A Kinetic and Surface Study of the Water-Gas Shift Reaction on

Manganese(I1) Oxide
BORDANWALTERKRUPAYAND ROBERTANDERSON
ROSS
Departtnetzt of Chemistry, Lakel~eadUtziuer.sity, Tlz~~nder.
Bay "P", Otltario
Received April 5, 1973

The kinetics of the water-gas shift reaction on a manganese(I1) oxide catalyst possessing surface
nonstoichiometry has been studied from 300 to 400 "C at atmospheric pressure. The experimental rate
expression obtained was r. = k(pco)0.75 in ihe carbon monoxide partial pressure range 20 t o 80 Torr
and r = k(pco)0.5 from 100 to 240 Torr. The rate of reaction has been related t o the Langrnuirian-type
adsorption of carbon monoxide and a redox mechanism involving surface oxygen species is proposed.
When the reaction rate was determined in increasing 10 "C intervals from 300 "C, two activation energies
+ +
were observed; 16 0.5 kcal mol-' from 350 to 400 "C and 11 0.5 kcal mol-' from 300 t o 340 "C.
The temperature at which the change occurs corresponds closely to the Curie temperature o f the oxide.
The possible use of manganese(I1) oxide as a catalyst or catalyst component in a commercial shift process
is critically appraised.
La cinktique de la rtaction de dCplacement eau-gaz sur tln catalyseur oxyde de manganese(I1) ayant
une surface non stoechiometrique a ete CtudiCe de 300 a 400 "C a la pression atmosphtrique. L'expression
de vitesse expkrimentale obtenue Ctait r. = k(pc0)0.75dans I'intervalle de pression partielleen rnonoxyde
de carbone de 20 a 80 Torr et r = k(pco)0.5 de 100 a 240 Torr. La vitesse de rCaction a CtC reliee a l'ad-
sorption du type Langmuir du monoxyde de carbone et un niCcanisme rCdox faisant intervenir une
espece oxygene a la surface a ete propose. Lorsque la vitesse de rCaction a Cte dCterminCe en augmentant
la temptrature par des tcarts de 10 "C a partir de 300 "C, deux Cnergies d'activation ont CtC observCes;
+ +
16 0.5 kcal mol-' de 350 a 400 "C et 11 0.5 kcal mol-' de 300 a 340 "C. La tempkrature a laquelle
le changement se produit correspond etroitement a la ternpirature de Curie de I'oxyde.
L'utilisation possible de I'oxyde de rnanganese(I1) cornme catalyseur ou constituant d'un catalyseur
dans le processus de dtplacement a CtC CvaluCe de faqon critique. [Traduit par le journal]
Can. J. Chern., 51, 3520 (1973)

Introduction extended to explain the results o f catalysis o n

It is well known that the rate of the water-gas
shift reaction is a controlling parameter in many
established industrial and technological catalytic
processes (1). In recent years, new impetus has
been given t o studies of the reaction over solid
catalysts by its importance in hydrocarbon fuel
cell operations (2) and in the suppression or re-
moval of gaseous p o l l ~ ~ t a n from
ts the exhausts
of internal combustion engines (3).
Although many catalytic studies of the water-
gas shift reaction have been reported, these are
mainly directed towards the various technologi-
cal aspects of the reaction and are generally
focused on iron oxide-based catalysts (4). In a
recent paper ( 5 ) the mechanism of the shift re-
action on iron(I11) oxide was re-examined using
an isotope tracer technique and two possible
reaction mechanisms were proposed; both of
which involve the reaction between adsorbed
carbon monoxide and either oxygen o r hydroxyl
species. Elsewhere, conclusions obtained from
rate studies on chromium oxide (6) have been
copper chromite.
N o detailed work has been reported on man-
ganese oxides as catalysts for this reaction but
their use as a catalyst stabilizer and promoter
has received attention for a commercial shift
catalyst containing zinc, copper, and chromium
components (7). Hence, a kinetic study of the
water-gas shift on manganese(l1) oxide containing
excess lattice oxygen, has been initiated. The
general catalytic properties of this oxide are not
yet well-defined and were only recently examined
specifically in the heterogeneous decompositions
of isopropanol (8, 9) and nitrous oxide (10).
Experimental
Apparat~rsand Procrd~rr.e
T h e all-glass flow system and quartz reactor were de-
scribed previously (1 1, 12). High-purity helium was used
as the carrier gas at atnlospheric pressure in the flow sys-
tem and in the Beckman GC-5 gas chromatograph.
Carbon monoxide, water, and carbon dioxide were ana-
lyzed by a thermal conductivity bridge at 110 "C using
stainless-steel columns, 72 x 0.125 in., o.d., packed with
"Poropak Q".
 KRUPAY AND ROSS: SHIFT REACTION ON Mn(I1) OXIDE
Surface areas were determined by low-temperature
krypton adsorption (B.E.T.; -196 "C; o = 21.5 A2).
T o establish the experimental conditions for which the
reaction rate was not influenced by external or internal
diffusion, the influence of space velocity, catalyst mass,
and particle size was studied in the usual manner (11). As
a result of these preliminary experiments, kinetic measure-
ments were conducted at a total flow rate of 350 ml min-'
(N.T.P.) which was equivalent to space velocities from
7.48 to 8.78 (cc gas) (cc. catalyst)-L s-' between 300 and
400 "C.
All reaction rate measurements were made after the
steady catalyst activity level was attained and the experi-
mental rates were determined from the rates of carbon
dioxide production. The validity of this procedure was
establ~shedby obtaining a quantitative mass balance for
all components at both 320 and 380 "C.
Mnfrrinls
Manganese(I1) oxide. A bulk quantity of cc-manganese-
(111) oxide was prepared as described (9). A calculated
amount of this oxide sample was placed in the reactor such
that, after reduction, it would yield one gram of
nlanganese(I1) oxide. All catalyst samples were pretreated
for 5 h at 380°C in the standard water-gas mixtureconsist-
ing of a 350 ml min-I (N.T.P.) stream of helium contain-
ing 40 Torr carbon monoxide and 16 Torr water vapor.
The methods used for the chemical and structural an-
alyses of the catalyst have been described (8, 9).
Carbon monoxide (C.P.; 99.5% minimum), carbon
dioxide (Coleman; 99.99%), hydrogen (ultra-high purity;
99.999%), and helium (high purity; 99.995%) were sup-
plied by Matheson of Canada Ltd. and the water in the
gas-saturators was de-ionized and boiled prior to use.
Electron transmission micrographs were recorded with
a Philips EM 300G electron microscope at 100 kV.
Specimens were crushed in an agate mortar and suspended
in 11-butanol. Drops of the s~~spension were placed on the
carbon-support film on 200 mesh copper grids, and the
alcohol subseq~~ently removed by evaporation a t lo-'
Torr.
Results
The Nature of the Catalyst
Analysis of the catalysts after reduction indi-
cated a bulk stoichiometry of MnO, ., but as re-
ported earlier (8) the samples contained enough
excess oxygen t o retain the black color associated
with manganese(II1) oxide (13). The colors of the
catalyst samples varied slightly with the tempera-
ture and time ofexposure to the water-gas mixture ;
catalysts used at 300 "C were darker than those
j used for periods longer than 24 h at 380 "C. The
1
X-ray powder diffraction patterns of all used
I catalyst samples showed characteristic lines of
I
I manganese(l1) oxide only and this together with
the chemical analyses of several samples, verified
the catalyst composition. Prior t o analysis, the
, pyrophoric catalysts were cooled to room tem-
3521
perature in heliuni at 100 ml min-' (N.T.P.) be-
fore removal from the catalyst reactor in order to
prevent spontaneous oxidation.
Rate measurements were recorded after al-
lowing the catalyst to equilibrate in the standard
water-gas mixture for 300 min. Constant activity
was observed after 100 min exposure time.
Stoichiometric manganese(I1) oxide, which was
prepared by reducing a-Mn,O, with a surface
+
area 16.5 0.5 m2 g-' for 12 h in 600 ml min-'
(N.T.P.) of hydrogen at 600 "C (14), yielded
catalysts with a surface area 14.5 m2 g-' and the
12% loss in surface area could 11ct explain the
very low activity; less than 1% of that prepared
by reduction in the standard water-gas mixture.
The stability of the latter catalysts, after con-
tinuous exposure to the water-gas mixture for
24 h, showed a decrease of activity per m2 of less
than 10% at 380 "C and a much smaller decrease
at 320 "C. Both surface areas and electron trans-
mission micrographs of the catalysts, determined
after various periods of exposure, indicated that
oxide sintering was an important factor in this
loss of activity.
Electron transmission micrographs o f the cat-
alyst immediately after the standard pretreat-
ment showed the presence of small crystallites,
approximately 700 A diameter, which were fused
into highly irregular macro-structures averaging
0.06 mm in diameter. The irregularity of the
fused crystallites diminished with prolonged re-
action times at the higher temperatures. Dark-
field electron transmission niicrographs of sin-
tered samples indicated that large assemblies of
crystallites were fused mainly into preferred
crystal orientations in contrast to the random
distribution expected in the absence of sintering.
Figure 1 shows ( A ) the electron transmission
micrograph typical of a freshly prepared catalyst
sample; (B) the transmission micrograph of a
sample exposed at 380 " C for 24 h to the standard
water-gas mixture (microscope magnification
x 26 000; total magnification x 120 000) and
(C) the dark-field micrograph of (B) (microscope
magnification x 26 000; total magnif cation x
55 000).
These observations were substantiated by sur-
face area measurements which were reproducible
on any given sample t o within +0.5 m2 g-'.
Thus, the surface area of a freshly-prepared
catalyst sample, 16.5 m2 g-', decreased to 16.0
rn2 g-' after 6 h exposure t o the standard water-
3522 CAN. J. CHEM. VOL. 51, 1973

TABLE1. The effect of variations of the partial

pressures of carbon monoxide, water, hydrogen,
and carbon dioxide on the rate of the
water-gas shift reaction

R a t e of reaction
x los
(mol m-2 s-')
Partial pressure
Component (Torr)
Carbon monoxide 20
(PHZO= 16 Torr) 30
40
60
80
100
120
174
240
Water 4 8.22 3.48
O 40 Torr)
( ~ C= 16 8.51 3.68
32 8.41 3.67
48 8.32 3.67
56 8.32 3.68
FIG.1. Electron micrograph ( A ) of a freshly prepared
catalyst sample; (B), a sample exposed at 380 "C for 24 h Hydrogen 5.4 8.59 -
to the standard water-gas mixture showing crystallite (pco = 40 Torr ; 21.7 8.71 4.03
sintering, (both microscope magnifications x 26 000 and p , , , ~ = 16 Torr) 32.6 - 3.98
total magnifications x 120 000); and ( C ) the dark-field 54.3 8.67 3.99
micrograph of (B) (microscope magnification x 26 000 65.1 8.61 3.98
and total magnification x 55 000). Carbon dioxide 10.9 8.51 3.85
(pco = 40 Torr ; 43.4 8.13 3.67
gas mixture at 380 "C, whereas exposures at 320 p,,, = 16 Torr) 65.0 8.13 3.76
"C for 7 h did not yield any measurable change 87.0 8.22 3.80
in the surface area. After exposure of the catalyst
for 48 h at 380 "C the surface area was 14.5 m2 carbon ~nonoxide and water vapor were kept
g-l. constant at 40 and 16 Torr, respectively. The
reaction-rate data are summarized in Table I and
The Relationsl7ip betbt'een Exposure Time a17d the
the logarithmic plots for the determination of the
Reaction Orders
reaction orders are shown in Fig. 2. Thus, sep-
Reaction orders with respect to carbon mon-
arate variation of the partial pressures of hydro-
oxide, hydrogen, carbon dioxide, and water
gen from 5.4 to 65.1 Torr, and carbon dioxide
vapor were determined at 320 and 380 "C on
from 10.9 to 87.0 Torr showed a n overall zero
catalyst samples which had been exposed to the
standard water-gas mixture for a maximum of order dependence of the rate of reaction on the
partial pressures of both con~ponentsat each
12 h. Further, reaction orders were re-determined
temperature. Similarly, variation of the water
on catalysts which had been exposed to the same
vapor pressure from 4 to 56 Torr, while main-
mixture for more than 48 h at both these tem-
taining the carbon monoxide partial pressure a t
peratures and no change was observed in the
order results. 40 Torr. did not influence the-rate of reaction.
The effect of varying the carbon monoxide
The Effects of Variations of the Partial Pressures partial pressure, while maintaining the partial
o f Carbon Monoxide, Water Vapor, pressure of water vapor at 16 Torr at both tem-
Hydrogen, and Carbon Dioxide on tl7e peratures, indicated a reproducible order of 0.75
Reaction Rate with respect to carbon monoxide partial pressure
Rate orders were determined at 320 and 380 in the range 20 to 80 Torr. At 320 "C, this order
"C. For carbon dioxide and hydrogen rate- changed to 0.5 in the partial pressure range 100
order determinations, the partial pressures of t o 240 Torr, Fig. 2.
 KRUPAY A N D ROSS: S H I F T REACTION O N Mn(ll) OXIDE
1 , . . . I . I . . , , . .
05 0 5
log,o PARTIAL PRESSURE (mml
FIG.2. The effects of variations in the partial pres-
sures of carbon monoxide (O), water vapor (O), carbon
dioxide (a),
and hydrogen (W) on the reaction rates at
320 and 380 "C.(for experimental details, see text).
Thus, the rate of reaction r(mo1 m-2 s-I), can
be represented as:
[I] r = k(pco)0.75 (20 < pCO< 80 Torr)
and
[2] r = k (pco)0.5 (100 < pCO< 240 Torr)
The Isolaterl Effcts of Coniponents of tlie
Water-Gas Mixture oil the Catalyst Sutface
A stabilized catalyst sample was exposed t o
50 Torr of carbon dioxide in a total gas flow rate
of 350 ml inin-' (N.T.P.). At 380 "C this resulted
in a 98% conversion to carbon monoxide after
7 min exposure. This conversion decreased t o
zero after 45 min, curve B, Fig. 3. When 40 Torr
of carbon monoxide was immediately introduced
in a separate experiment, an initial 53% conver-
sion t o carbon dioxide was measured 6 min later
which decreased to zero after 35 min, curve A ,
Fig. 3. Subsequent treatment with 16 Torr of
water vapor for 30 niin followed by 40 Torr of
carbon dioxide did not yield any carbon mon-
oxide. Then, the introduction of the standard
water-gas mixture immediately showed a 44%
increase in the rate of reaction which returned to
the steady level after 30 min ; inset Fig. 3, curve C.
These results imply that the manganese(I1)
oxide surface is subject t o a reversible redox pro-
cess with either water vapor or carbon dioxide
acting as oxidizing agents and carbon monoxide
as a reducing agent for the oxidized surface.
If this enhanced initial activity was associated
with the presence of excess surface oxygen, then,
an initially lower rate of reaction might be ex-
pected t o occur on a surface reduced with carbon
monoxide. Hence, the stabilized catalyst was
3523
1
, , 1 . , . , I
20
TIME ( min )
FIG. 3. The isolated effects of carbon monoxide (A)
and carbon dioxide (B) a t 380 "C.Inset: the rate of con-
version after carbon dioxide (C) and carbon monoxide
(D) treatments.
treated first with 40 Torr of carbon nionoxide for
30 niin followed inimediately by the standard
water-gas nlixture. Contrary to the expected de-
crease in reaction rate, a 38% increase was re-
corded that returned t o the original rate of reac-
tion after 20 min; inset Fig. 3, curve D.
Tl7e Efect of Te1nperatut.e oil the Reaction Rate
The rate of reaction was determined from 300
to 400 "C at progessive 10 "C intervals. After the
standard pretreatment, the temperature was
lowered to 300 "C and the catalyst left for 9 h in
contact with the standard water-gas mixture
before determining tlie rate.
Rate constants were calculated by integration
of the rate eq. 1 as a function of concentration
rather than partial pressure and the values ob-
tained used in an Arrhenius plot to establish the
apparent activation energy, Fig. 4. The plot,
curve A , shows two distinct regions with activa-
tion energies of 16 f 0.5 kcal mol-' from 350
to 400 "C and 1 1 f 0.5 kcal mol-' from 300 to
340°C. The pre-exponential factors were 1.8 x lo9
and 3.7 x lo7 m ~ l e c u l e s ~ . ~ ~m - 2 S-I, re-
spectively. This change in tlie value of the ap-
parent activation energy was easily reproducible
on fresh catalyst samples. When the rates were
measured at decreasing 10 "C intervals from 400
to 300 "C using either fresh samples or those pre-
viously exhibiting a change in activation energy,
3524 CAN. J. CHEM. VOL. 51, 1973

mite (19) catalysts. The possibility that rate con-

trol is exercised within the surface interactions
that take dace between adsorbed carbon mon-
oxide and water has been considered to occur
on iron(II1) oxide based catalysts (4) while a n
alternative mechanism involving the formation
of surface forniate species on zinc(l1) oxide (20)
and magnesiuni(I1) oxide (20, 21) has also been
suggested. However, studies of t h e decomposi-
tion of formic acid on nianganese(I1) oxide (22)
have indicated that the formation of formate
intermediates is not involved in the water-gas
shift reaction on this catalyst from 300 to 400 "C.
Various assumptions were made, in the usual
way, with respect t o the rate-determining step in
FIG.4. Arrhenius plots of the reaction rates of the the shift reaction and the most satisfactory model
water-gas shift reaction on manganese(I1) oxide from was obtained by a s s ~ ~ m i nthat
g rate control was
300 to 400 "C. Curves A and C determined for step-wise associated with the surface reactions. Thus, if the
temperature increments from 300 to 400 " C ; curve B, rate of reaction, r., is determined by the surface
determined from 400 to 300 "C.
coverage, 0, of both carbon monoxide and water
absorbed on sites specific to each species, then:
a reproducible linear relationship was observed
over the entire temperature range with an ap-
parent activation energy of 16 f 0.5 kcal mol- I,
and if Oco and 01,,0 obey the simple Langmuir
and a pre-exponentiaI factor 1.2 x 10' mole- relationship, eq. 3 becomes:
culeso.25 1-0.25 m - 2 s - ~ ,Fig. 4, curve B. It is

worth noting that the observed change in value

of the activation energy corresponds with the
Curie temperature of manganese(l1) oxide, 337
'C (15). which is commonly known t o describe the
In order t o substantiate these results, the water Langmuir-Hinshelwood mechanisni.
vapor partial pressure was increased from 16 to Since it is reasonable to assume from the effect
40 Torr while the carbon monoxide partial pres- of water-vapor partiat pressure o n the reaction
sure was maintained a t 40 Torr, and the catalyst rate that the amount of water vapor adsorbed is
temperature was again increased in a stepwise fixed, for example if the water adsorption sites
fashion. The Arrhenius plot, Fig. 4, curve C, are saturated, then the term (b,,,opH,o) could be
showed two distinct regions with activation considered constant, so that eq. 3 can be reduced
energies of 16 f 0.5 kcal niol-' from 350 to to :
400 "C and l l & 0.5 kcal niol-' from 300 to
340 "C with corresponding pre-exponential fac-
tors of 1.4 x lo9 and 2.2 x. lo9 molecule^^.^^
1-0.25 m-2 s-', respectively. An activation ener-
1
-- 1
gy of 18 kcal mol-' has been reported (16) for - (3-+a
this catalyst assuming first order kinetics. r Pco

Discussion
Previously, the mechanism of the water-gas
shift reaction on an iron(I11) oxide catalyst pro-
moted with chromium oxide (17) has been inter-
preted as proceeding via a two-step alternating
oxidation-reduction scheme while a concerted
redox mechanism has been proposed from results
on iron-chromium oxides (18) and copper chro-
where a + b ~ , ~ ~ ~ , ~ ) / ( k and
b ~ P, =
~ ~ ~ 2 0
albco.
The Langmuir-type plots of (Ilr) us. (lip,,)
are shown in Fig. 5. Linear plots were obtained
.over the entire partial pressure range studied
from 20 to 240 Torr a t 320 "C and 20 t o I00 Torr
at 380 "C.
The observation that the water-gas conversion
can be maintained a t the lowest water vapor
 KRUPAY AND ROSS: SHIFT REACTION O N Mn(l1) OXIDE 3525
face area 14.5 m2 g-', prepared by reduction of
E-Mn,O, in hydrogen at 600 "C, gave less than
I"/,f the rate of conversion obtained with the
catalyst prepared by reduction in the standard
water-gas mixture and a surface area of 16.0 m2
g-'. Clearly the conversion rate process is sensi-
tive to the stoichiometry of the catalyst studied.
On the basis of the present findings, the mech-
anism of the surface reaction may be sum-
marized :
-
-I-
161 + [Ol-> co,,,,+ [
CO(,d5, I
[71 1 I + H,O + [OI
->Hz,~,

where [O] and [ ] represent an oxygen atom

or ion and an oxide vacancy on the surface of
the catalyst, respectively. The rate-determining
I
step is then the reaction between adsorbed car-
~ 10 20 3o 40 do bon monoxide and some surface oxygen species
(6).
1 FIG.5. Langmuir-type plots for the water-gas shift Studies of the simultaneous dehydrogenation
I reaction on manganese(I1) oxide at 320 and 380 "C.
I and dehydration of 2-propanol on nianganese(I1)
oxide (9) have shown thatthe water vapor partial
partial pressure appears to justify the assump- pressure has virti~allyno effect on the dehydro-
tion that the amount of adsorbed water vapor genation process but that the dehydration pro-
is constant. Rapid saturation of adsorption sites cess is inhibited which implies that specific de-
specific to water or slow desorption would be hydrogenation and dehydration sites exist on the
expected to result in the observed zero-order cor- surface of this catalyst. The observed zero order
respondence in the experimental rate expression rate dependence on the water vapor partial pres-
(1). sure in the shift reaction suggests that reaction 7
The derived rate equation (4a) also predicts a may occur on the dehydrogenation sites since
decrease in the rate of reaction when a(l + this reaction can be regarded as dehydrogenation.
I
Dcopc0) > bcopc0. This is in agreement with the Also the decomposition of N 2 0 on manganese
experimental change detected in the carbon mon- oxides (10) of variable metal oxidation states has
oxide reaction order from 0.75 in the partial been explained by a redox-type mechanism which
pressure region 20 to 100 Torr, to 0.5 between is facilitated by the presence of Mn"' sites and it
120 and 240 Torr. Thus, the 38wncrease in the was proposed that oxidation reactions should be
rate of conversion observed after the carbon assisted by conditions that tend to preserve the
monoxide pretreatment, curve D, Fig. 3, may be 3 + oxidation state of the metal. Such a proposal
associated with an increase in the surface cover- is also consistent with the present results, and
age of carbon monoxide as a result of the pre- the following surface scheme may be suggested
treatment. here for steady-state catalysis.
A useful indication of the nature of the reac- The amount of excess surface oxygen would
tion mechanism can be obtained from the results be maintained at a constant level during the
of the experiments shown in Fig. 3. Thus the course of the conversion. An essentially similar
surface of the catalyst is susceptible to a revers- scheme has been proposed to account for cataly-
ible oxidation-reduction process since either car- sis on copper chromite (19).
bon dioxide or water vapor can act separately The results of oxygen-exchange reactions on
as oxidizing agents, as shown, for example, by manganese(1V) oxide indicate that non-uniform
the 4 4 2 increase in the rate of conversion of the oxygen species are present on the oxide surface
water-gas mixture immediately after the pre- (23). And while other relevant studies (24) have
treatments with water vapor and carbon dioxide. shown that surface Mn(II1)-0 bonds are
Further, the green manganese oxide with a sur- weaker than those formed between manganese(I1)
 CAN. J . CHEM. VOL. 51, 1973

CO(,dS)

CO(g) + + -
/

a n d oxygen, there is also clear evidence t h a t a t We thank Dr. E. F. McCaffrey and D r . I. M. Hoodless
least t w o f o r m s o f chemisorbed oxygen a r e pres- for helpful suggestions and Mr. A. J. MacKenzie and
Mr. S. Spivak for expert technical assistance.
e n t o n manganese(I1) oxide (10). H e n c e it is
proposed t h a t i i ~ ec h a n g e in t h e value o f t h e ap-
parent activation energy a t 340 t o 350 "C m a y be 1. 0 . A. HOUGENand K. M. WATSON.Chemical
associated with a switch f r o m o n e t y p e o f active process principles. Part. 111. John Wiley and
Sons Inc., New York. 1966. R. M . STEPHENSON.
surface oxygen species in t h e reaction to a n o t h e r Introduction to the chemical process industries.
d u r i n g the course o f t h e t e m p e r a t u r e rise. T h e Reinhold. 1966. p. 301.
exact n a t u r e o f these species is still uncertain (10) 2. K. R. WILLIAMS and A. G. DISON.III Fuel cell
b u t t h e close correspondence between t h e tem- systems. Vol. 2. Edited by R. F. Gould. Ameri-
perature a t which t h e a p p a r e n t activation energy can Chemical Society Publication. 1969.
3. W. C. GARDINER, JR. Rates and mechanisms of
changes a n d t h e C u r i e transition f r o m ferro- chemical reactions. W. A. Benjamin, Inc., New
magnetic t o paramagnetic properties o f t h e oxide York. 1969.
at 337 "C inay be significant. T h e c o n s t a n t value 4. H. BOHLBRO. An investigation o n the kinetics of
of t h e a p p a r e n t activation energy f o u n d f r o m the conversion of carbon monoxide with water
curve B, Fig. 4 is believed to be a consequence of vapour over iron oxide based catalysts. Gjellerup,
Copenhagen. 1969.
t h e removal o r destruction o f low-temperature 5. S. OKI,J. HAPPEL, M. HNATOW,and Y. KANEKO.
active oxygen sites d u e t o oxide sintering a t t h e Preprint, 5th International Congress on CataIy-
higher temperatures before a n d d u r i n g t h e step- sis, Florida, 1972. North Holland, Amsterdam.
wise decrease in teniperature f r o m 400 "C. T h e 6. G. K. BORESKOV, V. SH. GRUVER,and T. M.
YUR'EVA, Kinet. Katal. 10, 294 (1969); 10, 862
possibility o f characterizing these surface species
(1969).
presents a n interesting problem for f u r t h e r study. 7. P. PUTANOV and Z. JOVANOVIC. Chem. Abstr. 74,
It m a y b e concluded t h a t the use o f man- 130840n (1971).
ganese(I1) oxide as a niajor c o m p o n e n t in com- 8. E. F. MCCAFFREY, D. G. KLISSURSKI, and R. A.
mercial shift catalysts would be m o s t favored at Ross. J. Catal. 26, 380 (1972).
9. D. G. KLISSURSKI,E. F. MCCAFFREY,and
temperatures a r o u n d 300 "C. T h e m a j o r long- R. A. Ross. Can. J. Chem. 49, 3778 (1971).
t e r m deterioration i n t h e catalytic activity o f t h e 10. A. CIMINOand V. INDOVINA. J . Catal. 17, 54
oxide would be associated with solid sintering (1970).
a n d t h e loss o f excess surface oxygen. I t h a s been 11. R. A. Ross and B. G. WALSH.J. Appl. Chem.
observed previously t h a t t h e conversion efficiency 11, 469 (1961).
12. A. B. HART, J. MCFADYEN, and R. A. Ross.
o f commercial iron oxide (4) a n d mixed iron/ Trans. Faraday Soc. 59, 1458 (1963).
c h r o m i u m oxide (25) catalysts is k n o w n t o fall 13. M. ELLIS,T. E. MOORE,and P. W. SELWOOD.
off as a result of sintering. J. Am. Chem. Soc. 72, 856 (1950).
 KRUPAY AND ROSS: S H I F T REACTION ON Mn(I1) OXIDE 3527
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