodium sulfite solution to a par-
ticular pH varied for each experiment.
Two reasons for this observation have &en recognized.
First of all, due to the high pH of a sodium sulfite solution
059) (Fig. 7), carbon dioxide from the surrounding can be ab-
sorbed by the solution, which will influence the pH of the
solutions (and, thus, the reaction rate). The second source of
with inaccuracies was due to small errors in the pIi reading.
Because of the shape of the pH vs sulfuric acid concentration
f=A*& @IO) curye (Fig. 7), small errors in the pH measurement can lead
to large difference& in the amount of added sulfuric acid. In
and order to prevent a lack of reproducibility due to these causes,
the following procedure should be used: the absorption of
(Bll) carbon dioxide from the surrounding must be prevented
during the preparation and during the reaction of the so-
dium sulfite solution. Furthermore, the amount of sulfuric
APPENDIX c: PREPARATION OF THE SULFITE SOLUTION acid added can be controlled by weighing (which can be done
IN RELATION TO REPRODUCIBILITY much more accurately than by measuring only the initial pH
At the initial stage of the present research, it was observed of the solution). The necessity of this procedure is demon-
that a considerable variation in the experimentally deter- strated by the fact that following this procedure improved
mined reaction rate occurred. Furthermore, for these experi- the reproducibility of our experiments.