ACTIVATION

ENERGY
OXIDATION

VARIATION
FOR CATALYTIC
OF AQUEOUS
SO,t

W. PASIUK-BRONIKOWSKA*
Institute of Physical Chemistry, Polish Academy

and A. SOKOEOWSKI
of Sciences, 01-224 Warszawa, Kasprzaka44/52.

Poland

(Received 12 May 1982; accepted 16 August 1982)

oxidation in aqueous solutions catalysed with manganous sulphate was studied to determine
Abstrart-SO,
temperature dependencies of the reaction rate. The process was carried out at relatively high sulphuric acid
(reaction product) concentrations with regard to its application for SO2 removal from waste gases. Variation of the
apparent activation energy has been linked with alteration of reaction rate determining steps.
INTRODUCTION

The catalytic influence of some transition metal ions on

oxidation of SO, absorbed in aqueous solutions has been
known since the 19th century. However, there arc at
least two important reasons why research on this process
is

still

carried

on.

One

is

its

complexity

solution into the reactor,

mocouple for indicating
mixture. Both the reactor
tem were immersed in a
within f O.lC.

and a Pyrex jacketed thertemperature of the reacting

and the gas conditioning syswater bath and thermostatted

involving

laborious studies on the process mechanism and another

one is its practical importance for SO1 emission control.
To develop such a technology sufficiently safe data are
needed, particularly the optimum catalyst, its concentration, relative concentrations
of reagents, reaction
temperature etc.
In this work we attempted to determine experimentally
the activation energy of oxidation of SO, absorbed into
the MnSO. aqueous solution hoping to gain additional
information as to the reliability of the reaction model
proposed
prcviously[l].
Our intention was also to
explain discrepancies in the scarce literature on the
intlucncc of temperature upon the process. Some authors
reported relatively high values of activation energy
(Hoathcr et 01.[2]-27.3 kcallmol ? 4%, Huss[3]--19.8 +
0.7 kcallmol), whereas others indicated very low ones
(Tarbutton et a/.[41 did not observe any measurable
effect of temperature. the value evaluated from the data
of Copson et al. [5] is lower than 2 kcal/mol).
EXPERIMENTAL

Apparatus
Experiments on SO2 oxidation were conducted in a
semibatch foam reactor with constant flow of gaseous
reactants, previously passed through a mixer and a
humidifier. We have chosen this type of gas-liquid contact as it is directly transferable to industrial scale. A
vertical Pyrex tube was used as the reactor (Fig. I),
supplied at the bottom with the fine glass-frit as a gas
distributor and, at the top with the PTFE lid with
through-pipes. The pipes were coupled with a reflux
corklenscr discharging after-reaction gases, tube for
liquid sampling, separatory funnel applied for introducing initial or excessive (taken through the sampling tube)
Author to whom correspondence should be addressed.

tPart of this work was presented at the European Conference

of the Federation of European Chemical Societies: Chemical

Pathways in the Environment, Palaiseau, France 1980.

ikiatenals
Sulphur dioxide. The supply of sulphur dioxide was
from a technical cylinder placed outside through an
intermediate steel bottle (2 I.) placed in the vicinity of the
reactor and periodically loaded by distillation of liquid
SO* from the outer cylinder. The gas was also cleaned by
passing it through a silica gel column and then through a
fine porous glass plate.
Air. Molecular oxygen from air was used as an oxidizing agent. Air was sucked from the outside of the
laboratory with a diaphragm pump and next passed
through a silica gel column, cloth titer and fine porous
plate.
Manganous s&hate. The analytical grade reagent was
from PPH POCH, Gliwicc. It was applied without any
further purification.
Water. All solutions were prepared with redistilled
water.
Procedure
As soon as the bath temperature was fixed at the
desired level the flow of air was turned on and then the
reactor filled with the catalyst aqueous solution of known
volume and Mn concentration. Simultaneously with the
solution the proper stream of SO, was introduced into
the flowing air and hence the oxidation was under way.
From the start of supplying SOI a run was timed and
successive liquid samples were withdrawn. Only 1 ml
liquid portions were needed for analysis and the excess
of the withdrawn liquid was returned to the reactor.
The temperature of the reflux condenser was adjusted
according to the programme worked out on the basis of
preliminary experiments so as to keep the possibly constant volume of the reacting liquid, independently of the
increasing H2S04 concentration with the progress of
oxidation.
Samples were analysed for H2S04 to get information
on the extent of reaction and for Mn to allow correction
for changes in the reacting solution volume. Alkalimetric

122

W.

PASIUK-BRONIKOWSKA and

A.

SOKOLOWSKI

Fig. 1. Schematic drawing of experimental apparatus: 1, pyrex tube 0.07m i.d.; 2, gas distributor/glass-friitl; 3,
PTFE lid: 4, reflux condenser: 5, separatory funnel: 6, sampling tube; 7, thermocouple; 8, humidifier; 9, mixer of
gaseous reagents; 10, rotameter; 11, Ueometer; 12, fine porous plate; 13, cloth filter; 14, silica gel column; 15,
diaphragm pump.
titration
with metal masking
and calorimetric
determination
in the presence
of formaldoxime
were
employed respectively.
Below fundamental
parameters
of experiments
are
specified:
MuSO concentration
SO? concentration
flow of gaseous mixture
liquid volume
temperature

1.2 x lo--0.18 mol/dm3

0.5-3 vol.%
0.1 l-O.44 dm/s
0.134.25 dm
14.2-43.3C.

RILWLTSANDDISCUSSION
The rate of sulphuric acid production
which is equal to
the rate of SOz oxidation
can be obtained
from the
equation
r = (dnJdt)/

V = dc,/dt

- (dcJdt)(cJcM)

(1)

where n. = n.(t) and V= V(t) were not measured while

c, = c,(t) and CM = c&t)
were experimentally
determined concentrations
of sulphuric acid and manganese,
respectively.
The data points were expressed as higher order polynomial functions of time using the least squares method.
Exemplary fitted curves are shown in Pi. 2.
In view of previous reports[l-3.51
as well as of
observations made in this work sulphuric acid causes
significant retarding effect on the rate of its production.
Therefore to examine the reaction sensitivity to temperature one should compare reaction rates at diRerent
temperatures but alike acid concentrations or reaction
extents when starting with an aqueous solution containing no acid. Temperature
dependencies
for SO2 oxidation
at MnSOa concentration
5 x lo- mol/dm3 and various

10

15
tno-T

Fii.

20

25

30

2. Sulpburic acid and manganese concentration

14.2C; 0, 25.1C and Cl, 34.8C.

va time;

A,

reaction extents are plotted in Fig. 3. It shows results of

experiments
given as In r vs l/T instead of the typical
Arrhenius
plot, as the process is complex and the form
of its rate equation may he still in question. Under the
condition that experiments
were performed
at constant
concentrations
of both substrates
the value of the apparent activation energy found from Fig. 3 did not differ
from that determined
from the classic Arrhenius
equation.
Data points reported
in Fig. 3 are arranged in two
regions. one of variable
activation
energy which

Activation energy variation for catalytic oxidation of aqueous SOI

I
n

O,l

0.2
_

-t

123

a3
.

Ob

dnP/S

<

Fi.

32

,
3.3

3.L
iO?T,

K-

3.5

4. Dependence of the process rate upon gas flow rate for

cM= 5 x IOFmolldmand temperature 32.PC.

more probable. For this purpose experiments were carried out at all parameters constant but the gas Bow rate
which was varied to change hydrodynamic conditions
determining transfer of gaseous reactants. Figure 4
shows that at the gas flow rate 0.236 dmls applied in the
main set of our experiments the influence of hydrodynamic conditions was not detectable. Rates of SO2
oxidation plotted in Fii. 4 are the maximum ones
attained during runs at 32.7C (found by extrapolation to
c. = 0). These results allow more firmly to ascertain that
the simultaneous absorption of oxygen and sulphur
dioxide accompanied by the catalytic oxidation of the
latter goes in the kinetic regime throughout tbe conditions described in Fii. 3 up to the temperature as in
Pii. 4. However, further increase in the temperature
might partly bring dilfusional limits on the examined
oxidation process.
The effect of temperature on the rate of SO2 oxidation
at the relatively bigb MnSO., concentration
(up to
0.18 mol/dm3) was rather weak. It is illustrated in Fig. 3
(dotted line) as derived from initial process rates of
experiments with upper catalyst concentrations
(see
diffusional regime in Fig. 5). In this case the liquid side
resistance of the oxygen transport was the rate -controlling phenomenon. Nevertheless, the foam reactor is
not convenient for studying the process in the diffusional
regime. It is mainly because the area of gas-liquid interface, especially foam height, is dependent upon the physical properties of the reacting mixture which change
with the reaction going on.
For SOa oxidation catalysed with MnSOd in aqueous
solutions Pasiuk-Bronikowska and Bronikowski[l] have
reported that the SO, absorption rate may be given by
the empirical relation:

Pi. 3. Temperature dependencies for SO1 oxidation at c, =

5 x lo-mol/dm(exemplary points: + , c, = 0 mol/d&; A, c, =
0.408moI/dd;
0, E. = 0.816 mol/dm). Values of activation
energy at higher temperatures (left side of the diagram) are: 1.03.
2.75, 4.32. 6.10. 8.83. 10.70kcai/mol respectively with c. increasing.

decreases by several times with lowering sulphuric acid

concentration
and another one of almost constant
activation energy 24 f 2.4 kcal/mol. The latter is extended to higher concentrations of sulpburic acid and lower
temperatures.
To get further information on the character of the
regions it was necessary to answer whether they were
diffusional or kinetic. Therefore fluxes of gaseous substrates (sulphur dioxide and oxygen) from the gas phase
into the liquid bulk were calculated on the basis of
previously found rates of oxidation as well as of the
estimated mass transfer parameters k, = 5.5 x IO- m/s
and (I = 14.5 x 10rn-, and their values compared. The
mass transfer parameters were determined from the correlations suggested by Gestrich et af.161. The comparison
indicated that tbe slow reaction regime could be applied
to both regions. The calculations also disclosed that with
the additional increase in the rate of oxidation one might
expect the appearance of the liquid side resistance first
due to oxygen and not to sulphur dioxide. Oxygen
diffusional limitation calculated on this basis is shown in
Fii. 3 (dashed lime).
As the estimation of kr and a was rather rough it
seemed reasonable to verify practically the kinetic
regime, especially for the variable activation energy
region. In this instance the diffusional limitation wa*

llr= AdeM

+ B(c,/c,)

(2)

llr = A&,

+ B(c,/cM2)

(31

or by

depending on relative rates of appropriate step reactions.

Here, the equations have been written in a converted
form which allows to visualize that by examining a run

W. PASIUK-BRONIKOWSKAadd A. SOKOLOWSKI

124

where cm = [Mn]([Mn3] was negligible in comparison

with the concentration of MnS04 throughout experiments), k, is a composite rate constant being a product
of appropriate step reaction and equilibrium constants,
and K and K are equilibrium constants of particular
step reactions. Comparison of eqn (3) with eqn (4) leads
to A,= Klk, and B = Wk,.
When co= const which
may be a rough approximation for a run eqn (4)
becomes:

where k, = kc0 and K, = K(co/cM2).

As results from the equations contribution of the
oxygen solubility temperature effect to the empirical
value of the apparent activation energy should be considered. This effect is expected to be excluded when
K,c, B K. In this case
lo-

IO-'

1w2
cM

W, = (kJK)cM.

(6)

mol/dm

Fii. 5. The influence of c,,, on the slope of the line l/r = f(c,)
(eqns 2 or 3) disclosing diffusional limitation.
as l/r vs c, the regime of gas absorption may be easily
recognized. For both cases (eqns 2 and 3) when the
kinetic regime (slow reaction) takes place the slope of a
line should be inversely proportional to the squared
M&O4 concentration (S = B/ca) provided all relevant
parameters are kept constant. Similarly the intercept
I = A Jc, (eqn 2) can be based on for the reaction going
in the 0, independent region. The regularity vanishes in
the diiusional regime. This is demonstrated in Fig. 5. It
gives the slopes calculated for several runs performed at
different values of cIK and temperatures 20.0, 32.7 and
40.0C, plotted against c,,, (log-log coordinates). The
data points follow the expected relationship up to a
certain value of CM,being lower for the higher reaction
temperature. Further increase of the MnS04 concentration indicates transition from the kinetic to the
diiusional
regime for which the above relationship
ceases to hold.
The results conlirm that conditions for all experiments
shown in Fig. 3 below the dotted line corresponded to
those of the kinetic regime. Even at the temperature
4O.OCthe intbtence of diffusion appeared only when
cM >6~ lo- mol/dm whereas experiments in Fii. 3
were at C~ = 5 x lo-mol/dm3. Hence it can be concluded that the unusual effect of temperature observed in
Fig. 3 reveals mainly the complex reaction mechanism.
As the plot is curved downward this is not the case of
parallel pathways but of reaction successive steps.
According to Pasiuk-Bronikowska et a/.[11 who proposed the reaction model for oxidation of SOI catalysed
with MnSOd the theoretical rate equation for the set of
parameters applied in this work may be expressed as:

Plotting experimental data as rc, against c, the approached values of (t/K9cM2 = const could be found
for several temperatures in the lower range and hence
the single apparent activation energy as given in Fig. 6 (a
and b-l).
Values of the coefficient (&,/K)c, were also calculated from eqn (4) takine k&K
as the initial rate of
oxidation at c. = 0 (see b-2 in Fig. 7). Thus obtained
values for the activation energy are 20.2 -(b-l) and
23.4 kcal/mol (b-2) indicating discrepancy caused by the
way of data treatment. The results bear a slight compensating effect with respect to the second term of
denominator in eqn (4) as co decreases with the rise of c..
Huss[31 who supplied the best evidence for his
experiments gave the value of activation energy found
at
c0=7.S x lo-*mol/dm3,
c, = 0 and
c, = 3.31 x
lo- mol/dm3 for temperatures between 25 and 38C. In
view of previous considerations on reaction mechanism[l]
the conditions were fulfilled for the kinetics described by:

r = kocM2.

(7)

Therefore values of activation energy found in this work

and reported by Huss should not necessarily be equal.
CONCLUSIONS

Variation of activation energy for the reaction of SO?

oxidation catalysed with Mn has been proved experimentally. To cbstinguish between the tirst order reaction
and diiusion controlled kinetics with respect to oxygen
the influence of other reagents (MnS04 and H2S04) in
the complex reaction was successfully examined.
Attempts were made to link such a behaviour with the
reaction mechanism, which allowed to settle that SO*
oxidation kinetics may or may not significantly depend on
temperature according to the reaction order with respect
to oxygen. With the order increasing (from 0 up to 1) the
value of apparent activation energy diminishes from
19.8 kO.7 kcallmol in the absence of HJO,
or 24%

Activation energy variation for catalytic oxidation of aqueous SO*

Fig. 6. Determination

24kcal/mol
at relatively high
to about 1 kcal/mol. The latter
tors at high Mn concentrations
overcome
the energy-related
acid contamination.

of apparent activation energy basing on eqn (6) (a and b-l) or eqn (4) (b-2).

concentrations
of H2S04
is attained in foam reacencountered in practice to
problem of environment

NOTATION

specific interfacial area with respect to

gas-liquid volume, m-
kinetic constants in experimental
rate
equations,
mol s/dm and s respectively (eqns 3 and 4)
kinetic constant in experimental
rate
equations (3 and 4), s
manganous
sulphate
concentration,
molldm3
oxygen
concentration
(in
liquid),
mol/dm3
sulphuric acid concentration,
mol/dm
apparent activation energy of the reaction (process), kcallmol
intercept for I/r = f(c.) (oxygen independent region), dm3 s/m01
liquid side mass transfer

coefficient,

m/s

complex

rate constant

complex equilibrium constants

moles of sulphuric acid, mol
rate of the reaction, molldm s
slope for i/r = f(c,), s/mol* dm6
time, s
temperature of the reaction (process),
C
absolute temperature, K
volume of reacting liquid, dm3
gas flow-rate, mls

REFERENCF.S

Cl1 Pasiuk-Brouikowsks

Sci. 1981 36 215.

W. and Bronikowski T.. C/rem. Ensare

- _

Dl Ho&her R. C. and Goodeve

30 1149.

C. F., Trans. Faraday

Sot. 1934

Huss A. Jr., Ph.D. Thesis. Urbana. Illinois 1978.

E:; Tarbutton G., Driskell I. C., Jones T. hf., Gray F. J. and
Smith C. M., bd. Engng Chem. 1957 49 392.
PI Copson R. L. and Payne J. W., Ind. Engng Chem. 1933 25
9m
___.
WI G&rich W., Esenwein H. and Kmuss W.. ht. Chem. Engng
1978 18 38.