280

Chapter X

THE OXIDATION OF CA~BON MONOXIDE

The oxidation of carbon monoxide

CO + (X.1 )

at the ordinary temperatures of catalysis is irreversible, the

value of ~G~98 for reaction (X.1) being equal to - 61.4 kcal
mol- 1• The main contribution to L1 GO is given by a high negative
value of ~Ho values ( L1 H~98 = - 67.6 kcal mol-1). The entropy
change for reaction (X.1) is negative ( ~ S~98 = - 20.7 cal K- 1
mol- 1, so that the negative values of L1 GO become smaller at ele-
vated temperatures; nevertheless, even at high temperatures, the
equilibrium in reaction (X.1) is on right.
The heterogeneous catalytic oxidation of CO was discovered long
ago (H. Davy first reported this process on platinum /1/)and it
has been studied extensively /2-13/.
Carbon monoxide is a poisonous gas, and its destruction by ca-
talytic oxidation is of great practical importance: the method is
used for the protection of the atmosphere from exhaust fumes. In
addition, reaction (X.1) is widely used as a model process in sol-
ving various theoretical problems in catalysis.

The Oxidation of Carbon Monoxide Over Metal Catalysts

The most active metallic catalysts for CO oxidation are the

platinum metals which are usually active at 100°_600°C /14-17, 19,
23/. With platinum or palladium supported, in small amounts
(0.5 wt.%), on various carriers (A120 alumosilicates, porcela-
3,
in, activated clay) complete conversion is attained at 300°C and
with 1% CO concentration /22/. Rhodium and ruthenium are also ef-
fective catalysts /17/. With metals purified in ultravacuum, the
activity order Pt >Pd»Ag has been obtained, silver being inac-
tive up to 700°C /14, 15/. However, under ordinary conditions CO
is oxidized over silver at 400°-530°C /16/ and even at 90°_130°0
/19, 21/. At 150°C, palladium is nearly two orders of magnitude
 281

more active than gold /19/. The activity of Ni exceeds that of

Cu /18/.
The kinetics and mechanism of CO oxidation have been studied
using mainly Pt /14, 15, 20, 23/ and also using Pd, Ag, Au and Ni.
According to reference /20/, the reaction on platinum above
0C
230 proceeds via the interaction of gaseous CO with adsorbed
(0) species:

1)02+2( )-2(0)
2) CO + (0) - - - CO 2 + ( 2

At lower temperatures, the reaction is assumed to be between

adsorbed CO and weakly adsorbed oxYgen.
On platinum purified in ultravacuum, the reaction kinetics with
great excess of O2 and above 350°-400°C are simple /14, 15/:

1 0
r= k~O ~

The whole complex of observations with this catalyst have been ex-
plained /14, 15/ using the mechanism:

1) O
2 + ( )~(02)

2) CO + ( )~ (CO) 0
3) (02) + ( ) 2(0) (X.4)
~

4) (02) + CO- CO 2 + (0 )
°1
5) (0) + CO--C0 2 + )

The adsorbed CO species thought not to be active in the catalytic

reaction. The following rate equation, which applies to Scheme
(X.4), was obtained /14, 15/:
282

where k.~ are rate constants and b.~ are adsorption coefficients re-
ferring to steps 1) and 2). The calculated accomodation coefficient
of 02 (~0.2) as well as the activation energy for oxygen desorp-
tion are in a good agreement with adsorption measurements. At great
k k
4 5
excesses of 02' Eq. (X.5) reduces to (X.3), where k = ------
k + k
4 5
The data /14, 15/ cannot be described on the basis of Langmuir-Hin-
shelwood kinetics.
Similar studies with purified Pd /15/ have led to the mechanism:

1) CO +
2) 02 +
)~(CO)

)~(02)
°
3) (02) + )-2(0) 1 (X.6 )
4) (0) + CO ---C0 + ) 2
2

This gives rise to the rate equations:

~ k" POz ~O
(X.7)
k~ ~O + k~ ~O ~~

(X.8)
 283

where beo b
and b ' are the equilibrium constants for steps
O
'2
O2
1), 2) and 3). Eq. (x.?) corresponds to the absence of equilibrium
in steps 2) and 3) while equilibria in these steps are assumed in
deriving Eq. (X.8). These equations agree with the experimental
data. Scheme (X.6) is similar to Scheme (X.4). Here, the partici-
pation of gaseous CO in the catalytic process is also assumed, CO
molecules interacting with the adsorbed (0) species. With excess
of 02' the reaction follows Eq. (X.3) which is an extreme form of
Eqs. (X.?) and (X.8). Under these conditions, the CO 2 molecules
are formed by the collision of gaseous CO molecules with the cata-
lyst surface almost completely covered with (0) species; the cor-
responding probability of reaction is close to 0.1.
It has been shown by tracer methods /23/ that in the course of
catalysis on Pt the CO molecule is not decomposed and surface car-
bonate species (C0 ) are not intermediates. Hence, it follows that
3
mechanisms such as:

1) CO + ( )-(CO) 1
2) CO + (CO) - (C) + CO 1
2
3) (C) + °2--- C02 + ( )
(X.9)

2CO + °2 = 2C0
2

1) + )- (°2) 1
°2
2) CO + ( 0 2 ) - (C0 )
3
3) (C0 ) + CO-2C0 + ) 1
3 2

2CO + °2 = 2C0
2 (X.1 0)

1) + ) - (°2)
°2
2 ) CO + )-(CO) 2

3)(°2) + (CO) - (CO3) + ( ) (X.11)

4) (C0 + (CO)----2e0 + 2( )
3) 2

are not valid. However, (C0 complexes (reversibly formed, for

3)
284

example, from CO and (0», can exist on a surface but they are
2
not intermediates in the catalytic reaction. The main routes will
be (X.2) or (X.4) and (X.6). Similar results were obtained /24/
with silver. Rate equation (X.J) is true for Ag /21/, suggesting
that a mechanism such as (X.2) is valid.
Catalysis on Ni proceeds via the interaction of CO with (0) /18/.
The reaction is not influenced by CO 2• (The same was observed on
Pt, Pd and Ag). Thus, mechanism (X.2), with the participation of
adsorbed 0 2- or 0- species, is likely to be true. The authors /18/
believe that the unstable intermediate NiO - ° - CO, found by IR-
spectroscopy /25/, was formed from (0) and CO.
Some studies were made with metal alloys. The addition of Au
(up to "'50%) to Pd leads to a significant decrease in the activity;
with further enrich of the alloy with Au(up to 60%), the activity
increases slightly and then keeps constant up to 100% Au. 'rhe reac-
tion rate on Pd is proportional to Po and is inhibited by CO
2
while, on Au, zero order kinetics are observed /19/. The latter
result is somewhat doubtful since, in the case of zero order ki-
netics, it is difficult to explain the extremely low value of the
preexponential factor for Au. The supposition /19/ that there is
a very low fraction of active sites, d, is hardly acceptable for
one should assume a z 10-15 /J8/.
Introduction of 5 at. % Pd into Ag enhances its activity in
process (X.1) /16/.
Attempt to explain the results for alloys on the basis of the
electronic theories (d-band filling)encounters definite difficul-
ties /5/. First of all, data on the bond energies of oxYgen and
CO with the alloys are required to explain the empirical relation-
ships observed.

The Oxidation of Carbon Monoxide Over Simple Oxide Catalysts

According to reference /28/, the activity drops in the sequence:

CO J O4;> CuO» Mn0 2 > Fe 20 > V2°5> Si0 2• Conversions at 150°C decrease
J
in the order: C020J>NiO>CuO>Fe20J:>Cr20J>Ce02>U02 /26/; the
oxides BeO, WO and HgO are relatively inactive /27/. Co ca-
J J0 4
talyses reaction (X.1) even at - 60°C /42/ while Mn0 2 acts at
- 20 0C /2/. The general activity pattern at 150 0C is: Mn0 2>CoO>
;> CO J O4> MnO '> CdO '> Ag20 '> CuO '> NiO:>Sn0 > CU
2 20;;- co 20 J:> ZnO :> Ti0 2 :>
 285

7Fe203'> Zr0 2> cr 20 >Ce0 2 »V20 5 »HgO »w0 3» Th02» BeO :>MgO;:> Ge02:>
3
»Al 20 Si0 2 /34/.
3>
The results of latter studies are in agreement with the above
data. For example, the specific activities at 170 0C decreases in
the order: Co /29/, and at 227 0C, C0 cuO>Mn20
304,>NiO,>Sn0 2 304, 3,
NiO, Cr203>Fe203,>znO:>V205 /30/. The oxides of the rare earth
metals are poorly active; of these, the relatively more active
catalysts are the oxides of EU, Ce, Nd and Pr which are more ac-
tive than the oxides of La, Gd, Sm, Er, Y, Dy, Ho, Tm and Lu. The
oxides of Sm, Er and Y operate at nearly the same temperatures as
does Al 20 /33/. According to reference /32/, the specific activi-
3
ty order Nd 20 :> Dy203> La 20 3 holds at 300 o C.
3
Thus, the most active catalysts for the oxidation of CO are the
oxides of Co, Mn, Cu and perhaps Ni. The oxides of the other tran-
sition metals (Fe, Cr and Ag) as well as CdO, Sn0 2, ZnO are mode-
rately active, while the higher oxides of polyvalent metals (Ti,
Zr, Ce, Th, V and W) and most of the non-transition metal oxides
(BeO, MgO, Al 20 Si0 2 and Ge02) are relatively inactive.
3,
Nevertheless, the above orders are slighly affected by chan-
ging the temperatures used for comparison when definite differences
exist. Thedifferencesaredistinctive on going from low (100°-150°C)
to higher (300 0-400°0) temperatures /26, 27/.
Before the further analysis of the experimental data, we shall
consider the most probable schemes of the oxidation of carbon mo-
noxide and the corresponding rate equations. According to referen-
ces /35-37/, the catalytic oxidation of CO as well as of other
substances cannot follow mechanisms involving phase transformations
of the catalyst. Nevertheless, some authors (see, for example, /29~
accept schemes of that kind.
Among different possible reaction routes including the formation
of intermediate chemical compounds on the surface, two types of
mechanisms should be distinguished.
The first mechanism consists of reduction of the surface with
CO and its reoxidation with 02. The simplest example of such a
mechanism is given by Scheme (X.2) in which (0) represents surface
oxygen anions and ( ) is an oxygen vacancy on a surface. This
scheme can be expanded. The step of reoxidation is likely to in-
volve the formation as intermediates of unstable molecular oxygen
anions which are immediately transformed into (0) species. Rever-
sible adsorption of CO 2, with the formation of surface carbonate
286

anions 110/, is also taken into consideration. Thus, the final

scheme will be:

1)0 ) (0) ( )"2(0)

2 + - 2 fast
2) CO + (0)-C0 2 + 2 ex. 12)
.3) CO 2 + (0) - (C0.3) o

The rate equation

ex. 1.3)

relates to mechanism (X.12). Here, k i are rate constants and K

is the equilibrium constant for the third step. When KP CO «1,
2
Eq. (X.1.3) is reduced to

r=

(X.15 )

If Eq. (X.1]) is approximated by a power rate law:

(X.16 )

the values of m,n,l should vary between 0 and 1 (m + n = 1) /62/.

If equilibrium is set in step 1), the equation:

~~ pCOp~5
1+ Vo'?2 P0 (1-1- /(P
c~
)
(X.17 )
 287

will be valid, where b O is adsorption coefficient for O2•

2
One may suppose /57/ that the interaction of CO with (0) leads
to the formation of adsorbed CO 2 species:

1) °2 + )- (02 ).i...-..t.2 (0)

fast
2) CO + (0)-(C0 ) 2 (X.18)
2
3) (C02 ) - CO 2 + ( 2

Then

With fast CO 2 desorption (k ) ' Eq. (X.19) is reduced to

3»k 2P CO
k2
Eq. (X.14). If the desorption is slow (i.e. k P CO » 1 and
k1 .3
2-P
k O2 »1), Eq , (X.19) is transformed into a zero order equation:
3

In this case, the rate of catalysis is equal to the rate of desor-

ption of the CO 2 species covering almost all the surface.
The above schemes may involve the formation of intermediate
(C0 ) species from CO and surface oxygen /.39/. Several mechanisms
3
of such a type have been proposed /3,4,7,10,39/. One can distin-
guish the following schemes:

1) 02 + )----(02) ( )"'2 (0)

fast
2) CO + 2(0)-(C0.3) + ( ) 2

3)(C0 3 ) - CO 2 + (0) 2
288

1) .. 2(0)
°2 + ( )-(°2)
fast
2) CO + ) ____ (CO) 2
3) (CO) + 2(0)~(C03) + 2( 2 (X.22)
4) (C03)~C02 + (0) 2

2CO + 02 = 2C02
1) °2 + )-(°2) , 2(0)
fast
2) CO + 2(0)~(C03) +
3) (C0 + CO -2C0 2 + ( (X.23)
3)
2CO + 02 = 2C02
( )
1) )----(02) - 2(0)
°2 +
fast
2) CO + ) _(CO) 2 (X.24)
3) (CO) + 2(0) - (C0 3) + 2( ) 2
4) (CO) + (C0 + 2( ) 2
3)-2C0 2
2CO + 02 = 2C02

In Schemes (X.21) and (X.22), monomolecular decomposition of (C0

3)
takes place, while in Schemes (X.23) and (X.24), the (C0 species
3)
react with CO. In Schemes (X.22) and (X.24), the adsorption of CO
is assumed, while in Schemes (X.21) and (X.23), gaseous CO molecu-
les take part in the reaction.
If the formation of (C0 ) and its decomposition proceed faster
3
than the adsorption of 02' the rate equation will be:

r=2k!~ .
'2

With very slow decomposition of (C0 ) , Eq. (X.20) will be valid

3
for Scheme (X.21) while the equation:

(X.26 )
 289

will be observed in the case of Scheme (X.2J). When the adsorp-

tion of O2 and the decomposition of (CO are fast and the (CO
J) J)
species are formed very slowly, Eq. (X.15) will apply for Schemes
(X.21) and (X.2J).
Thus, mechanisms (X.21) and (X.2J) like (X.12) and (X.18) lead
to rate equations in which reaction orders in O2 and CO can change
from °to 1. Scheme (X.21), in contrast to Scheme (X.2J), may give
an equation of zero order in both reagents. Since the adsorption of
CO is assumed to be weak /10/, the rate equations for Schemes
(X.22) and (X.24) are similar to those for Schemes (X.21) and
(X.2J).
Some further detail of the intermediates (0), (CO), (C02) and
(CO has been given /J,4,7,8,10,11,25/. Usually, the (0) species
J)
are supposed to be similar to 0 2- anions, the (C0 2) to carboxylate
anions, the (CO to carbonate anions (CO; or COj-) with the struc-
J)
ture

°'~C/ °
I
o
I
Me

The adsorbed CO molecule is likely to be positively charged.

Using the above approach, the step

can be rewritten in the form:

CO + 2(02-)----(CO~-) + 2e + ( ),

Me z+ + 2e _Me(z-2)+

and so on.
For mechanisms (X.12), (X.18) and (X.21)-(X.24), separate in-
teraction of the initial reagents (CO and 02) with the catalyst is
necessary. The first step in these schemes corresponds to the re-
oxidation stage while the further steps represent the complex re-
duction stage.
290

For the alternative schemes, essential differences in the me-

chanisms and the rates of catalysis and the separate reactions
of surface reduction and reoxidation are assumed.
One of the differences is the state and reactivity of surface
oxygen. For example, catalysis and reoxidation can proceed via ve-
ry reactive (O-)-radicals which do not exist in the absence of O2,
i.e. under reduction conditions; in the latter case, only (0 2-)
species take part in the reaction. Thus, the catalytic mechanism
will be:
) ~(O-) ( ) +e.. 2 ( 0 - )
2 fast
2) CO + (0-)-C0 2 + e + ( 2

Because of the lower reactivity of (0 2-) species in comparison

with that of (0-) species, the rate of catalysis will exceed the
rate of a separate reduction process, but nevertheless, the rate
equations for catalysis and reduction are the same. In this case,
special evidence is required for the fact that, in catalysis, (0-)
species are present in rather high concentrations to provide a
fast reaction while these intermediates are absent under conditions
of reduction.
Essentially different mechanisms for catalysis and surface reduc-
tion may be another reason to account for their different rates.
Thus, in catalysis, both the reagents (CO and O2) may simultaneous-
ly form the intermediate on the catalyst, giving rise to "associa-
tive mechanism" of the type shown in Scheme (X.11). Under definite
conditions (at lower temperatures), such mechanisms may gain an
advantage over the mechanisms with separate interactions.
Provided that the adsorption equiJ.ibrium is attained in mecha-
nism (X.11) 1401, i.e. we have:

1) °2 + )=(°2)
2) CO + )~(CO) 2
3) (02) + (CO)-(C0 3) + ) (X.28)
4) (C0 (CO)--2C0 2 + 2( )
3) +
2CO + 02 = 2C02
 291

a rate equation of the Langmuir - rlinshelwood type:

will be valid. Eq. (X.29), in contrast with the above equations,

gives a maximum in the rate and negative orders with respect to
the reagnets with increasing Po and Peo• With bO Po + bcoP eo «1,
222
Eq. (X.29) is reduced to a second order equation:

(x, 30)

For the mechanisms with separate interaction, the total order of

reaction did not exceed unity. Small activation energies should
be expected for Scheme (X.28) since:

where E] is the activation energy for the rate-determining step

and qi are adsorption heats.
Some variations of the schemes involving the interaction of eo
(or of surface complexes formed from CO) with adsorbed oxygen have
been proposed. In particular, the interaction of (0 2) with carbo-
nate ions, facilitating their decomposition, has been assumed:

2) CO + 2 ( 0 ) - (CO]) + (

]) (0 2 ) + 2 (CO]) + ( )- 200 2 + 4 (0 )

According to reference /59/, the Itassociative route lt involves 02

adsorption in the form of (0;) with further interaction of CO with
2)
(O and (0- ) :
292

1) 02 + )-(°2)
2) CO + (02)-C0 + (0)
2
)) CO + (0) - CO 2 + ( )

This scheme leads to the rate equation:

If Aj 14 ~O
r =- -----~=------
~;74 ( 1+ :; ) + k2 10
. k2
which is like Eq. (X.19). ihth k2PCO«k1PO 1 +""k) and (
2 )
k)~k2' Bq, (X.1)) is transformed into Eq , (X.15), but in this ca-
se,the activation energy (E 2) for mechanism (X.))) should be expec-
ted to be considerably lower than that for mechanism (X.12) since
the (0-) species are more reactive than (0 2-). Thus, "associative"
mechanism will be preferable at lower temperatures.
The experimental data on carbon monoxide oxidation have been
obtained mainly with the oxides of the transition metals of the
fourth period as catalysts. In reference 131/, the catalytic acti-
vities, r, were compared with the rates, r s t' of the reduction and
oxidation steps carried separately out at PCO = 2 Torr and Po =
2
1 Torr. Fig. 100 shows sudden discontinuities in most of the Ar-
rhenius plots: at lower temperatures, the catalytic reaction pro-
ceeds with lower activation energies and higher rates than the
steps of reduction and reoxidation; at higher temperatures, r> r s t•
From this fact, it follows that at lower temperatures, the "asso-
ifr I
15 r "ci'4l;::m,.
2
14 \. ~
14-
13 \QC- ~:ft, 13
12 l¢¢~x:
/.It. c~
~,./I
e 4 .~ I
12
n 'f.\ "\5 1 1
10 L....L.....I.......L......l,="""':'J......o.--l
{/ 1.5 1.9 2.3 2.7 .11 I.! 1.5

Fig. 100 - Temperature dependences for the rates of catalysis (1-8)

and reduction-reoxidation (1'-8') for the oxides: 1 - C0304, 2 -
CuO, ) - Cu20, 4 - ZnO, 5 - Fe 20 6 - Mn2 0) , 7 - NiO, 8 - Cr20)1311
3,
 293

TABLE 34

Kinetic Characteristics of the Oxidation of CO Over the Oxides

of the Metals of Fourth Period at P = 2 Torr and Po = 1 Torr.
CO
2

Catalyst Ig r Ig r s t E Est Temperature

/kcal mol- 1 /kcal mol- 1 region of
transition/oC

C0 14.7 13.9 9 12 320-390

304
CuO 14.7 13.6 9 9 270-455
Mn20 1303 10.9 10 24 410-500
3
NiO 13.3 10.4 10 30 400
Cr 20 13.3 12.2 10 30 300
3
Fe 20 12.6 12.2 9 26 245
3
ZnO 12.0 9.7 9 27 420
V 9.2 8.1 16-17 16-17 460-590
20 5
Ti0 2 8.1 7.1 17-18 17-18

ciative" mechanism prevails while at higher temperatures, it is

transformed into a mechanism involving separate interaction (al-
ternating surface reduction-reoxidation) /31/.
For co the differences in rand r s t' E and Est are not high.
304'
One may suppose that with this catalyst (having low oxYgen bond
energy), the stepwise mechanisms of type (X.12) make an important
contribution even at low temperatures. The corresponding rate equa-
tion (X.13) predicts retardation by CO 2, The latter effect is re-
ally observed, especially below 80°C /42/. At 170°C, the rate equa-
tion
1 0.25
r=K~O ~2

has been found /29/. Since the total reaction order exceeds unity,
the "associative" mechanism of type (X.28) is possible under these
condi tions •
In earlier studies of the oxidation of CO on Mn0 2 at low tem-
peratures /63, 64/, the reduction-reoxidation mechanism has been
shown not to be valid. An influence of the reaction mixture on the
294

chemical composition of the catalyst has been found. 'I'he data of

recent studies with 0 18 tracer are conflicting: a conclusion re-
garding the participation of surface oxygen of Mn0 2 in catalysis
(i.e. evidence in favour of reduction-reoxidation mechanism) /67/
and a contrary conclusion /68/ have been reached. A similar situ-
ation is observed with the data concerning a comparison of the
rates of catalysis and of reduction /45, 46/. However, it should
be noted that these rates, at 250-3500C, are of the same order
/45/. On Mn0 2 (which is also characterized by surface oxygen with
low bond strength), the oxidation of CO is likely to follow reduc-
tion-reoxidation mechanism and "associative l1 mechanisms simultane-
ously. In contrast, with Mn20 (for which qs is higher than that
3
for Mn0 2) at 410°-500°0, the latter mechanism prevails (see Tab-
le 34) since the higher qs values are not favourable for reduc-
tion-reoxidation schemes. The reaction kinetics at 25°-350°0 and
excess of 02 are described by Eq. (X.15) /44, 45/. Water vapour
inhibits the process /45/. Dehydration of the surface (300 0-3500C)
enhances the catalytic activity /43/. The kinetics on hydrated man-
ganese oxide catalyst /47, 48/ at 117°C follows Eq. (X.14). A me-
chanism such as (X.12) is supposed to be predominant. The inhibi-
ting effect of CO 2 is ~ttributed to the reaction

According to reference /48/, the reaction over a hydrated manga-

nese oxide catalyst proceeds via mechanism (X.2) combined with a
scheme including the interaction of adsorbed 00 with 02.
It was firstly shown with CuO that the mechanisms at low and
high temperatures are different /39/. At low temperatures, CO is
assumed to react with weakly bonded oxygen (maybe (02» different
from the oxygen of the oxide. At elevated temperatures, the ordi-
nary reduction - oxidation mechanism is more likely.
In reference /50/, the rates of catalysis and surface reduction-
reoxidation over the steady-state catalyst have been compared at
150°-300°C. The temperature dependence of the rates of catalysis
(3% CO + air) and those of the reduction (370 CO + He) are presen-
ted in Fig. 101. It can be seen that, up to 250°C, the rate of ca-
talysis exceeds the rate of reduction while, at higher temperatu-
res, the rates coincide. The rate of reoxidation with 02 of the
reduced catalyst depends on the t Lme interval ,Ll t", be tween the
previous reduction and further reoxidation. Fig. 102 shows that
 295

C01/m! Fig. 101 - The dependence of

0.15
the amount of CO 2 formed on
0.12 the temperature: 1 - cataly-
sis, 2 - surface reduction of
CuO /50/.

20!;.

o 2 ...•
I.....-_ _.l....-_ _-'--_ _...J..-_

200 250 JOOtj°C

the reoxidation rate increases considerably as ~r ~ O. This

effect is explained by suggesting that the oxygen vacancies(which
were formed during reduction) are gradually filled by the oxygen
of the bulk of the oxide by means of oxygen ion diffusion. Such
a filling increases with At"', giving rise to lower reoxidation
rates proportional to the concentration of oxygen vacancies on
the surface. It is evident that the rates of catalysis should be
compared with those of reoxidation for L1 r-o. Under these con-
ditions, it was shown that O2 reacts rapidly with the reduced sur-
face. ThUS, it was shown that the reduction - reoxidation scheme
is true above 250 0-2700C for CuO while the other mechanism is li-
kely to be also valid at lower temperatures. In the first case,
Eq. (X.15) is observed /49, 50/ suggesting that the interaction
of CO with (0) is the rate-determining step on the surface almost
completely covered with oxygen.
Differences in the mechanisms of CO oxidation at lower and higher
temperatures have been found with NiO /8/.
In the first case:

(X.35 )

while, in the second:

f 0.2
r= *,0 .,0 (X.36 )
CO 0 .
'.2
296

Fig. 102 - The dependence of oxy- ·-2

gen readsorbed on CuO (0.022 ml x-J
of oxygen had been removed pre-
viously from 0.95 g of CuO) on 12
0 0
fJ r : 1 - 20 6 C, 2 - 248 C, 3 -
0C
300 /50/. 8

4-

4- 6' 8 t1r/mill

At low temperatures, the interaction of CO with weakly bonded oxy-

gen is likely to prevail. At elevated temperatures, the schemes
of the type (X.2), (X.21) and (X.23) are valid. The data obtained
do not allow one to favour a single scheme since there is evidence
in favour or against of the formation of (C0 /10/. Eq. (X.36)
3)
is likely to indicate that the interaction of CO with (0) is a
slow step at 8 ~ 1. That there are two regions of the reaction
on NiO with different mechanisms are supported by data of referen-
ces /31/ and /40/ (see Table 34). The total first order (m + n =

=1 for r = kpm pn
) observed in references /8/, /51/ and /52/
CO O2
is consistent with Schemes (X.33); Eq. (X.35) is then likely to be
an approximation of Eq. (X.34). On the other hand, it was observed
in reference /52/ that m + n = O. According to reference /53/ the
reaction rate on NiO is determined by the interaction of (CO) with
(C0 Different kinetic relationships were found in reference
3).
/40/ for which maxima were observed with increasing values of Pi
(at low temperatures). These facts maybe evidence in favour of
the mechanism of the type (X.28) (see Eq. (X.29».
With cr20 (like NiO), a sharp transition from low temperature
3
to high temperature mechanism is observed /31, 40/ (see Fig. 100,
Table 34). The kinetics at 300 0C /55/ obey the equation

r = k~oPg ,
2
 297

where m = 0.9-1. 0. For some sample s , n ~ - 0.1 to - 0.2, for

others, n ~ - 0.8 to - 0.9 (at low Po ). Carbon dioxide does not
2
affect the process. One can assume that the reaction at 300 0C fol-
lows several routes. At high values of Po ' the surface is almost
2
completely covered with (0) and the reduction-reoxidation mecha-
nism is valid (i.e. Eq. (X.15) is observed). At lower Po values,
2
an "associative" mechanism (X.28) is essential. The corresponding ra-
te law(Eq. (X.29)) predicts retardation by 02' Infrared spectrosco-
pic studies /41/ made above 300 0C have shown that complete decom-
position of the surface carbonates formed on Cr 20 occurs, carbon
3
monoxide not influencing the process. This suggests that Schemes
(X.2) and (X.21) are more probable than Scheme (X.23). At 150 oC,
the rate of reduction of the surface is equal to that of the de-
composition of (C0 both being less than the rate of catalysis.
3),
The decomposition of (C0 in the presence of 02 is fast and its
3)
rate is equal to the rate of catalysis. This evidence favours
Scheme (X.32) /41/. A different mechanism has been proved for the
low temperature (75 0-140oC) oxidation of CO over cr20 /56/; in
3
this work, the reaction was stUdied using tracers. The authors of
reference /56/ arrived at the conclusion that the reduction-reoxi-
dation mechanism is true. with the rate-determining step

only '" 1% of the surface being catalytically active.

"Associative" type mechanisms are thought to be essential for
the CO oxidation over V20 /31, 40/. With this catalyst, the ra-
5
tes of catalysis and reduction-reoxidation were equal only at
590°C /40/. Significant differences in r and rat were observed
with 1% V20 on silica: at 460°C with 22% CO and 11% 02' the rate of
5
catalysis is nearly three orders of magnitude greater than the
rate of reoxidation /59/. Taking into consideration the high re-
activity of anion-radicals of oxygen, the authors /59/ proposed
the following scheme:
2-
1) CO + (0 ) - CO
+ 2e
2
2) 2e + 2(V 5+)_2(v4+) ] catalyst reduction
298

3) (y4+) + °2-(y5+0;)

4) (y5 0-)
2
+ (y4+) _ 2(y5+0-) catalyst reoxidation
5+) + (0 2-) (X.)7)
5) (y5+0-) + (y4+)-2(V
6 ) (y5+ 0-) + CO - C 0 + (y5+0-)
2 2
7) (y5+ 0-) + CO-(v4+) + CO 2 ] reaction

Two routes can be distinguished here. Steps 1) to 5) give the re-

duction-reoxidation mechanism of the type (X.2):

1) 02 + )~(02)~(0-)~2(02-)
(X.)8)
2) CO + (02-)-C0 + ( ) + 2e 2
2
2CO + 02 = 2C02

while steps 3), 6) and 7) give a type (X.))) mechanism. The re-
action rate for the second route is assumed to be higher than
that for the first since the reactivity of (02) is higher than
that of (0 2-). At elevated temperatures, differences in the re-
activities disappear. According to reference /59/, an increase in
the concentration of free electrons in the catalyst facilitates
the transformation of (02) and (0-) into (0 2-). The latter is pro-
ved by the fact that, at Y205 contents exceeding 1%, the cataly-
tic activity decreases: vanadium ions become less isolated, which
favours steps 4) and 5), and decreases the concentration of oxy-
gen anion-radicals, providing enhanced activity. With massive
samples, an electron transfer between y4+ ions, via the crystal
lattice, is possible which leads to decay of (02) and (0-) spe-
cies by their transformation into (0 2-). The rate equation for
vanadium oxide catalyst at )80 o_4)OoC and excess of 02 /51/ was
found to be:

APC{)
r=-~-

/+B~O
The authors /51/ explain Eq. (X.)9) using a reaction mechanism
which is similar to (X.18). On the massive sample studied, the
main contribution is likely to be given by a mechanism like
 299

(X.18). At the same time, a partial contribution of Scheme (X.33)

is also possible, since Eq. (X.39) is like Eq. (X.34).
However, i t is not now clear why under conditions where the re-
duction-reoxidation mechanism is not the major one /31/ activation
energies for catalysis and for the reduction-reoxidation steps are
nearly the same (see Table 34). Similar problem appears in the
case of Ti0 2 /31, 40/. It should be noted that with massive samp-
les of V20 and Ti0 2 the differences in rand r s t are rather small.
5
According to reference /61/, the oxidation at 450 0-6000C of CO
over Ti0 2 follows a mechanism of type (X.2).
With ZnO, the transition from a low-temperature mechanism into
a high-temperature one occurs rather sharply at ~4200C (see
Fig. 100). At elevated temperatures and excess of 02' Eq. (X.15)
is observed /60/, suggesting that the interaction of CO with (0)
(at 8 ~ 1) is the rate-determining step. At lower temperatures,
Scheme (X.32) is probable since the catalysis rate is equal to the
rate of decomposition of the surface carbonates in the presence of
02' and to that of disappearance of (0;) species /41/.
Thus, one can arrive at the general conclusion that, in most
cases with a given oxide catalyst, the reaction at higher tempe-
ratures follows a reduction-reoxidation mechanism while, at lower
temperatures, mechanisms of other types are possible. The data ob-
tained are insufficient for reliable discrimination between Sche-
mes (X.12), (X.18) and (X.21) to (X.24) at high temperatures.
Although we cannot make jUdgements about the details of low tem-
perature-mechanisms, all hypotheses put forward involve adsorbed
(0;) radicals. Besides the schemes discussed, the following mecha-
nism, which includes simultaneous (L;e , truly "associative") in-
teraction of CO and 02' should be considered:

(X.40 )
2) CO + (0-) - CO 2 + ) + e

2CO + 02 = 2C02

In the first step, both the reagents form on the surface a common
activated complex, (CO 2) * , decomposing into CO 2 and (0-). The
o0

formation of the complex can be favoured by electron transfer from

CO to 02 via the lattice of the catalyst. Scheme (X.40) is the re-
verse of the low-temperature mechanism for the decomposition of
300

oxygen-containing compounds over oxide catalysts. It can be re-

written as:

1) R + O2 + ) -RO + (0)
2) R + (O)-RO + (X.41)

2R + O2 = 2RO

what is the reverse of the mechanism for the decomposition of RO

shown in Chapter VIII (Type I mechanism).
The oxidation of CO at large excesses of O2 usually proceeds
according to the rate equation

The value of k can be accounted for by different steps, depending

on the type of mechanism, but in all these steps, oxygen-catalyst
bonds either are broken:

e.g. CO + (0 2-) - - CO 2 + ) + 2e;

CO + (0-) - CO 2 + ( . ) + e
or are broken and reformed with the predominance of the first ef-
fect:
CO + 2 (0) - (CO 3) ;
CO + (0) - (C02) ,

the number of broken oxygen-catalyst bonds exceeding the number

of those formed. Thus, a decrease in catalytic activity with in-
creasing oxygen-catalyst bond strength should be expected as is
observed (see Fig. 103).
The existence of a definite correlation between qs and semi-
conducting properties of metal oxides leads to correlations bet-
ween the catalytic activities and electrophysical characteristics
of the oxides / 6, 10 /. Hence, the dependence of the catalytic
activity on the ability of the oxides to chemisorb CO / 28 /
becomes clear. In the irreversible chemisorption of CO, sur-
face carbonates are formed from CO and 2(0). The concentration
of the (C0 species increases as the oxygen-catalyst bonds be-
3)
come weaker, which gives rise to a correlation between qs and the
chemisorptive abilities of the metal oxides.
 301

!7r
2.5

Fig. 103 - The dependence of

2
specific catalytic activities
of metal oxides for the oxi-
1.5 dation of CO /6/ on the values
of qs'
!

0.5

20 40 50 80 /00
t'
flJ/KcaL (7- ato

The Oxidation of Carbon Monoxide Over

Complex and Promoted Oxide Catalysts

Among complex catalysts, the highest activities are exhibited

by systems containing the oxides of Mn, Co and CU, which are the
most active catalysts on their own. "Hopcalite-type" systems can
catalyse CO oxidation even at - 20 0C. A standard composition of
such a catalyst (wt.%) is 50% Mn0 2 + 30% CuO + 15% C020 + 5% Ag20
3
/69/. Almost the same activity is shown by 40% Mn0 2 + 60% CuO /70/.
Rather active systems are (Mn0 2 + Co 20 and (Mn0 2 + Fe 20 /27/
3) 3)
as well as (Mn0 2 + Ag20) /71/. On the addition of Ag20 to Mn0 2' the
reduction of silver oxide is retarded; Ag20 itself exhibits only
an initial high activity. Promoted silver permanganate is also ac-
tive /2/.
The system (c0 20 + Fe 20 (3 : 7) should be distinguished
3 3)
among cobalt catalysts; the system can act at OOC, even at small
concentrations, but it is readily poisoned by water vapour /27/.
With Cucr 20 50% conversion is attained at 115 0C (at ~11£0)
4,
as with C0 /30/; (CuO + Ti0 2) is also active but is rapidly po-
304
isoned by water vapour /26/. For purification from CO, the (CuO +
+ Al 20 (1 : 1) catalyst is used at 200 o_2700C /72/.
3)
Metal chromites, as well as (cr 20 + Al 20 accelerate the oxi-
3 3),
dation of CO at higher temperatures /74, 75/. The additives of
Mo0 3 inhibit the activity of cr20 /82/. Ferrites and manganites
3
have been also tested /75/.
302

Less active systems based on NiO, with addition of the oxides

of Li, Cr, Ag, Mn, Fe and W, have often been used /8, 76/ for
studying electronic factors incatalysis. The same applies to ZnO
with addition of Li 20 or Ga20 /77/.
3
The poor activity of V 20 is enhanced by doping with Mo0 3
5
/58, 78/ or K S0 /78/. With the (V 20 + Mo0 system, the acti-
2 4 5 3)
vity passes through a maximum at 25 mol. % M00 A similar pic-
3•
ture is observed with (V 20 + K2 S0 ) . (The optimum is 33 mol. %
5 4
K S0 ) /78/. Small amounts of P
2 4 20 5 (1-5 mol. %) promote V 20 5; fur-
ther addition of P20 leads to inhibition /79/. A significant pro-
5
moting effect on CuO /69/ or V 20 /80/ is given by small additions
5
of Pd.
At high excesses of 02' a first order dependence on CO and a
zero order dependence on 02 is usually found with the above cata-
lysts. It has been observed with (CuO + A1 20 /72/, (Cr 20 +
3) 3
+ A1 20 /73/, (V20 + Pd) /80/, etc. The rate-determining step
3) 5
in these cases is likely to be the interaction of CO with (0)
(at 8~1).
For NiO, mechanism (X.27) is accepted /53/. With (V 20 + Mo0
5 3),
a mechanism of surface reduction-reoxidation has been proved using
tracer methods (370 0C, PCO = 10 Torr and Po = 5 Torr) /58/.
The oxidation of CO over V20 promoted 2 by Pd follows the
5
rate equation

carbon dioxide inhibiting the process /80/.

Using (Cr 20 + Mo0 systems, the authors of reference /82/
3 3)
compared their experimental kinetic data with 34 theoretical me-
chanistic models. Agreement was found for a limited number of
schemes (only four). All these models turned out to be similar and
involved the interaction of (CO+) with (0 2-) to form (C0 2)
plus
( ) as the rate-determining step. Thus, a mechanism like (X.18)
to which is added a CO adsorption step is most probable.
The above considerations predict a dependence of r on the oxy-
gen-catalyst bond strength /83/. Such correlations have been ob-
served. The activity of (V 20 + Mo0 systems change in parallel
5 3)
with the eqUilibrium pressure of desorbed oxygen /84/ (Fig. 104)
and the reducibility of the catalysts by hydrogen /85/. A similar
picture is observed with (V20 + P20 /79/ and (Cr 20 + Mo0 /82/;
5 5) 3 3)
in these cases, the measure of the bond energy of the oxygen was
 303

Fig. 104 - A comparison of the

equilibrium pressures of desorbed
oxygen at 550°C (1) and 500°C (2)
with the catalytic activities of
(V 0 + Mo0 ) in the oxidation of
2 5 3
CO (3) /84, 85/. (X CO is the carbon
monoxide conversion at 465°C /78/).

-/

-2 L.----I..._.L.---l._....l-~
o 20 40 60 !lfo~/%

reducibility of the oxides.

Correlations between qs and the electrophysical properties of
similar catalysts (e.g. electrical conductivity and work function)
/82, 86/ lead to correlations of the latter with the catalytic ac-
tivities.
The promoting effect of heterophase additives like palladium
is of a different nature. The bond strength of the oxygen does
not change in this case but doping by palladium facilitates the
activation of the CO /80/. With (CuO + Pd), an enhancement of the
adsorption of CO (in comparison with CuO)has been observed /81/.

The Oxidation of Carbon Monoxide Over Zeolites

Containing Transition Metal Ions

The catalytic activity of Y-zeolites substituted by metal ions

for the oxidation of CO decreases in the order /87/: AgY, CoY>
>CuY,>NiY, CrY>FeY>MnY~NaY. According to reference /88/, the
order is: FeY> CoY >CuY>MnY~naY. The activity of CoY increases
sharply with the CO content. The rate equation for this catalyst:
O. 5
r = k PCO P °2
has been interpreted on the basis of Scheme (X.2) (dissociative
304

oxygen adsorption is assumed to be reversible and weak). The re-

duction-reoxidation mechanism was proved by comparison of the
steady-state rate of catalysis with the rates of the supposed
steps. The catalytic activity per addedgatom increases in the
sequence: isolated ions in the zeolite <clusters of the ions <
<discrete oxide phase /88/. In the above sequence, the covalent
character of the oxygen-metal bond increases, giving rise to the
increase of oxygen reactivity /89/. The oxygen bond strength is
also of great importance. There is no correlation of the activi-
ties of the metal-zeolites with the heats of adsorption of CO
/88/.

A Comparison of the Reactivities in Catalytic Oxidation of

Hydrogen and Carbon Monoxide

Under definite conditions, the oxidation of H2 and of CO over

metal oxide catalysts follow the same mechanism:

1) O2 + ( ) - ( 0 2) ~2(0) 1
(X.42 )
2) R + (0) - RO + ( ) 2
2R + O2 = 2RO
where R is H2 or CO. The corresponding rate equation will be

(X.43)

where surface coverage, 8, by oxygen is given by:

(X.44)

At the same values of Pi and T, the relative reactivities of H

2
and CO (rH and r CO) are determined by the values of k and
2 2
e.
Since the entropies of activation of the second step for both re-
actions are close /38/, the differences in k should be accounted
2
for to the differences in activation energies E2• On the basis of
the Bronsted-Temkin relationship, the value of E should decrease
2
with increasing heats (q2) of the second step, the latter being
 305

equal to (qRO - qR - qs) where qRO and qR are the heats of forma-
tion of RO and R, respectively. For R = CO, the value of (qRO- qR)
is 10 kcal mol- 1 higher than that for it. = H2, sO that lower E2
and higher k 2 values should be expected for the oxidation of CO.
As a result,the values of 8 in Eq. (X.44) should be greater for
the oxidation of H2• Thus, the values of k 2 and 8 will change
in opposite directions.
On a given catalyst, with PR and T constant,

(X.45)

where the subscript denotes the reactant R. At sufficiently high

values of (k 2)CO / (k 2 )H ' the latter will cause higher rates of
2
CO oxidation. (Nevertheless, 8 CO / 8 H <.1). Fig. 105 presents
2

!ColrNz- - - - - - - - - - -/-
10
2
Fig. 105 - The dependence of re-
lative reactivities of CO and
H on the reaction mixture com-
2
5 position. 1he model calculation
for various k 1/(k2)cO values:
1 - 10, £ - 1,2 - 0.1.
1 "'-- --'- .....
o 5

the results of model calculations of rCO/rH for (k 2)co/(k2 )H =

2 2
= 10 and various values of k 1/(k2)CO ( and k 1/(k2)H ' respective-
2
ly). One can see that at higher ratios of Po /P R, where 6'-1, the
value of rCO/rH trends to tnat of (k 2)CO / 2 (k 2 )H (which fol-
2 2
lows directly from Eq. (X.45». At lower values of Po /P R, the va-
2
lue of rCO/rH trends to unity since, when 8 _ 0, Eq. (X.43) is
2
reduced to an equation which is first order in O2• In this extreme
case (i.e. B~O), the rates of both reactions compared are equ-
306

al and are determined by the rate of adsorption of 02.

Higher values of k 1 favour high oxygen coverage s, B, at wh i.ch
the higher reactivity of CO is exhibited to a maximal extent
(see Fig. 105). Hence, it follows that for catalysts with higher
values of qs (and k 1), the difference in reO and r H should be
more marked. 2
It should be noted that the higher reactivity of 80 leads to
lower reaction temperatures; under these conditions, the mecha-
nisms of "associative" type, for which high rates are typical,
may be most important. Thus, in catalysis over metal oxides, car-
bon monoxide should be expected to be oxidized more readily at
lower temperatures. The experimentRl data prove this conclusion,
see Fig. 106. The parallel changes in reO and r are explained
H2
by the correlation of both rates with qs'
For (E2)eo«E 2)H at elevated temperatures, the ratio
2,
(k 2)CO / (k 2)H should decrease and r H will tend to reO' Thus,
2 2
for higher reactivities of CO (in comparison with H high values
2),
of qs' lower temperatures and higher values of Po / PR are all
favourable. 2
The above considerations are also valid for the oxidation of
H2 + CO mixtures,and hydrogen in a mixture with co is oxidized
more slowly than the carbon monoxide /44/.
A different picture is observed in catalysis over the transition
metals. In this case, the rate of oxidation of hydrogen is signi-
ficantly greater because of the preliminary dissociative adsorp-
tion of the H2 enhancing its reactivity. There is no such activa-

19' /co
Fig. 106 - A comparison of ca- 14
talytic activities of the oxides
of the transition metals (belon- 12 12
ging to the fourth period) for
2 I
r
the oxidation of hydrogen (1) m 11 10
and carbon monoxide (2). The ra- I
I
tes, r, are expressed in molecu- 8 ; (MTlO;J 8
les em-2 s -1 • The temperature / rz~ Mnto" [OJ04 CliO
was 227°e and PR = 2 Torr /31/.
riol crZoJ rflOJ triO Z110
 307

tion in the oxidation of CO. Hence, one can expect the oxidation
of hydrogen over the transition metals to proceed more rapidly
than the oxidation of CO. The former process can, in fact, be ac-
celerated by Pt even at liquid nitrogen temperature while the lat-
ter begins only at 80 o-1000 C. It is clear that the differences in
the rates of oxidation of H2 and CO over the transition metals
will be less exhibited at a large excesses of 02 since, under
these conditions, the dissociative adsorption of H2 is hindered.
At elevated temperatures, when the transition of the reaction
into gas phase is possible (i.e. heterogeneous-homogeneous cata-
lysis occurs), the oxidation of hydrogen is also preferable to the
oxidation of carbon monoxide since, in the latter case, the radi-
cal chain process in the gas phase cannot proceed without water
vapour or other hydrogen donors.
The significant activation of hydrogen on transition metals, in
contrast to that on metal oxides, and in contrast to the oxidation
of CO on metals and metal oxides,helps to explain the different re-
lationships between the catalytic activities of the metals and of
the oxides in the reactions considered. This activation gives rise
to much higher activities with the transition metals (in compari-
son with the oxides) in the oxidation of H2 (at ordinary tempera-
tures, the optimal metal catalyst, pt, is 5-7 orders of magnitude
more active than the optimal oxide catalyst, C0 0 ) while, in the
3 4
oxidation of CO. such differences are not observed. Moreover, the
most active catalysts for the oxidation of CO (Mn0 2 and C0 0 )
3 4
cause reaction below OoC when Pt is inactive. This may be attri-
buted to the fact that in the catalytic oxidation of CO at low
temperatures, the prevailing mechanisms involve anion-radicals
(02) or (0-). Due to the high concentrations of free electrons in
the metals, these radicals are rapidly transformed into (0 2-) spe-
cies so that the advantageous mechanisms involving (02) and (0-)
cannot be realized.

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