482 CALDERBANK-CATALYTIC OXIDATION OF SULPHUR DIOXIDE

THE MECHANISM OF THE CATALYTIC OXIDATION OF SULPHUR

DIOXIDE WITH A COMMERCIAL VANADIUM CATALYST :
A KINETIC STUDY
By P. H. CALDERBANK
The kinetics of the oxidation of sulphur dioxide with oxygen using a commercial vanadium
pentoxide catalyst has been investigated. Experimental conditions have been chosen such that
the reaction has been carried out isothermally in a flow-type reactor at temperatures (360" to 450")
and conversions (up to 10%) where the reverse reaction may be ignored.
The results, analysed in conjunction with the relevant adsorption isotherms and rates of adsorp-
tion on the clean catalyst, indicate that the rate-determining step is the rate of reaction between
gaseous oxygen and chemisorbed sulphur dioxide.
The adsorption isotherms, which are Langmuir in character, indicate the presence of at least two
different types of active centres. Both oxygen and sulphur dioxide are reversibly chemisorbed, oxygen
being weakly bound with a heat of adsorption of 6 ' 4 kcal. and sulphur dioxide strongly bound with a
heat of 28.8 kcal. There is evidence that both adsorbed species possess considerable mobility on the
surface.
Measurements of the rates of adsorption of SO, and 0, on the clean surface indicate that oxygen
is adsorbed by a second-order mechanism at a slower rate than the observed rate of reaction, whereas
sulphur dioxide is adsorbed by a third-order mechanism at a much faster rate than the rate of re-
action. Adsorption equilibrium of SO, may be assumed, under the conditions of reaction, without
sensible error.
Adsorption-rate measurements of both SO, and 0, indicate that the number of active centres
(defects) increases with temperature, according to a relationship of the type d l n L / d T = A / R T a
where L = no. of active centres, as suggested by Volkenstein (1949).
With SO,, reaction between it and an active centre requires no activation energy, the increase
in rate with increase in temperature being due entirely to the increase in the number of active centres.
With 0,,a small activation energy may be required, although the main increase in rate of adsorption
with temperature is similarly due to the increase in the number of active centres with temperature.
Some interesting comparisons are made between the results of these adsorption measurements and
recent work on the semi-conductivity of oxide catalysts, notably by Bevan & Anderson (1950) and
Garner, Gray 8z Stone (1950). Several points of similarity are noted which indicate lines for further
work.
Finally, a mechanism for the catalytic oxidation of sulphur dioxide is proposed, the main features
of which are :
I. SO, + 2 e + SO; (fast third-order chemisorption)
2. SO; - + 0, -+ SO, +0 - (slow second-order reaction between gaseous 0, and
chemisorbed SO,)
3. 0-- + 40, + 2 e (fast oxide dissociation or desorption)

The kinetics of the oxidation of sulphur dioxide

The reactor used in studying the rates of oxidation of sulphur dioxide (Fig. I) consisted of a
cylindrical aluminium block, g in. in length and 6 in. in diameter with a &in. hole drilled axially
through it. The catalyst was held in the reactor on a stainless-steel wire gauze and had a Pyrex
thermocouple sheath running through it from the bottom of the pre-heater. The reactor was
wound with Nichrome over thin mica and lagged with a 2-in. thick asbestos pre-form.
The temperature of the block was kept constant to within by means of a sensitive expan-
sion element embedded in it, the temperature of the catalyst bed being measured to within iqo by
means of an iron-constantan thermocouple standardized by the N.P.L., used in conjunction with a
sensitive potentiometer. The pre-heater and outlet tubes were of aluminium, screwed into the re-
actor. The outlet tube was fitted with a water-jacket and turned down to B.14 cone size at its
extremity to enable a glass trapping system to be simply attached and removed. This joint was
unlubricated.
The sulphur dioxide and oxygen-nitrogen feed, dried by bubbling through concentrated
sulphuric acid, were metered through separate rotameters, passed through the reactor and trapping
system and vented through a calibrated wet gas-meter.
The feed composition was varied by adjustment of the two flow rates and by using different
proportions of oxygen to nitrogen, accurate proportions of which were supplied in cylinders by
the British Oxygen Co.
Isothermal operation of the reactor was achieved by the use of low rates of flow (10-30 l./hr.)
and the maintenance of low conversions (up to 10% conversion of SO,). The relatively low
conversions enabled the reverse reaction to be ignored.
Sulphur dioxide and sulphur trioxide were determined by a modification of the method of
Dooky & Whittington (1946)~ in which the gases produced are bubbled through water containing
a few drops of glycerol to inhibit the further oxidation of SO,. .

J. appl. Chem., 2, August, 1952

 CALDERBANK-CATAL YTIC OXIDATION OF SULPHUR DIOXIDE 483
The sulphuric acid mist was filtered through an X3 sintered-
glass filter plate ( 6 - 5 cm.), then through a precautionary X 4 filter
plate (3.0 cm.) and the sulphur dioxide was absorbed in 20-vol.
hydrogen peroxide. It was very rarely found that any sulphuric
acid mist passed through the first filter plate. Sintered-glass
distributors were used throughout to ensure steady rotameter
reading and to prevent the formation of sulphuric acid mist in
the hydrogen peroxide absorber. Starting with dry filter plates,
the resistance to flow was negligible and did not increase sensibly
over an hour’s run.
At the end of a run, the filter plates were washed back into the
water absorber and disconnected. A splash head was fitted to the
water absorber and the sulphur dioxide boiled off through a con-
denser into the hydrogen peroxide, the apparatus being the same
as that generally used in the Kjeldahl distillation of ammonia.
Two titrations with standard sodium hydroxide solution thus gave
the SO, and SO, contents of the product gas.
The catalyst used was that described by Maxted (1933) and
was screened to ~o-~q-rnesh fragments. Complete details of the
preparation are given by Maxted.
Analysis after a period of use showed the following results (per
gram of catalyst):
Vanadium E 620 pmoles of V,O,
1400 pmoles of sulphate ion attached to vanadium
1000 prnoles of sulphate ion attached to sodium
Remainder is silica gel.
The vanadium was estimated by reduction of a suspension of
the catalyst with sulphur dioxide and subsequent titration with
potassium permiinganate.
+=P-
FIG. I. Reactor and trapping
The vanadium sulphate was estimated by titration with alkali; system for the oxidation of SO2
the result is probably too high in view of the difficulty of com-
pletely desorbing SO, from the catalyst. The total sulphate was
estimated gravimetrically as BaSO,, thus giving the amount of alkali sulphate present, by difference.
Almost all of the vanadium was present in the quinquevalent state and it would appear therefore
that the catalyst consists of V,05 together with some vanadic sulphate [probably (VO),(SO,),] and
sodium sulphate adsorbed on the silica-gel support. [N.B. It has recently come to the author’s
notice that modern catalyst preparations employ potassium sulphate in preference to sodium sulphate.]
Data for rates of reaction have been presented, following Hougen & Watson (1g47), with the
following nomenclature:
W = weighr of catalyst (g.)
F = mass feed rate (g./sec.)
x = conversion (moles converted/g. feed).
Thus, taking a mass balance over an element of catalyst of weight dW:
r.dW = F.dx
dW
&/ - F = r in moles converted/g.catalyst/sec.
cf. dxldt = r
WIF has the units of time and is simply related to the contact time tc

Thus, tc = w -@ where PF = density of feed

F Pc pc = apparent density of catalyst bed.
The time factor W/F has the advantage of being independent of temperature and of the porosity
of the catalyst bed.
The more conventional co-ordinates, percentage conversion and contact time, have also been
included in the curves given (Figs. 2,3 and 4). The plot of conversion against contact time showed

J. appl. Chem., 2, August, 1952 .

48.4 GALDERBANK-GA TAL Y TIC OXIDA TION OF SULPHUR DIOXIDE

'/o CONVERSION TO SO,

s0/os02 10% so.

FIG.2 (left)
PSo, = 0,167atm.
Po, = 0.180 ,,
rN, = 0.668 ,,

FIG.3 (below)
PS4 = 0.167 atm.
Po, = 0.040 ,,
r~~ = 0'793 >>

that the reaction was of pseudo zero order over

a considerable range, as is particularly demon-
strated in Fig. 4.
The slopes of the straight lines obtained
thus gives the rate of reaction at the partial
pressures of the reactants in the feed.
A set of typical results are shown in Figs.
2, 3 and 4, the complete rate data being given
in Table I.
The results show that the kinetics under
the conditions investigated, are described by
the equation :
r =K. p 0 . 4 . P O ' S
SOa 0 3

if we neglect the results at 410°, which appear

to be inconsistent.
Previously published work, notably by
Russian workers, on the kinetics of the
oxidation of SO, using vanadium catalysts, is
summarized by Krichevskaya (1947).
These results appear to vary considerably
between themselves. Thus the rate equations
=K.p"'SO? *PA,;
r =K.p0ea
so .PA, ; r = K .PSO, 1 1
PO, -
have all been proposed to describe the kinetics using commercial vanadium catalysts; Krichevskaya
finds
-
r = K P ~ o*P&,
using pure vanadium pentoxide.
The published results for commercial vanadium catalysts are inconsistent, probably because of a
failure to obtain isothermal reaction conditions (high conversions were obtained).
The results of Krichevskaya with pure V,O, as catalyst have not been confirmed by the present
author (in a paper to be published shortly). This may be because Krichevskaya used carbon
dioxide as a diluent. Carbon dioxide is probably chemisorbed on the oxide catalyst (see Garner,
Gray & Stone, I ~ S O ) whereas
, nitrogen, used as a diluent in the work by the present author (mentioned
above), has been shown nor to be adsorbed.

J. appl. Chem., 2, August, 1952

 CALDERBANK-CATAL YTIC OXIDATION OF SULPHUR DIOXIDE 485

FIG. 4
Pso, = 0.167 atm.
Po, = 0.180 ,,
rN1= 0.668 ,,

I I I I I 1 1 -
o 20 40 60 eo 100 120 140 160 ieo 200
(5) rnofr. SO, converted / g feed x 10

Table I
Rates of oxidation of sulphur dioxide (moles SO, convertedlg. caralystlsec.)
Temp., Feed composition
O c . Pso, = 0.167 atm. Pso, = 0.800 atm. Pso, = 0.167 atm.
Po, =o.rSo ,, Po, =0*040 ,, Po, =0*040 ,,
PN, =0*668 ,, PN% =0.160 ,, = 0.793 ,,

Rate x 107 Rate x 10' Rate x 107

360 - - 0.91

370 7.06 4'1 2.36 r370o a . p;sm

380 10'33 6.5 3-27 r3800 a p: '
~
,
*:
P
390 15.46 10'0 5.22 rzso0 a plz: . pga"
400 21-43 13.2 6.61 r4000 a pig: . p&78
410 28'75 19.2 8-04 r4100 a p: . P:,'~
420 - 25.0 11.5 r4,0a a pgg .-
430 - 33'3 17'5 r4300 a pgg .-
450 - 49'3 25.0 r469° a PSO,
0.43

The adsorption isotherms for sulphur dioxide and oxygen

Adsorption isotherms for the two reactants on the commercial vanadium catalyst have been
found.
The apparatus and technique used in carrying out the measurements was essentially the same
as that described by Tompkins & Young (1951) (see Fig. 5). The catalyst was baked out at 490"
in vucuo for 12 hours, the temperature lowered to that at which measurements were required and
known amounts of the gas were let into the constant volume apparatus by means of the calibrated
doser. From the measured pressure developed in the apparatus, the amount of gas adsorbed
was deduced at a given temperature and pressure in the manner described by Tompkins & Young.
The results at a given temperature were found to fit the Langmuir isotherm very closely. The
Langmuir isotherm may be expressed as:
K, . P . ( L - e,) = K, . oE
where, in the work to be described,
P = pressure of adsorbate, expressed in mm. of mercury
L = total number of active centres expressed as moles of adsorbate which I g. of catalyst
can accommodate

J. appl. Chem., 2, August, 1952

486 CALDERBANK-CATAL YTIC OXIDATION OF SULPHUR DIOXIDE

-
'3II
$10
-59
aE e
x7
1 6
Es
g- 4
z 3

50 100 I50 2 0 0 2 5 0 3 0 0 350 400 450 5 0 0 550

P, mm.Hg
FIG. 6. Langmuir isotherm far oxygen
VJHg
To Reservoir

FIG. 5 .

OE = moles of gas adsorbed at equilibrium/g.

of catalyst
and K , / K , = K (the adsorption equilibrium
constant), in (mm. of mercury)-l.
On rearranging, this gives P/& = P/L + x/KL.
I n Figs. 6 and 7, P/OE is plotted against P d
for 0, and SO, at 410' and 450' (no adsorp-
100' ' ' ' ' 300
*O0 P, mm. ~g
' ' '
400 5 0' 0 ' '
tion of nitrogen was detected over a wide range FIG. 7 . Langmuir isotherm far sulphur dioxide
of temperatures). For both gases at 450°, the
Langmuir isotherm is seen to apply. From the slopes of the straight lines, the values of L have
been deduced.
For O,, L = 63 p.moles/g. catalyst; for SO,, L = 88 pmoles/g. catalyst.
At 410°, for both gases, the active centres become saturated at these calculated values and the
straight line changes slope abruptly into another straight line of different slope as adsorption begins
on a new type of active centre, the Langmuir isotherm again being followed.
The most feasible explanation for this abrupt change of slope at the saturation point would
seem to be as follows. Before active centres of the first type are saturated, adsorption occurring on
those of the second type gives rise to a mobile complex which migrates to the first type until all
such active centres are saturated. Adsorption then begins on the second type of active centre. It
is possible that at lower temperatures further types of active centres may be observed, and in fact
their presence is indicated by the adsorption-rate measurements to be discussed later, where values
of L greater than 3x0 pmoles/g. catalyst are met with. As Taylor (1950) pointed out, there is
evidence from the study of the conductivity of oxide catalysts that a whole spectrum of energies is
involved, corresponding to a series of active centres of varying activity.
In Table 11, the adsorption equilibrium-constants at a number of temperatures have been
calculated from corresponding measurements of OE and P, taking the values of L previously
calculated. In all cases, eE was kept at a value less than L, so that adsorption on one type of
active centre only was studied.
In Fig. 8 the van't Hoff isochore, logK/(I/T), has been plotted and the values of the heats of
adsorption of 0, and SO, have been deduced.
It is seen that oxygen is loosely bound to the surface (AH = --6.qkcal./mole), but sulphur
dioxide is much more strongly bound (AH = -28.8 kcal./mole).
Adsorption rates
Adsorption rates were measured by following the rate at which an enclosed volume of the gas
at constant pressure was taken u p by the catalyst, the doser in Fig. 5 being replaced by a gas burette.
The Langmuir adsorption-rate equation
dB
- = K, . P . ( L - 01 - K,e
dt
J. appl. Chem., 2, August, 1952
 CALDERBANK-CATAL YTIC OXIDATION OF SULPHUR DIOXIDE 487
Table I1
Adsorption equifibrium-constants for sulphur dioxide and oxygen
K = eE/[P (L -sE)] in (mm. Hg)-l
PSO,' BEY so,, Kso,,
mm. Hg pmoles/g.catalyst pmoles/g. catalyst (mm. Hg)-'
410 116.5 63 96- 88.0 0*0228
420 139.5 62-51 88.0 0.0176
430 175'0 60.27 88.0 0.0124
440 210'0 58.14 88.0 0.0093
450 248.5 55-85 88.0 0.0070
460 287'5 53.60 88.0 0'0054
470 341.5 50.52 88.0 0.0040
480 403.0 47.01 88.0 0.0029

Temp., PO,, 0% 02, L, KO,,

O c. mm. Hg pmoles/g.catalyst pmoles/g. catalyst (mm. Hg)-'
410 334 53-01 63'0 0.0159
420 344 52'67 63.0 0.0148
430 359 52-01 63.0 0.0132
440 370 51.64 63-0 0.0123
450 380 51-36 63.0 0.0116
460 391 51-04 63'0 0-0109
470 402 50.73 63.0 0.0103
480 412 50.52 63-0 0.0098
490 423 50.26 63.0 0.0093

reduces to
de
-dt
- K , * P ( L - e) ..............(1)
when K, is small (i.e. when K is large, which will be so
at relatively low temperatures) and particularly when
8 is small (i.e. at the beginning of adsorption on the
clean catalyst).
Equation (I), apart from the usually emphasized
assumptions, implies a second-order reaction, in
which one molecule of gas reacts with one active
centre of the substrate. If, however, one molecule of
gas reacts simultaneously with two neighbouring
active centres (a ' dual site ') the equation becomes:
d0
-
dt
= K,. P . (L - el2 ............
(2)

again when the rate of evaporation is small..

From (I), if P is kept constant,

From (2), if P is kept constant,

I - I
FIG.8. Van't Hoffisochores for rhe adsorption
._
L
~

L-0
=K,. P.t ..........(4) of oxygen and sulphur dioxide

I n order to bring the rates of adsorption to within conveniently measurable limits, lower
temperatures than those used in the measurement of the isotherms were generally employed, so
that the assumptions made in deriving equations (3) and (4) (low rates of evaporation) were justified.
This is particularly true for SO,, where K is very large at the temperatures investigated, but only
approximately so for 02,where the temperatures investigated were higher and did in fact overlap the
reaction temperatures previously studied.
Moreover, under these conditions of low rates of evaporation OE (moles of gas/g. of catalyst
at equilibrium) is approximately equal to L as previously defined.

J. appl. Chem., 2, August, 1952

488 CALDERBANK-CATAL YTIC OXIDATION OF SULPHUR DIOXIDE
L was therefore measured by observing values of 6 three hours after adsorption was
started, when the rate of adsorption was very small, and by plotting these values against the reciprocal
of the time and extrapolating to rjt = 0.
i.e. 0 at t = 00 = OE = L
This procedure may be compared with that adopted by Garner et al. (1950)~ in which the
conductivity (A) of cuprous oxide is assumed to be proportional to the amount of chemisorbed oxygen.
Garner et al. follow the process of adsorption of oxygen by means of the plot of log (A, - A)
against t, where is the conductivity at t = 00 and A is the conductivity at time t, and find a
straight-line relationship at a constant pressure and temperature.
The equivalent plot of log ( L - 0) against t in this work reveals a similar relationship (Fig. 9)
for the rate of adsorption of oxygen at I atm. and at a number of temperatures. Other measurements
carried out at a partial pressure of oxygen of ; atm. (air), showed that the rate was directly
proportional to the oxygen pressure, as was found by Garner et al. with cuprous oxide.
A series of independent observations using a quite different technique confirms these results
and throws some light on the mechanism of oxygen chemisorption. In many papers Neumann
(1928, 1929, 1933, 1935) and Neumann & Goebel (1934) have proposed a mechanism for the
oxidation of SO, involving the alternate reduction and reoxidation of VzO,. This hypothesis has
been tested by measuring the rate of reoxidation of catalyst which has been reduced with SO, and
the observation was made that the rate of this reoxidation is many times less than the rate of the
catalytic oxidation of SO, over the same catalyst. Neumann’s hypothesis is thus disproved, as
it had previously been by Boreskov & Ruderman (1940).
In this series of experiments, a quantity of the catalyst was powdered and placed in a fluid-bed
reactor (Fig. 10). The powder was fluidized with a stream of nitrogen and SO, and baked at 490’.
After several hours the SO, stream was cut offand the nitrogen stream was continued until all the SO,
had been desorbed. A sample (0.1-0 * 5 g.) of the catalyst was then removed, suspended in hot
dilute sulphuric acid and titrated with o.oog~-KMnO,,the end point being detected potentio-
metrically. (A calomel-platinum electrode assembly was used in conjunction with a direct-reading
pH meter). It was found that the catalyst was reduced by the N,-SO, stream to a constant maxi-
mum KMnO, titre/g. of catalyst.
The temperature of the reduced catalyst was then lowered to a convenient value and the bed
was fluidized with air, the rate of reoxidation being followed by sampling and titrating as before.
This technique ensured that the whole of the catalyst was vigorously agitated and the whole of it
subjected to the same oxygen pressure during the reoxidation. It was found that no reoxidation
occurred below 350’. Above this temperature reoxidation occurred and proceeded to a minimum

w
0 -
FIG.9. Adsorption rates for oxygen
‘static’ results. = ‘fluid bed’ results. FIG.10. Fluid-bed reactor

1. appl. Chem., 2, August, 1952

 CALDERBANK-CATAL YTIC OXIDATION OF SULPHUR DIOXIDE 489
KMnO, titre, the value of this minimum depending on the temperature of reoxidation, being the
lower the higher the temperature. It was then found that the reduction of the catalyst could be
brought about by the nitrogen stream alone, in the absence of SO,. It then became clear that what
was being observed was the dissociation of an oxide going to completion at a high temperature in a
continuously renewed inert atmospheric and its reassociation on treatment with oxygen at a lower
temperature. At equilibrium the value of the KMnO, titration depended on the temperature and
upon the partial pressure of the oxygen, as would be expected from the equilibrium dissociation

o--- -
pressure of an oxide:
+0,+2e

It was then found that the rate of reoxidation of the catalyst followed exactly the same
relationship as had been observed for the chemisorption of oxygen (Fig. 9), the velocity constant
having the same values at the same temperature. It will be noted that, owing to the greater state
of subdivision of the catalyst in the fluid-bed experiments, the values of ' L ' are much higher than
for the static experiments where 10-14-mesh fregments were used.
Taylor (1950) has already called attention to the effect of added substances in raising the
dissociation pressure of oxides and simultaneously lowering their catalytic activation energy, and
has suggested that such data should be compared with that stemming from the study of semi-
conductors. Flood & Kleppa (1947) give the dissociation pressure of V,O, at 500' as 5 x I O - ~atm.,
and the much higher dissociation pressures observed with the vanadium catalyst are yet one more
example of the observations made by Taylor.
Since the process of reoxidation of the dissociated oxide has been shown by kinetic identity to
be the same as the process of oxygen chemisorption, oxygen chemisorption on the vanadium catalyst
is therefore regarded as a second-order reaction of the type :
+
$0, 2e + 0--

-
as suggested by Bevan & Anderson (1950) for zinc oxide, or
02+2e+0--+ 13 + O -
(semi-conducting ion-pair)
as suggested by Garner, Gray & Stone (1950) for cuprous oxide, where 0 represents a positive hole
in the lattice and where the negative oxygen ion and the positive hole form a localized ion-pair giving
rise to conductivity.
Two further points revealed by the oxygen-adsorption rate measurements and which are referred
to in more detail later are:
I. The rate of chemisorption of oxygen on the clean catalytic surface is considerably less than
the rate of catalytic oxidation of SO, at the same temperature and partial pressure of oxygen. (This
would seem to imply that chemisorbed oxygen plays little part in the reaction.)
2 . The number of active centres increases with the temperature (from 43 at 350" to 63 at 370').
3. No van der Waals adsorption of oxygen was detectable even at temperatures as low as rooo
when all chemisorption had ceased.
Sulphur dioxide adsorption
Rates of chemisorption of SO, were then measured using the static technique previously
described. As the adsorption was very rapid at reaction temperatures, considerably lower tempera-
tures (230-300") had to be used.
It was found that the third-order mechanism [equation (4)] fitted the results very well, suggesting
that one molecule of SO, reacts with two active centres to give the chemisorbed complex. Moreover,
it was found that no activation energy is required in this union (Fig. 11).
As with oxygen adsorption, a considerable increase in the number of active centres with
temperature was responsible for the increased rate of chemisorption with increase in temperature.
Volkenstein (1949) has suggested that the classical conception of activated adsorption requiring
an activation energy for the formation of the adsorbed complex may be replaced by the idea of an
activation-less adsorption on active centres which increase in number with the temperature by a
relationship of the type d In LjdT = A/RT2,where A is the energy of activation for the formation
of an active centre. This conception would seem to find full justification in the results that have
been obtained with SO, as adsorbate.
It should be noted at this stage that the adsorption isotherm found for SO, was the Langmuir
isotherm in its standard form Kl . P(L - 0 ~ =) K 2 . 0Ey whereas the kinetics of the adsorption
would appear to demand the modified isotherm
Kl * P ( L - 0 E ) 2 =KZ . OE
J. appl. Chem., 2, August, 1952
490 CALDERBANK-CA TAL Y TIC OXIDATION OF SULPHUR DIOXIDE

The isotherms were determined at 410' and 450Q, whereas the rate measurements were conducted
at z30-300°, and it seems probably therefore that different mechanisms are operative over the two
temperature ranges studied.
The explanation of these two different mechanisms is probably as follows: At 410-450' it has
been shown that the adsorbed SO, complex is mobile over the surface. It seems probably therefore
that the active centres themselves are similarly mobile. A molecule of SO, striking the surface
could therefore be expected to capture two active centres (mobile electrons) and be adsorbed.
If we assume that at the lower temperatures (230-300') the active centres are no longer mobile,
it is only those molecules of SO, which strike a part of the surface that has two active centres
conveniently near to each other, which are adsorbed.
Again, the Langmuir isotherm has been used to calculate the.heat of adsorption of SO,. The
isotherm implies a constant number of sites of equal adsorption potential where the heat of adsorption
is independent of coverage. The Volkenstein treatment, however, assumes that the number of
sites is temperature-dependent and that the apparent heat of adsorption therefore decreases with
coverage.
However, it was shown in the adsorption-equilibrium studies that at least two types of
adsorption sites are present. Adsorption was studied on the first and most active of these. The
number of these more reactive sites did not change with temperature and consequently the use of
the Langmuir isotherm in conjunctionwith the Van't Hoffisochore to calculate the heat of adsorption
was justified.
Increase of temperature increases the number of the less reactive sites. As has already been
suggested, if adsorption occurs first on less active sites, the adsorbed complex, being mobile, migrates
to the more active type of site until all these sites have been lilled. The kinetics of the adsorption
is, however, determined by the total number of sites of all kinds.
Returning to the case of oxygen (Fig. g), there appears to be a small energy of activation associated
with the adsorption process itself, although an additional energy of activation is associated with the
increase in the number of active centres. As has
been pointed out previously, the conditions under
which ' L ' has been measured in the case of oxygen
adsorption do not lend themselves to its accurate
evaluation and it remains doubtful as to whether
the apparent energy of activation for this adsorption
process is real. It may be that the whole of the
energy of activation for oxygen adsorption is bound
up with the formation of active centres as with
SO,, where ' L ' has been evaluated with reasonable
exactness.
Following Volkenstein, in Fig. 12 log eE has
been plotted against I/T for the catalytic surface
under a pressure of I atm. of SOz.

(+jx105, OK-'

FIG.12. The variation of the number of active centres

(L) with temperature for the catabtic surface
PIG. 11. Rates of chemisorption of sulphur dioxide saturated with sulphur dioxide

J. appl. Chem., 2, August, 1952

 CALDERBANK-CATAL YTIC OXIDATION OF SULPHUR DIOXIDE 491
At temperatures below 170'~van der Waals adsorption is apparent and the adsorption decreases
with increase in temperature. Above 170' chemisorption becomes apparent, L increasing with
increase in temperature, the energy of activation being 5 - 6 kcal. up to about 290'. Above this
temperature, a new energy level is apparent having a much higher energy of activation, and L
increases very rapidly with temperature. Finally, when the adsorption equilibrium constant is no
longer very large (i.e. the rate of desorption is appreciable), the adsorption decreases with increase
in temperature in the manner expected from the adsorption isotherm.
These results should be compared with measurements on the conductivity of oxides in which
the conductivity is assumed to be proportional to the number of defects (active centres). Thus
the log A / ( I / T )relationships observed with oxide catalysts may be compared with the log O,/(I/T)
relationship in Fig. 12for that portion of the curve where f3E = L.
Most observers find two energy levels in the conductivity/remperature relationships of oxide
catalysts (e.g. Anderson & Greenwood (1949) find two levels at 7-and 23 kcal./mole for Cu,O,
whereas Wright & Andrews (1949) find two levels at 7 and 24 kcal./mole for NiO). The analogy
with the results quoted for SO, is obvious.
Bevan & Anderson (1950) find that the conductivity of zinc oxide decreases with the oxygen
pressure according to Wagner's equation (Wagner, 1933) which they interpret as being due to the
destruction of conducting centres by a mechanism such as:
30, $- 2e e 0--
Garner et al. (1950)~working with cuprous oxide, find that the conductivity increases on adsorp-

-
tion of oxygen, which may be interpreted as being due to the formation of conducting centres by a
mechanism such as :
0,+2e+O--+ ~ i - 0 -
conducting centres
In either case, it would appear that the conductivity is a measure of the amount of chemisorbed
oxygen, increasing (Cu,O) as oxygen is adsorbed or decreasing (ZnO) with increased oxygen pressure,
+
owing to a shift in the equilibrium $0, 2 e + 0 - -.
Bevan & Anderson find at very low oxygen pressures (below IO-, mm.) a state where the
conductivity A, is independent of the oxygen pressure, and at higher pressures (up to atmospheric)
a state of the surface where A, is proportional to PZ25as predicted by Wagner. This latter state,
if we take A, as inversely proportional to O E , corresponds to a Freundlich isotherm of the type
OE a Pg:'.
Garner ef al. (1950) examined cuprous oxide over the low pressure range (up to 9 x IO-, mm.
of mercury) and found that A, was substantially independent of the oxygen pressure. They do
not appear to have carried out measurements at oxygen pressures greater than this and consequently
it is possible that Wagner's equation may hold for Cu,O at higher oxygen pressures.
If catalytic activity is to be associated with a pressure independent state of the surface we should
expect that for all reactions in which the rate of reaction is the slowest step and where adsorption
equilibrium may be assumed to hold (Langmuir-Hinshelwood kinetics), the rate would be independent
of the oxygen pressure, since A, a OE # f(P0,). This is in fact found to be so in the oxidation of
carbon monoxide at a cupric oxide surface (see Schwab, 1942).
If, however, catalytic activity is associated with a pressure dependent state of the surface, such
as is observed with ZnO, the same reaction conditions as above would be expected to give rise to a
kinetic equation involving the term P&:s provided Wagner's equation applies and provided there
is no van der Waals adsorption.
It should be emphasized that the adsorption measurements carried out in this work did not
embrace a sufficiently low pressure range to enable any pressurevindependent state of the surface to
be recognized clearly. It follows, therefore, that although the rate of adsorption of oxygen, measured
on a pressure-dependent state of the surface, is considerably less than the rate of reaction, it is
possible that a pressure-independent state exists which has not been detected and where adsorption
may be more rapid.
The kinetics of the oxidation of SO,, where r is proportional to P;:, would suggest, however,
that this is not so and it would appear to be more probable that oxygen in the gas phase reacts with
chemisorbed SO,. From the very high rates of chemisorption of SO, it may be assumed that
adsorption equilibrium is established for it.
From the SO, isotherm (Fig. 7) it is possible to read off the values of f 3 for ~ any given partial
pressure of SO,. If, then, these values of fIE are substituted for the corresponding partial pressures
in Table I it may be seen that the kinetic equation

J. appl. Chem., 2, August, 1952

492 CALDERBANK-CATAL YTIC OXIDATION OF SULPHUR DIOXIDE

becomes
The mechanism of the oxidation of SO, is tentatively suggested as being:
I. SO, + 21 + SO,- - (A H = - 28.8 kcal./mole) (fast third-order chemisorption of
gas active chemisorbed SO,)
centres complex
2. 0, + so:!+ so, + o-- (slow second-order reaction)
gas chemisorbed chemisorbed
so2 oxygen atom
3. 0- - + $ 0 ,4-2e (AH = + 6 - 4 kcal./mole) (fast desorption)
The chemisorbed SO, complex has been tentatively represented as SO, -, and it was hoped
that conductivity measurements would show the validity or invalidity of this representation.
Unfortunately, V,O, exhibits a large bulk-phase conductivity with a very high temperature-coefficient
and although changes in conductivity were observed on chemisorption of both SO, and 0,, indicating
that the process was essentiallyelectronic, the need for very precise temperature-control made accurate
observations very difficult.
Chemisorbed oxygen atoms are represented as oxide ions since oxygen chemisorption has been
shown to be the reverse process to oxide dissociation, and in line with Bevan & Anderson's conception
of the mechanism of the dependence of the semi-conductivity of ZnO on the oxygen pressure.
The chemisorbed oxygen, formed in reaction 2, is loosely bound to the surface (AH = - 6 '4
kcal./mole) and is imagined to associate rapidly to oxygen gas in reaction 3, playing little part in
the reaction. It will, however, react to some extent with chemisorbed SO, simultaneously with
reaction 2, but at a slow rate owing to the small stationary concentration present on the catalyst.
This complication may well be responsible for the observed factor of P;;" instead of PA;"in the
rate equation.
Ramsay Laboratory of CherniGl Engineering
University College
Gower Street
London, W.C.I
Received 16 October, 1951

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J. appl. Chem., 2, August, 1952