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I . Introduction
formation for the theory, but also find immediate practical applications in
process optimization and reactor design. The calculations of this kind are
performed now with electronic computers on a large scale.
This chapter presents an account of the main results of studies of kinetics
of some industrial heterogeneous catalytic reactions. The studies have been
carried out by the author with his co-workers at the Karpov Institute of
Physical Chemistry (Moscow, USSR). The presentation is not chrono-
logical ; the reactions are arranged based on the character of interpretation
of their kinetics.
For compactness and to avoid repetition, some general aspects of experi-
mental methods and theoretical principles developed in the course of our
investigations are formulated prior to the discussion of individual reactions.
A more detailed analysis of many of the subjects dealt with in this part of
the chapter can be found in the contributions by Kiperman (1) and Snagov-
skii and Ostrovskii (2).
The limits of this article did not allow inclusion of the results of the com-
parison of kinetic equations with experimental data. They are given in the
referenced original papers.
- - II
Some time after the beginning of the operation, the system comes to a
steady state and the composition of the outgoing gas mixture in pipe 2 ceases
to change. In essence, it is sufficient to pass through the system a volume of
the gas mixture 5 times that of the system. After that the reaction continues
indefinitely under constant conditions. Because of the large circulation rate,
the degree of conversion at each single passage of the gas mixture through
the reactor is small; therefore, the composition and temperature of the
mixture at the reactor inlet and outlet are almost the same. Conversely, the
composition of the mixture at the cycle inlet and outlet can differ consider-
ably; the overall degree of conversion possibly being high since the gas mix-
ture repeatedly passes through the reactor and is renewed to only a small
extent by the feedstock.
It has already been mentioned that the experiments of this sort realize a
practically nongradient course of reaction. Specifically, large-scale non-
gradient conditions exist in the reactor, viz., the composition of the gas mix-
ture and its temperature in the space between catalyst grains are virtually
identical in the whole volume of the reactor. But this does not preclude
considerable temperature and concentration gradients directed from the
surface to the center of the catalyst grain. These gradients can be eliminated,
INDUSTRIAL HETEROGENEOUS CATALYTIC REACTIONS 177
however, if sufficient small grains are used. On the other hand, experiments
with grains of the size which is used in industry can provide data on the effect
of diffusionin the pores of the catalyst and heat transfer in the grains on the
course of reaction under the industrial conditions.
The measurements with small grains characterize a reaction in the kinetic
region. The composition of the gas mixture flowing out of the cycle, which is
determined by analysis, is just the composition of the reaction medium.
The reaction rate is easily calculated from the same results of analysis; the
extent of the reaction, t, during some time, t , is equal to the increment of the
amount of any product or to the decrement of the amount of any reactant
when the gas mixture has passed through the system divided by the respective
stoichiometric coefficient. Since the reaction is steady state, 5 is proportional
to t ; and since the reaction proceeds under nongradient conditions, 5 is
proportional to the surface of the catalyst, s. As a result, the general Eq. (3)
reduces to
r = lyts. (4)
If the reaction is conducted in a closed system and an identical course of
the reaction on the whole surface of the catalyst is achieved, e.g., by circula-
tion, then
r = (l/s)(d(/dt). (5)
If the reaction is steady state and carried out in a flow reactor, then
r = (l/t)(d</ds). (6)
The comparison of (5) and (6) with (4)demonstrates that the reaction rate
in the circulation flow system is found in the simplest way.
By changing flow rate and the composition of the gas mixture at the inlet
of the cycle, we vary the composition of the reacting gas mixture and deter-
mine the corresponding variation in reaction rate. We may also add dif-
ferent amounts of the reaction products, inert gases, or catalytic poisons to
the initial gas mixture.
The advantages of the circulation flow system over static or flow systems
become particularly essential in the studies of the reactions occurring simul-
taneously along several pathways with the formation of a variety of products.
The circulation flow method is applicable for the studies of almost any
heterogeneous catalytic reaction. At high pressures steel equipment is used
instead of glass. The first circulation flow reactor for high pressures was
designed by Sidorov (6);the gas mixture is circulated in this reactor by means
of steel bellows that are actuated by a rod introduced into the reactor also
through bellows, without any packing.
After the circulation flow method had been developed, various authors
178 M. I. TEMKIN
where r is reaction rate per unit surface, t~ is the specific surface area, and
pg is the grain density.
Effective diffusion coefficient of substance Bi in the grain will be denoted
as Di* ; for the simplicity we assume Di* to be constant.
In the case of a kinetic equation of an arbitrary form, the well-known
differential equation describing a combined progress of a reaction and
diffusion cannot be integrated. The first terms of series expansion of the
efficiency factor in powers of the grain radius, a, can be found. A rather
cumbersome calculation gives (ZI)
Here ci is the concentration of the substance Bi;index u shows that the corre-
sponding value refers to the periphery of the grain (i.e., to the distance from
the center of the grain equal to a).
The term of the series (10) containing u2 is, as a rule, negative; therefore,
diffusion usually inhibits the reaction. Indeed, if Bi is a reactant, then bi < 0
and, usually, do/&, > 0; if, on the other hand, B , is a reaction product,
bi < 0 and, usually, do/&, < 0.Thus, all nonvanishing products bi(8w/dci),
are usually negative (although exceptions do exist). The term of (10) con-
taining u4 is, as a rule, positive.
The greater q differs from 1, the slower the series (10) converges; when
the difference is large, the series becomes divergent. Limiting the expansion
as given above, i.e., terminating it by the term with u4, one may obtain q
with a sufficient accuracy at the level not less than ca. 0.85. In order to judge
whether the kinetic region is achieved, a formula adequate for q values still
nearer to 1 is sufficient; therefore, the series can be terminated by the term
with u2. Let us introduce a symbol
Y = - a2 1(bi/Di*)(do/dci),.
i
The minus sign in the definition makes Y usually positive. For q close to
unity
q x 1-Ar. (12)
Therefore, the effect of diffusion may be neglected if the absolute value of
the dimensionless criterion, Y, is sufficiently small. Thus, if /TI6 0.3, then,
according to (12), 0.98 < q 6 1.02.
INDUSTRIAL HETEROGENEOUS CATALYTIC REACTIONS 181
where ni is the order of the reaction with respect to substance Bi,k is the
rate constant. Then, according to ( l l ) ,
r = -azw, ci (binjoi*(ci),). (14)
where
cp = a(k/D*). (16)
Therefore, cp = f l .
There was an opinion that a2w,/D*c [or ~ ( w l , l D * c ) / ~is] a generally
applicable criterion of the attainment of the kinetic region. However, this
is not always true. In the case of a reversible first-order reaction
A P B. (17)
w = k + c A - k - c , where k , and k - are rate constants for the forward
and reverse reactions, bA = -1 and bB = 1. It follows from (11) that
T = a2(k+/DA*+ k-/D,*). Since the problem is linear, an exact solution
can be obtained; if we have
cp = a(k+/D,* + k-/DB*)2, (18)
then Eq. (15) is again valid (13). According to (15) and (18), the efficiency
factor, q, is constant regardless of the degree of approach to the equilibrium.
It follows that can be much smaller than unity no matter how small the
reaction rate on the periphery of the grains, 0,. Thus, in the case of a re-
versible reaction, one cannot conclude that the reaction occurs in the kinetic
region only on the basis that its rate is small; for a correct judgment, the
value of the criterion Y should be found as defined by (1 1).
One should take into account the specific features of gas diffusion in
porous solids when measuring effective diffusion coefficients in the pores
of catalysts. The measurements are usually carried out with a flat membrane
of the porous material. The membrane is washed on one side by one gas
and on the other side by another gas, the pressure on both sides being kept
182 M. I. TEMKIN
identical. Often hydrogen and nitrogen are used. The amount of one gas
passing through the membrane per unit time is determined from its content
in the stream of the second gas after the membrane and the velocity of the
stream. Having known the thickness and the area of the membrane, the
effective diffusion coefficient of the first gas is calculated. Starting from this,
further calculations of effective diffusion coefficients of participating gases
for the required values of temperature and pressure are performed, calcula-
tion depending on the interpretation of diffusion; namely whether it is of
the Knudsen, bulk, or intermediate type.
Bulk diffusion coefficients in binary gas mixture are almost independent
of the ratio of components of the mixture. Therefore, it was supposed that
if diffusion in the measurements described above is of the bulk type, i.e.,
the free path of molecules is much lesser than the diameter of pores, then the
first gas diffuses into the second gas at the same rate as the second gas dif-
fuses into the first.
However, as early as in 1833 Graham described in a number of articles
(14) the results of his experiments on diffusion of various gases in porous
bodies, mainly gypsum. He concluded that gases diffuse into each other not
at equal velocities, but at velocities that are inversely proportional to the
square roots of their densities or, in modern terms, to the square roots of
molecular weights. In the concluding paragraph Graham wrote :
The law at which we have arrived (which is merely a description of the appearances, and
involves, I believe, nothing hypothetic), is certainly not provided for in the corpuscular
philosophy of the day, and is altogether so extraordinary, that I may be excused for not
speculating further upon its cause, till its various bearings, and certain collateral sub-
jects, be fully investigated.
Later, after the works of Knudsen on gas flow at low pressures, the result
of Graham was explained supposing that in his experiments the free path of
molecules exceeded the diameter of pores [see, e.g., the book by Herzfeld
(IS)].Only in 1955 Hoogschagen proved experimentally that even with pores
considerably larger than the free path of the molecules, the velocities of the
counterflows of gases are inversely proportional to the square roots of
molecular weights (16). Subsequently, this result was confirmed by a number
of authors (17, 18); none of them, however, like Hoogschagen, mention
Grahams work. In justice, this relationship must be called Grahams
law, as named by Maxwell (19).
The explanation of Grahams law given by Hoogschagen is not com-
plete, as subsequent authors (17,18) stated. However, the attempts of these
authors to give a more complete explanation for the law are not convincing.
It is known that at conventional measurements of diffusion coefficients in
binary gas mixtures using wide capillaries, equal velocities of counterdif-
fusion of the components are observed. From the considerations developed
INDUSTRIAL HETEROGENEOUS CATALYTIC REACTIONS 183
in the referenced articles, the reason for the difference between narrow
capillaries where Grahams law is followed and wide capillaries where this
law is not obeyed cannot be seen.
Let steady-state diffusion of components A and B of a gas mixture occur
in opposite directions at a capillary diameter that exceeds many times the
free path of the molecules, the pressure along the capillary being constant.
The concentration of A decreases from left to right and that of B from right
to left. Let us assume that the gas mixture at the beginning does not move.
A small section of the wall of the capillary is impinged upon by the molecules
hitting the wall from the distance of the order of the average free path. Since
the concentration of the molecules of the component A on the left is larger
than on the right, more such molecules will be coming from the left. As a
result, the section will be subjected not only to the normal force of partial
pressure of A, but also to a tangential force directed in parallel to the axis
of the capillary. The tangential force owing to component B has the opposite
direction. However, if the molecular weights of A and B are different, these
tangential forces do not equilibrate. According to the law of action and
counteraction, the gas mixture in this case will be affected by a force equal in
value to the resultant of these tangential forces, but oppositely directed.
Such forces will arise at all elementary sections of the capillary surface.
Under their action the gas mixture will be accelerated until, as the result of
addition of the velocity of the gas mixture as a whole and velocities of mole-
cules relative to the gas mixture, the velocities of the molecules relative to
the capillary will change so that the total momentum transfer to the wall
would vanish. Then the force applied to the gas mixture and, consequently,
the acceleration will also vanish and the gas mixture will move at a constant
velocity. This gas flow, the necessity of which has not been recognized by
the previous authors, may be called concentrational effusion, in analogy to
a long known phenomenon of thermal effusion. The flow occurs in a form
completely different from the usual flow of a gas in a capillary under the
effect of pressure difference, viz., the velocity of the gas mixture in the case of
concentrational effusion is identical at all distances from the axis of the capil-
lary, except for the layer adjacent to the wall, the thickness of which is of
the order of the free path, in which the velocity decreases up to zero. The
requirement that the tangential momentum transfer to the wall per unit
time be equal zero immediately leads, as it has been already demonstrated
by Hoogschagen, to Grahams law.
Such is the explanation of Grahams law from the viewpoint of corpuscu-
lar philosophy; from it follows that this law should be valid for a capillary
of any width on the condition that the pressure along the capillary is constant.
Why then does Grahams law not manifest itself in wide capillaries?
The reason is that the requirement of the constancy of pressure becomes
stricter, the wider the capillary. It is known that, according to Poiseuilles
184 M. I. TEMKIN
law, the volume flowing through the capillary per unit time is proportional
to d4 where d is the diameter of the capillary. A small and therefore imper-
ceptible difference in pressures in wide capillaries creates a Poiseuilles flow
compensating the concentrational effusion. It can be calculated, for instance,
that in the case of counterdiffusion of H2 and N, at 1 atm and 20C, this
compensation at d = 0.01 mm requires the pressure difference, AP = 3.4
Torr and at d = 2 mm it is sufficient to have AP = Torr. Let a vessel
containing hydrogen be connected through a valve and a capillary of 2 mm
diameter to a vessel containing nitrogen and let, as long as the valve is closed,
the pressure in both vessels be exactly 1 atm. When the valve is opened,
concentrational effusion directed towards the vessel with nitrogen starts ;
at the moment the pressure in the vessel with nitrogen becomes higher than
in the vessel with hydrogen by Torr, effusion will be compensated by
Poiseuilles counterflow and the gases will counterdiffuse at equal velocities.
The discussion of diffusion in pores of a catalyst requires taking into ac-
count the specific features of diffusion in narrow capillaries.
mobility of the particles is low and the exchange of particles between the
surface and the volume is not sufficiently rapid. Then, as a result of the reac-
tion, the probability of encountering the particles of reactants on neighboring
sites is lower than the probability at an entirely chaotic distribution of the
particles on the surface. This reservation is not important for the examples
we shall discuss below; mass action law holds true for them.
In contrast to spatial distribution, the equilibrium energy distribution of
adsorbed particles cannot be violated to any substantial degree by reaction
since energy is rapidly transferred between adsorbed particles and solids.
Therefore, the activated complex method may be applied to rates of surface
reactions. For this we consider the activated complex (transition state) of a
surface reaction as a likeness of adsorbed particle (21). But, assuming that
each adsorbed particle occupies only one site, it is necessary, even in the
simplest kinetic model, to consider that activated complexes are able to
occupy not only one, but also several surface sites (21). For example, the
usual picture of a reaction between two particles adsorbed on neighboring
sites involves, in fact, the notion that the activated complex occupies both
sites. When the activated complex occupies several sites, this does not create
any difficulty for the theory since the surface concentration of activated
complexes is an infinitesimal quantity, and so the possibility of overlapping
the required sites is excluded.
If particles enter the surface activated complexes directly from the volume,
e.g., when the reaction occurs as a result of impact of molecules from the gas
phase upon the adsorbed molecules, the expression for the reaction rate
will contain, together with surface concentrations, the values of volume
concentrations. These impact mechanisms were long ago proposed by
Langmuir (22) for the reactions of CO and H, with 0, on the surface of
platinum; the reaction occurs at the impact of a CO or H, molecule against
an adsorbed 0 atom. Such reactions seem to be numerous (23). Along with
this, the above-mentioned adsorption mechanisms that involve the reaction
between two adsorbed particles are possible. Elementary acts of surface
reactions in which more than two particles participate are hardly probable.
It is convenient to consider the processes of adsorption and desorption,
being the constituents of heterogeneous catalytic reactions, as particular
cases of surface reactions. Thus, the reversible process of adsorption and
desorption of substance A can be expressed as follows :
AfZ#ZA (19)
where Z is the free site of the surface and ZA is the site occupied by the mole-
cule A. Applying mass action law, we obtain
186 M. I. TEMKIN
Here the state with [ZA] = [ZIis taken as a standard state of the adsorbed
layer; thus, in the case when only one gas is adsorbed, the layer is in the
standard state at the coverage 1/2. It can be easily seen that l/a is the equi-
librium pressure at [ZA] = [Z], i.e., at the standard state of the adsorbed
substance. This value may be called desorption pressure; we shall denote
it as b. It is analogous to vapor pressure or dissociation pressure in mono-
variant systems (24). Indeed, in the case of equilibrium of liquid with its
vapor, the surface from which evaporation occurs is equal to the surface
for condensation; the same equality is realized at the adsorption equilibrium
if the fraction of the occupied surface is equal to that of the free surface.
This analogy explains the applicability of the Nernst approximate formula
to desorption pressure (24):
log,, b = -(AHO/4.58T) + 1.75 log,, T + i* (26)
INDUSTRIAL HETEROGENEOUS CATALYTIC REACTIONS 187
0, + 2SOZ = 2s0,
In this scheme, as always in the following, Z denotes a site on the surface of
the catalyst, the arrows denote elementary reactions, and in the overall
equation the equality sign is employed. Stoichiometric numbers by which
the stage equations should be multiplied to obtain the overall equation are
given on the right side. In this instance intermediates are Z and ZO. Another
scheme equivalent to the previous one may be used :
1. 22 + o2 P 2 Z O 4 (34)
2. zo + so* # Z + so, I
The overall equation of scheme (34) is obtained from the overall equation
of scheme (33) when it is multiplied by 1/2. The possibility of multiplying
overall equations by arbitrary numbers is shown by the use of the equality
sign. Such an operation is not permissible for the equations of simple stages;
e.g., the equation
Z++02#ZO
is senseless: it would mean that 1/2 of the 0,molecule participates in an
elementary act. On the contrary, the equation
:o, + so, = so,
means only that from n 0, molecules and 2n SO, mdlecules 2 n SO3 mole-
cules are formed, where n is some number; the equation describes the stoichi-
ometry of the process, but not its mechanism.
In this example the exclusion of the intermediates could be effected,
essentially in one way only, since the column of stoichiometric numbers (i2)
is obtained from the column (i)by multiplication by an arbitrary factor;
this holds for any other suitable column of stoichiometric numbers. However,
this is not always the case-even when the reaction is described by one over-
all equation. Thus, a possible mechanism of oxidation of hydrogen on plat-
inum is (25)
Mi) 2
1. +
02 2Z+2ZO 1 1
2. H, +
2ZFt2ZH 0 2
3. ZO + ZH+ZOH Z + 0 2 (35)
4. ZOH + ZH + H 2 0 + 2 2 0 2
5. ZO + H, + Z H 2 0 + 2 0
where C, and C2 are arbitrary constant numbers, we shall say that route
N 3 )is a linear combination of routes N()and N() and express this relation-
ship by a symbolic equation
3 = C,1 + C,? (37)
Such a definition can, evidently, be extended to any number of routes. It is
clear that if N ( l ) ,N(), N 3 ). . . areroutes of a given reaction, then any linear
combination of these routes will also be a route of the reaction (i.e., will
produce the cancellation of intermediates). Obviously, any number of such
combinations can be formed. Speaking in terms of linear algebra, the reac-
tion routes form a vector space. If, in a set of reaction routes, none can be
represented as a linear combination of others, then the routes of this set are
linearly independent. A set of linearly independent reaction routes such that
any route of the reaction is a linear combination of these routes of the set
will be called the basis of routes. It follows from the theorems of linear
algebra that although the basis of routes can be chosen in different ways,
the number of basis routes for a given reaction mechanism is determined
uniquely, being the dimension of the space of the routes. Any set of routes
is a basis if the routes of the set are linearly independent and if their number
is equal to the dimension of the space of routes.
It may occur that when stoichiometric numbers of stages are chosen to
form a route, the cancellation of one intermediate at the summing up of
the stage equations inevitably leads to the cancellation of another. Thus, in
the mechanism (33) this is the case with the intermediates Z and ZO. This
results from the equality
[Z] + [ZOI = 1. (38)
We shall call such relationships balance equations. If there were two types
of sites on the surface, we would have two balance equations.
It can be shown algebraically that the number of basic routes, P,is deter-
mined by
P=S+ W-J (39)
where S is the number of stages, W is the number of balance equations, and
J is the number of intermediates. In the example (35) S = 5, W = 1, and
J = 4 (intermediates Z, ZO, ZH and ZOH); therefore, P = 2. Since N)
and MZ) are linearly independent and P = 2, N1) and N2)form a basis.
The relationship (39) was given in a somewhat different form by Horiuti
(26).
A linear independence of routes does not imply linear independence of
the respective overall equations. For instance, as mentioned, the basic routes
of the reaction (35) result in the same overall equation. A more complicated
192 M. I. TEMKIN
a certain group of reaction acts. This implies that a run along a certain route
of a given complex reaction is completed, the route by no means being an
obligatory basic one.
Now each route of the reaction can be represented as a linear combination
of its basic routes; therefore, a run along any route can be expressed as a
corresponding linear combination of runs along the basic routes. In accord-
ance with this, let us substitute for the runs along nonbasic routes (i.e., the
runs that are the actual constituents of a reaction) the equivalent runs along
basic routes. This means, for example, that if there was a run along a route
[C,N() + C2iV2)+ C,M3)] where N), M2), and M3) are basic routes, we
shall say that there was C , runs along the route N), C2 runs along the
route M2), and C , runs along the route M3). Let us consider a sufficiently
long period of time to neglect the runs along the routes that have begun
before this period and not terminated before it, or the routes that have begun
during this period and not terminated before its end. It is always possible,
since the reaction is at steady state and, hence, the period of time is not
limited. Then, neglecting uncompleted routes, we shall have all eventuated
reaction acts distributed singularly and without remains between basic
routes, forming runs along these routes. The ratio of the number of runs
along the basic route obtained in this manner to the period of time and the
size of the reaction space (volume or surface) is the rate of the reaction along
this basic route.
The notion rate along a basic route has a rigorous sense only for steady-
state reactions; in the general case the runs along stages cannot be singular
and without remains divided between basic routes. The rate of a steady-state
reaction is determined by the rates along the basic routes, as a vector in the
usual three-dimensional space is determined by its components along the
coordinate axis.
Let us denote the rate of the sth stage as rlsl;if this is a simple stage, then
rlsl= r, - rPs (41)
where r, and r - s are the rates of the forward and the reverse elementary
reactions comprising the stage. The rate along the basic route W)is denoted
as d p ) ; according to its definition there are v$)#~)runs of the sth stage per
unit time per unit reaction space, which was the share of the NP) route after
the distribution of the runs of stages between basic routes. The total number
of runs of the sth stage per unit time per unit reaction space is obtained by
summation over all P basic routes. Thus,
P
formal manner, the rates along basic routes being defined as the coefficients
in linear relations connecting vip) and rlslvalues.
In the most general case the rates of all elementary reactions are mutually
comparable, then all stages are simple and not at equilibrium. Equation
(42) is applicable to each stage. Expressing rls,in this equation through the
concentrations of species (volume of surface concentrations) in accordance
with (41) and mass action law, we obtain S equations according to the num-
ber of stages that relate rates along basic routes with concentrations. To
these S equations, W balance equations are added. J concentrations of in-
termediates and P rates along basic routes are the unknowns. According to
(25)
J + P = S + W, (43)
so the number of equations is equal to the number of unknowns.
If, for some stage r, x r - , B rlslthe stage is called fast, it may also be
called a quasi-equilibrium stage. In addition, strictly equilibrium stages are
also possible; namely, if stoichiometric numbers of a stage for all basic
routes are zero, then r, = r - , (ie., rlsl= 0). Herewith r, and r - s may be
small. Reversible adsorption of a catalytic poison may serve as an example
of such a stage. Quasi-equilibrium and strictly equilibrium stages will be
united under the general name equilibrium stages.
If a stage is an equilibrium one, then instead of the steady-state condition
(42) the equilibrium condition according to the mass action law is employed;
this does not change the number of equations and unknowns. Fast non-
equilibrium stages do not give equations, but then the number of unknowns
decreases correspondingly since some concentrations of intermediates are
not considered. Thus, (42) always solves completely the problem of the rate
of a steady-state reaction, at least in principle. The problem is reduced to
the solution of a set of algebraic equations. We shall call (42) stage steady-
state conditions. In fact, we need to apply this equation only to nonequi-
librium, and hence, simple stages; therefore we may substitute for rlsl the
difference r, - r - s without loss of generality and use the equation in the
following form :
P
When a reaction occurs in an ideal system (i.e., in ideal gas mixture, ideal
solution, or ideal adsorbed layer), then r, and r - , in (44)are determined by
simple mass action law. We shall call linear the stages whose rate, rlsl=
r, - r - , , depends linearly on the concentrations of intermediates (including
free sites of the surface); the stages whose rate depends nonlinearly on the
concentrations of intermediates (i.e., includes squares of concentrations of
196 M. I. TEMKIN
s:
s= 1
vpxjs= 0. (45)
V(Xj) = c c
S
s=l
xjs
P
p=l
v:p)r(p)
INDUSTRIAL HETEROGENEOUS CATALYTIC REACTIONS 197
From this and (45) it follows that r ( X j ) = 0. This conclusion holds for all
intermediates. Thus, if (42) is fulfilled for all stages, the reaction is at steady
state.
The conditions of steady state in the form of Bodenstein are obtained
having r ( X j ) = 0 in (46). In contradistinction to (42), these conditions may
be called the intermediates steady-state conditions. They define only a part
of the unknowns, viz., the concentration of intermediates, Xj, but there is
usually no difficulty in the determination of the reaction rate from these.
In a number of cases the application of states steady-state conditions for
obtaining kinetic equations is more convenient. Besides that, these condi-
tions are a source of certain general relations to be discussed later.
If the number of basic overall equations, Q, is smaller than that of basic
routes, P,it is expedient to use a stoichiometric basis of routes for a descrip-
tion of the reaction. In this case we need to know only Q rates along non-
empty basic routes; the remaining P - Q rates are not required (but this by
no means implies that they equal zero).
N2),. . N p ) ,find the rates r), r() . . . r) that answer to another basis
of routes, N),N2). . MP)(31, 32).
Let the passage from the first basis (not primed) to the second (primed)
be defined by equations of the form
i = c1 1 v()
s + c12 v s( 2 ) + . . . C,,v:p+
v p = cp 1 v(sl) + cPZ P)
s + . . . + cppv:p
where C l l , etc. are coefficients. Then the sought for rates will be found
by solving, with respect to r(),P),. . . r(), the set of equations
= c11r(l) + c . . . + Cplr(P)
2 1r ( 2 ) +
r(2) = + . . . + cP2+P)
C1 2r(1) + cZ2+2) (48)
. . .
rp = c1Pr(l)+ cZ P r(2) + ... + Cppr(P)
It is composed in such a way that the coefficients of each row of the set (47)
198 M. I. TEMKIN
,..
A, + A, = B, + B2
In scheme (53) I denotes an intermediate particle adsorbed on site Z,A,,
A,, B,, and B, are the molecules of gaseous reaction participants.
The rates of the elementary reactions are
rt = kl[Z]PAl; r - l = k-l[ZI]PB,
(54)
T2 = k,[zI]p~,; Y-2 = k_2[z]P~,.
Canceling [ZI],
we find
lCZpA2 -k k-lPB,
[Z]= r (57)
klPAlk2PA2 - k-1PB1k-2PB2
Taking s1 = 2, s2 = 1, in accordance with (52)
whence, according to ( 5 9 ,
This deduction illustrates the method of application of (52) that also can
be used in more complicated cases. The intermediate steady-state conditions
lead to the same result (35).
If both stages of scheme (53) are irreversible, then, having k - = k - 2 = 0
in (61), we obtain
k l P A l k2PA2
r=
klPAl + k2PA2'
This equation can be written as follows:
llr = ( l / k l p A ~ ) + (l/kZpAz)* (63)
It can also be easily obtained directly from the stages steady-state condi-
tions. Indeed, applying these conditions to each stage, we have
Therefore,
[z] = r/klPAlr [a]= r/k2PA2.
As a result of (55), we obtain (63) by summing these equations.
In general, (51) and (52) are useful for the deduction of kinetic equations
of such reactions, all stages of which (or at least a considerable part of
those stages) are reversible. If all stages are irreversible, it is convenient to
use stage steady-state condition (44).
It is easy to see how the obtained kinetic equations are to be changed
when, in a reaction analogous to that described by the scheme (53), the
number of gaseous participants differs from that in the scheme. If, e.g., two
species A, and A,' participate in the forward direction of the stage 2, there
will be the product P A I P A 2 t , instead of PA2,in the kinetic equation. If species
A2 is absent, 1 must be substituted for PA2,and so on.
The steady-state rate of a many-stage reaction is not attained immediately;
202 M. I. TEMKIN
Here L is the number of catalytic centers (i.e., sites for adsorption of par-
ticles I) on unit surface.
The ratio r/L is called turnover number of a catalytic site. The reverse
value u = L/r is of the dimension of time. It may be called turnover time;
it is the average time required for a catalytic center to complete the cycle
of transformations and to return to the initial state. The designation u
corresponds to the German word die Umschlagszeit [i.e., the time of turn-
over (of stock)]. On the basis of (61) and (67), it can be demonstrated that
t <$U, (68)
where u, = L/r,; the sign of equality is obtained if, first, the stages of
4
mechanism (53)are irreversible and, second, LZ] = [ZI] = [see Temkin
(36)l.
Thus the u value, which can be easily calculated directly from experi-
mental data, permits one to estimate the upper limit of z. It follows from
the meaning of u that in a mechanism more complex than (53) t also usu-
ally does not exceed u.
A reaction in a closed system cannot be strictly steady state. If, however,
during a period of the order of relaxation time the concentrations of reaction
participants vary negligibly little, the rate of the reaction at each moment
is practically the same as it would be at constant concentrations equal to
the concentrations at this moment. It is said in this case that the reaction
is quasi-steady state.
INDUSTRIAL HETEROGENEOUS CATALYTIC REACTIONS 203
All equations that are strictly correct for steady-state reactions are also
approximately correct for quasi-steady-state reactions. The method of ap-
proximate treatment of quasi-steady-state reactions as steady state is due
to Bodenstein.
and
r- lr-2r-3 '..rPs
r- = vlr2r3"'rs 4-r-lv2r3..ars+ r-,r-,v,.,-r,+..' + r-1r-2r-3**-vs (72)
_+ -- - lPB1 k - 2'B2
(74)
r- klpA1k2pA, '
Here AG, is the Gibbs energy change in the stage number s. According to
(80), 5 is the weighted average of the stoichiometric numbers v, with their
weights proportional to AGs. For equilibrium stages, AGs x 0; thus only
nonequilibrium stages are to be taken into account in the determination
of i . In particular, if only one stage number d is nonequilibrium and, there-
fore, is rate determining, then 5 = vd.
It follows from the theory of absolute rates of reactions that
AG, = - RT ln(r,/r-,). (81)
From chemical thermodynamics it is known that
vlAGl + v2AGz + . * . + vSAG = AG
= - RT In K + RT ~I[(B)~(B')~'/(A)~(A')"']
(82)
where AG and K are the Gibbs energy change and the equilibrium constant
of the reaction (79), (A), etc., are the activities of substances A, etc.; for the
reactions in ideal gas mixtures they are equal to partial pressures PA, etc.
Equations (73), (80), (81),and (82) imply that (31)
The number V is in the general case variable since the reaction conditions
affect the values AG,. However, 5 cannot exceed the largest of stoichiometric
numbers of stages, v,, and since v, are of the order of 1, ij is a number of the
same order. Therefore, (83) could possibly aid in deciding, without knowing
the reaction mechanism, whether r - may be neglected as compared with r + .
If stoichiometric numbers of all the slow stages are the same, then i
equals these numbers and, consequently, is constant. In these cases it is
always possible to write the overall reaction equation in such a way that
5 = 1. If this is done,
as in a single-stage reaction.
Generally speaking, the concept of forward and reverse reaction rates
is inapplicable to many-route reactions, but it can be applied in some par-
ticular cases. Such is the case of a double-route reaction with one of basic
routes being at equilibrium (38).
Indeed, let one of two basic routes, N") and N('), e.g., route N2),be an
equilibrium one. Let us only include in (51) all nonequilibrium stages of
the reaction. All stages participating in route N") are equilibrium ones;
206 M. I. TEMKIN
hence, for all nonequilibrium stages viZ) = 0. Therefore, the factor at r(2)
in (51) equals zero. Thus the equation obtained coincides with the equation
of a steady-state single-route reaction including all nonequilibrium stages ;
it is just the equation used above for the introduction of r+ and r - values.
Another case occurs if a mechanism of a many-route reaction includes
a block that has only one basic route; then, as was explained in Section
VII, the equation of single-route steady-state reactions and, consequently,
the concept of forward and reverse rates can be applied.
It may be noted that a rate of a many-route reaction can generally be
represented as a sum of rates of some imaginary irreversible reactions;
the number of these items, however, may exceed two (39).
Anticipating somewhat, we shall discuss now the relationship between
the forward and reverse rates of a single-route reaction on a nonuniform
surface. The surface under consideration consists of several kinds of sites
differkg in their rate of reaction; their number can be very large.
Let us denote the contributions of a site number i to the values of r+ and
r - as r$ and r?. Let us suppose first that intermediates do not migrate
from sites of one kind to sites of another; thus the reaction proceeds on
sites of each kind as if there were no others. Then according to (83)
]
(B)~(B)~lIp
(A)(A) .
If the same stages are equilibrium ones on all sites and the stoichiometric
numbers of nonequilibrium stages are the same (namely, are equal to a
certain number v), then (85) is applicable to all sites with the same i j = v
so that the ratio r?/rV is identical for all sites. Then
r+ = 1 - (K-~[(B)~(B)*/(A)(A)I) (87)
Langmuir equation for a uniform surface, but by the Zeldovich and Rogin-
skii equation or by the Bangham equation. Adsorption equilibrium is de-
scribed not by the hyperbolic Langmuir isotherm, but by the Freundlich
isotherm or the logarithmic isotherm (40).
The kinetics of catalytic reactions in a number of cases also agrees only
qualitatively with the equations obtained on the basis of the model of an
ideal adsorption layer; experimental data often lead to fractional reaction
orders (such as cannot be accounted for by dissociative adsorption).
These facts require a complication of the adsorbed layer model. The
experimental agreement can be improved by discarding at least one of the
initial assumptions, viz., either adsorption sites should be taken different
or a mutual influence of adsorbed particles is to be assumed. In the literature
all surfaces for which the assumptions of the ideal adsorbed layer model do
not hold are often called nonuniform. If surface sites are different, this
is according to Roginskiis terminology, biographical nonuniformity ;
if there is some mutual influence of adsorbed particles, this is the induced
nonuniformity. For the description of kinetics of heterogeneous catalytic
reactions, the model of biographical (i.e., true) nonuniformity was ap-
plied most often. We will discuss this model.
The notion of nonuniformity of catalytic surfaces has been originally
advanced by Langmuir (20)and particularly by Taylor. The physical nature
of nonuniformity is insufficiently clarified. To some extent, it results from
the difference in properties of crystal faces, from dislocations, and other
disturbances of crystal lattice. It is possible that admixtures of some foreign
substances is of greater importance. The particles of admixtures change
adsorption energy on adjacent surface sites. The model of nonuniform
surface probably describes the overall result of the effect of particles of
admixtures on adsorbed particles and of the mutual influence of adsorbed
particles (i.e., to an approximation the model takes into account not only bio-
graphical, but also induced nonuniformity).
There are conceivable CI priori different functions determining the frac-
tion of the total number of surface sites characterized by definite adsorption
energy of a given substance, various combinations of these functions at
simultaneous adsorption of two or more substances and, finally, various
combinations of adsorption energy with kinetic characteristics of surface
sites with respect to adsorption and elementary reactions.
The diversity of possibilities of the general picture of a nonuniform surface
makes it indefinite and hence scarcely suitable for concrete applications.
On the basis of experimental data on heat of adsorption, adsorption equi-
libria, adsorption and desorption kinetics, the kinetics of reactions and
electrode processes, a special model of a nonuniform surface has been
formulated (41) that describes the experiments satisfactorily and without
excessive mathematical complexity.
INDUSTRIAL HETEROGENEOUS CATALYTIC REACTIONS 209
A+Z+B+ZI (89)
the Gibbs activation energy, AG, is a linear function of the standard Gibbs
energy of adsorption of particles I that is denoted as GOo:
AG = .(AGOo) + const; 0 ICI I 1 . (90)
The constant a is called transfer coefficient; often a = 1/2. It can be
easily seen that (90) is equivalent to a linear dependence of AG* on the
standard change of the Gibbs energy at elementary reaction (89), AGO :
AG = a(AGo) + const. (91)
Indeed, the change in AGO corresponding to a passage from one site of the
surface to another is equal to the change in AGOo.
Equation (89) includes, as a particular case, the process of adsorption,
namely when B is absent and I coincides with A. In this case (90) and (91)
are identical.
2. The values of GOoon different sites of the surface lie between a certain
minimum value, (AGao)min,and a certain maximum value :
involving (instead of AGO and AG) the variation of internal energy change
A U (which in an adsorbed layer virtually coincide with enthalpy change
AH) and activation energy E. Then Assumption 1 (i.e., rule of transfer)
takes the form of a linear relationship between E and AU, etc. To avoid
the necessity of making assumptions about entropy, we prefer the formula-
tion in terms of the Gibbs energy.
Let the gas pressure that corresponds to adsorption equilibrium be de-
noted asp. The value o f p for the standard state of a site is denoted as b and
is called desorption pressure of the site (Section IV). Each site of a non-
uniform surface is characterized by a certain b value or by an adsorption
coefficient, a = I/b (for a given temperature). At adsorption equilibrium,
the probability that a site is occupied
0 = p/(p + b) = ap/(l + up). (96)
It is often more convenient to consider not b or a but ( = In b = -In a ;
it was proposed to call this value the desorbtion exponent. According
to (25)
4; = AG,O/RT. (97)
Let us number the sites of a surface of unit area in the sequence of in-
creasing b or ( (i.e., in the sequence of decreasing adsorbtion power). We
shall denote the number of a site as I ; its ratio to the total number of sites
on a section of unit area,
s = l/L, (98)
will be called relative number of the site. The value of s varies from 0 to 1.
Experimentally observed quantities pertaining to the whole surface, such
as the amount of adsorbed substance, heat of adsorption, reaction rate, are
sums of contributions of surface sites or, since the number of sites is extremely
great, the respective integrals. As 5 increases monotonously with s, each of
them can be taken as variable for integration; both methods of calculation
are used. If 4; is chosen as an independent variable, a differential function of
distribution of surface sites with respect to desorption exponents, (p((), is
introduced such that p(()d( is the number of sites with AG:/RT values
within the limits of ( and ( + d5. Let us denote the largest and the smallest
values of 4; as (,, and C1, respectively, and introduce the notation
y = T/O. (99)
Then by virtue of the second assumption the function ~ ( 4 ; )is expressed as
follows :
212 M. I. TEMKIN
e =p lo1
ads. (109)
1 l h p
e = ( I / L ) ~ Y1 loop [uY-'/(1 + u)]du. (132)
As etl = l/al, eco= l/a, and a, % a,, we may neglect eyro compared to
eYc1in (105). Then AIL = yaIYand, hence
t? = (yn/sin yrt)(alp)Y. (134)
Therefore
e = cpy (135)
where
C = (yn/sin yn)aIY. ( 136)
Equation (135) is the well-known Freundlich adsorption isotherm. In a
number of instances this isotherm accurately describes experimental data.
The interpretation of the Freundlich adsorption isotherm as resulting from
exponential nonuniformity of surface is due to Zel'dovich (43).
A kind of nonuniformity of surface with negative y is also conceivable.
If -1 -=
y < 0, then a similar derivation gives for the region of medium
coverages the following adsorption isotherm (44) :
e = 1 - (C/rlYI) (137)
where Iy( is the absolute value of y.
To derive equations of the rates of adsorption and desorption we shall
assume that the rate of migration of adsorbed molecules along the surface
INDUSTRIAL HETEROGENEOUS CATALYTIC REACTIONS 217
is sufficiently high for the equilibrium within the adsorbed layer to exist
even when the layer is not in equilibrium with the gas phase. Then the
probability for each surface site to be occupied is determined by a certain
value p that is one and the same for the whole surface, p being the pressure
in the ideal gas phase that would be in equilibrium with the surface at the
given coverage. This value will be called fugacity of adsorbed substance.
When there is no equilibrium with gas phase, p differs from the actual gas
pressure, which we shall denote as P ; if p < P, the amount of adsorbed
particles increases with time; if p > P, this amount decreases. We shall
consider the rate of change of number of adsorbed particles on unit surface,
r ; it may be positive or negative, as it is the difference between the rates of
adsorption (i.e., condensation),r + ,and desorption (ie., evaporation), r - :
r = r+ - r - . (138)
On a uniform surface
Y+ = K + p ( 1 - 6) = (K+P)/(l + Up) (139)
where K + is the adsorption rate constant. Thus, the contribution of one
+ up),
site of a nonuniform surface to the rate of adsorption is (l/L)(~+p)/(l
and the rate of adsorption on a nonuniform surface is
Since we assume the linear relationship between AG+* and AG,, (91),
we obtain for a nonuniform surface, on the basis of (25) and (31),
K + = K+Oe-a(C-Co)
(141)
where K + is the value of K at ( = to(i.e., on the most strongly adsorbing
sites). Applying (101) for q(l),we obtain from (140) and (141)
r+ = (142)
y+ =-. (144)
218 M. I. TEMKIN
where
n=1-m. (145)
For the region of medium coverages we approximate the integral substitut-
ing integration limits 0 and co for uo and u l . Making use of (133) under the
condition that 0 < n < 1 (and hence, 0 < m < 1) and bearing in mind
that t1 - to= f and sin nn = sin mn, we obtain
n Y K+OP
r + =-*-.
sin mn eyf - 1 (sop)"'
Equation (146) is also valid at y = 0 if, for the factor y/(eyJ- l), its limit
at y = 0 (i.e., l/f) is substituted; additionally, at y = 0, m = a. Therefore,
for evenly nonuniform surface we have
r + = k+Pe-"f' ( 150)
where
k + = (n/sin an)(lc+O/f). (151)
INDUSTRIAL HETEROGENEOUS CATALYTIC REACTIONS 219
Equation (159) contains constants rc-' and n that describe the process of
desorption.
For an evenly nonuniform surface we express p in terms of 0 by means
of (123). Introducing the frequently used symbol
j?=l-Cr, (160)
we have in this case n = B and
r- = (n/sin fin)(.- '/f)ePfe (161)
or
r- = k-esfe
where
k- = (n/sin Bn)(rc-'/f).
The comparison of this equation with (107) shows that the integrand of
(171) can be obtained from the integrand of (107) by substitution of p cp+
for p . Therefore, if (107) leads to some adsorption isotherm of a pure gas A,
0 = F(p), (172)
where F is a function determined by the form of dependence of a on s,
then for the adsorption of A from a mixture with A we have
These results can be generalized naturally for the case of adsorption equi-
librium of more than two gases with proportional adsorption coefficients.
Thus, the passage from an adsorption isotherm of a pure substance to
the corresponding adsorption isotherm of a mixture is very easy, supposing
that the model of a nonuniform surface is applicable and adsorption coeffi-
cients are proportional. If, for instance, adsorption of pure gas A is described
by the Freundlich isotherm (135), then for adsorption of A from mixture
222 M. I. TEMKIN
e=c P
(p + cp')' - y'
(175)
r+ = jo+ 1
Ic+Pds
+
u(p cp')'
(1771
r- =
' K-upds
1 + u p + alp"
if the rate of desorption from a surface containing only particles of A is
r- = H(p) (182)
where H ( p ) is a function of p , then for desorption from the same surface
INDUSTRIAL HETEROGENEOUS CATALYTIC REACTIONS 223
The larger the decrease in the Gibbs energy at a chemical reaction, the
larger the accompanying loss in the ability to perform a useful work, and
hence the less perfect the process is from the viewpoint of thermodynamics.
Therefore, it seems not to be accidental that in commercial large-scale pro-
cesses reactions are utilized that occur at conditions close to equilibrium
[i.e., reactions with small (-AG) values]. Such are the industrial processes
of ammonia synthesis, sulfur dioxide oxidation, hydrogen production by
reactions of methane and carbon monoxide with steam, methanol synthesis,
ethylene hydration, stepwise butane dehydrogenation to butadiene, and a
number of other reactions.
If a system that is in equilibrium with respect to all stages of a complex
reaction is being shifted to states more and more distant from equilibrium
by gradual variation of concentrations of substances participating in the
reaction, then, since the rates of elementary reactions may differ to any
224 M. I. TEMKIN
extent, it is natural to expect that not all the stages will become nonequi-
librium simultaneously. First of all, it will happen to the stage whose ele-
mentary reactions are the slowest. It is not surprising, therefore, that the
rate of single-route reactions at conditions near equilibrium is determined,
as a rule, only by one stage; other stages are at equilibrium. In such cases, as
the numeration of the stages of a cyclic steady-state reaction is arbitrary,
we shall ascribe the number one to the rate-determining stage; equilibrium
stages, if there are several of them, will be united into one common complex
stage, the number of which will be two.
We shall confine ourselves to the consideratiofi of a simple two-stage
mechanism when the surface contains in a significant amount only inter-
mediate particles of one kind, the degrees of coverage by other particles,
if there are any, being small. Such mechanism may be described by the fol-
lowing scheme (48):
I. + Z $ B1 + ZI
A, 1
(188)
2. a2A2+ a2A2+ ZI = b2B2 + b2B2 + Z 1
Here A,, A,, etc. are substances, and a,, etc. are stoichiometric coefficients.
The sign = denotes equilibrium (or quasi-equilibri~m).~
The reaction direction, taken as forward, in particular cases may corre-
spond to either the forward or reverse direction of stage 1 of scheme (1 88).
Therefore, we distinguish the directions of stage 1 as follows. The direction
that results in the occupation of a free site on the surface is called the ad-
sorption direction, and the direction that results in a site becoming un-
occupied is called the desorption direction. The rate of stage 1 in adsorp-
tion direction [i.e., in the forward direction in our record (188)] is denoted
as r, and the rate in desorption direction [i.e., in the reverse direction in
scheme (188)] is denoted as rB. When applied to concrete reactions one of
these values will stand for the forward reaction rate, r , , and the other will
stand for the reverse reaction rate, r - . Transfer coefficients for adsorption
and desorption directions will be denoted as a and p, respectively; so
a+P=l.
Adsorption and desorption processes are particular cases of stage 1;
namely, when substance B, is absent, and I coincides with A , , r, is the rate
of adsorption and r, is the rate of desorption. Since the equilibrium of
stage 2 is maintained as a result of mutually reverse elementary reaction,
the particles I very frequently leave some surface sites and appear on others.
Previously the author had proposed a more expressive sign, (the sign of constellation
Libra or balance), for this purpose. It turned out, however, that its use caused difficulties in
typesetting.
INDUSTRIAL HETEROGENEOUS CATALYTIC REACTIONS ' 225
where k , and k , are constants and m and n, as before, are defined by (143)
+ +
and (164) (i.e., m = CI - y and n = /3 y, so that m n = 1).
+
At equilibrium r,, = r,; since m n = 1 , this gives k A / k , = pB&/PA1.
Hence
kA/kB = KA (191)
where k Ais the equilibrium constant of the reaction of formation of particles
,
I from A in the gas phase :
A, = B, + I. (192)
The equilibrium of stage 2 can be considered as the difference of gas phase
chemical equilibrium
I + a2A2 + a2'A2' = b2B2 + b,'B,' ( 193)
and adsorption equilibrium
I + z = ZI. ( 1 94)
The term "adsorption chemical equilibria" has been suggested for equi-
libria such as those shown by stage 2; they can be observed directly by
experimentation (49-52).
Denoting the equilibrium constant of (193) as K,,we have
whence
226 M. I. TEMKIN
and
rB = (kBIK?) P, ,(Pg2Pg2',/p"A',PA';,
)". ( 197)
Equations (196) and (197) are valid under the condition that 0 I m 4 1 or
under the equivalent condition that 0 I n 5 1.
The results obtained indicate the interpretation of fractional reaction
orders frequently obtained in experimental studies of heterogeneous catalytic
reactions.
If in the course of a reaction, not one, but several adsorption chemical
equilibria exist, it is always possible to write the chemical equations of the
equilibria in such a way that the stoichiometric number of one of these equa-
tions be l and that of other equations be zero. Confining ourselves to two
equilibria, we have the following mechanism instead of (1 88) (48):
1. + Z 3 B, + ZI
A,
'0
1
We suppose that only substances I and J occupy essential parts of the sur-
face; then the form of equations for r, and rB results from the equation for
the simultaneous adsorption of two gases (1 80).
Let us consider now the kinetics of a reaction following the simple two-
stage mechanism (53) on a nonuniform surface with none of the stages of
the reaction being assumed to be at equilibrium (53).Since, in contradistinc-
tion to scheme (188), both stages of scheme (53) are equivalent, we may
always ascribe number one to the stage whose positive direction is of the
adsorption type. Therefore, without loss of the generality of the analysis,
we can distinguish the directions of the elementary reactions in scheme (53)
as forward and reverse. Accordingly, the rate constants of the elementary
reactions of stage 1 will be denoted as K~ and K - ~and those of stage 2 as
K~ and K - ~ For
. <
brevity we introduce A = - t o .Its largest value is - c1
5 0 ="f
We accept the simplifying Assumption 4 of Section IX (i.e., assume that
the transfer coefficient c1 is identical for both stages). Then, from the linear
'
relationship between AG+ and AG,' for each stage and bearing in mind
that rate constants K , and K - ~refer to adsorption directions, and K - ~
and K~ refer to desorption directions, we obtain, in a manner similar to
INDUSTRIAL HETEROGENEOUS CATALYTIC REACTIONS 227
K - 2 = K!Ze-".
Since
J 50
where the distribution function, cp(<), is given by (101) and (105),we obtain,
passing over to the variable 1,
Equations (57) and (59) show that u, as in Section X, is equal to the ratio
of the probabilities for site to be free and to be occupied. It follows from
(199) and (203) that
228 M. I. TEMKIN
where 0 s n I 1.
The comparison of (63) and (217) that answer the same simple mechanism
reveals graphically the difference in the features of kinetics on uniform and
nonuniform surfaces.
3
h
z
i
Lo
J
- 0.2
I I
!!I+,
10-3, IO't, lo-', at. %
0.001 0.01 0.i LO e,,
FIG.2. Modifying of the silver catalyst with selenium. (SC2H,)0x 0.5.
232 M. I. TEMKIN
the parallel course of partial and full oxidation of CzH4 on Ag and a very
fast oxidation of acetaldehyde CH,CHO to C 0 2 and H 2 0 at the condi-
tions of C2H, oxidation reaction. This allows us to consider CH,CHO
as an intermediate product of complete oxidation (however, Twigg himself
supposed that formaldehyde, HCHO, was the intermediate product).
Important features of the reaction mechanism were clarified by Orzechow-
ski and MacCormack (70). These authors simplified the problem by con-
sidering the initial reaction rates for (218) and (219), obtained by extrapola-
tion (i.e., the rates in the absence of reaction products). They arrived at a
conclusion that the reaction is basically composed of irreversible adsorp-
tion of oxygen and the removal of adsorbed oxygen by ethylene with the
formation either ethylene oxide or an intermediate substance, most likely
acetaldehyde, that is rapidly oxidized to C 0 2 and H 2 0 .
The reaction scheme given below is more complex since it takes into ac-
count the retardation of the reaction by reaction products and changes in
selectivity. It is a development of a number of earlier schemes (59-62,71,72),
but still it cannot be regarded as final.
N"' "2' 1v(3'
1. +
ZO2 C2H4 --* ZO C2H40 + 1 0 1
2. ZO, +
C2H4 --C ZO CH3CHO + 0 1 0
+
2'. CH3CHO 5ZO2 2C02 2HZO + 5 2 + 0 1 0
+
-+
3. Z C2H4O ZC2H4O 0 0 1
4.
4'.
5. Z02 +
+
z o2--C ZO2
2 2 0 z zo2
-+ +
C2H40 = Z 0 2 . C 2 H 4 0
i
0
3
3
0
0
1
0
(220)
6. Z02 +
H2O 3 ZO2' H2O 0 0 0
7. zo2 + co2= zo2'co2 0 0 0
8. Z02 +
C2H4 = Z02'C2H4 0 0 0
9. ZC2H,O-+ZO +
C2H4 0 0 1
From (232) and (235) [Z] and [ZO,] can be found. Let us introduce the
following symbols :
L = (k, + 6k2)/2k4 (236)
M = 3k9K3/k4 (237)
and
From (242) and (243) we find the ratio r(l)/r(') that fixes selectivity:
INDUSTRIAL HETEROGENEOUS CATALYTIC REACTIONS 231
= 1 PC2H4
(249)
+ K8PC2H4 + L(pc2H4/po2)
Equations (249) and (250) coincide in their form with equations proposed
by Orzechowski and MacCormack for the initial rates.
The comparison of more complete kinetic equations (242) and (243) with
experimentation is hampered by the instability of activity of silver catalysts
(59). The effects arising from the penetration of oxygen into the subsurface
silver layer (63) and the formation of a polymer film on the surface (70),
an extremely high sensitivity of the catalyst to the traces of compounds of
such elements as S and C1 that may be present in the reactants as impurities,
can be the sources of this instability.
To reduce the number of parameters in the kinetic equations that are to
be determined from experimental data, we used the following considerations.
The values k, , k 2 , and k, that enter into the definition of the constant L,
(236), are of analogous nature; they indicate the fraction of the number of
impacts of gas molecules upon a surface site resulting in the reaction. So the
corresponding preexponential factors should be approximately the same (if
these elementary reactions are adiabatic). Then, since k, , k, , and k, are of
the same order of magnitude, their activation energies should be almost
identical. It follows that L can be considered temperature independent.
Similar considerations are applicable to M . Indeed, according to (237),
-,
M = 3k,k,/k4k . Elementary reactions 9 and - 3 (i.e., the reverse direc-
tion of 3), are of the same type; since k, and k-, are similar in order of
magnitude, we may take the ratio k9/kW3as temperature independent.
Analogously, we arrive at the conclusion of approximate temperature inde-
pendence of k,/k4. Thus M , as well as L, may be considered as temperature
independent.
K , ,Ks, K 6 , Kl ,and K , appearing in the kinetic equations are adsorption
equilibrium constants and their dependence on temperature is determined
by respective heat of adsorption. Since these constants are of the same order
of magnitude, the heat of adsorption should be approximately the same.
Thus the temperature dependence of K , , K , , K s , K l , and K , can be de-
scribed with some common value of the heat of adsorption.
It is easily seen that constants k, and k2 with the rates referred per unit
mass of the catalyst should be proportional to the specific silver surface
INDUSTRIAL HETEROGENEOUS CATALYTIC REACTIONS 239
0.1 0.2
PNO/otm
solution are determined by their partial pressures over the solution, P,, and
P,, , we shall consider reaction rate as a function of PHIand P,, .
The kinetics of the reaction was found to be unusual. The rate of hy-
droxylamine formation, r('), and that of ammonia formation, I-(,),at con-
stant P,, and increasing PN, , has a maximum at the PNovalue that we shall
denote as (PNO)max. This value does not depend on P,, and temperature, and
equals 0.11 atm. At P,, = 2(PN&,axthe formation of NH,OH and NH3
virtually ceases (Fig. 3).
The rate of formation of nitrous oxide by (253), I - @ ) ,features quite a dif-
ferent behavior, viz., it permanently increases with increasing PNo (Fig. 3).
The regularities observed are accounted for by the following scheme of
reaction mechanism :
"1) "2' N(3)
1. Z + H2 = ZH, $ $ 4
2. ZH2 + NO -+ ZH,NO 1 1 1
3. ZHZNO + ZH, 4 2 2 + (H) + H2NOH 1 0 0
4. 2(H) + Z ZH2 f -f f (254)
5. ZHZNO + ZH, + Z + ZOH + NH3 0 1 0
6. ZOH + (H) Z + H 2 0
-+ 0 1 0
7. 2ZH2NO 2(H) + H2O + N2O + 2 2
-+ 0 O f
r(2' =
r5 (258)
it follows that
r2 = r3 + r5. (259)
[The relationship (259) expresses the steady-state condition of the inter-
mediate ZH,NO.] Since
and
= [k2/(k3 + k5)]aNO*
Using a similar method we find, from (258) and (262), that
r(') = k(2)P,,PNo(l - AP,,)
where
/v2'= k(1)(k5/k3).
The equations obtained are approximately correct also if the formation
+
of N,O is not neglected since r(3)< (r(') r(')). The steady-state condition
of stage 7
r ( j ) = $k7[ZH,NOIZ (270)
leads to the equation
+3) = k(3)p2
NO
where
k'3' = {3k7[k2/(k3
1
+ k5)laNO}2.
The value of (PNO)max quoted above corresponds to A = 4.6 atm-'. Experi-
ments gave the following values of other kinetic constants at 25C expressed
in units of mol NO/(cm2 Pt)(hr)(atm)z :k(')= 3.4; k(') = 0.65;
/d3)= 0.75. Solid curves in Fig. 3 were calculated from (268), (269), and
(271) with the use of these constants; the points show the experimental
results. It can be seen that the equations describe the general character of the
kinetic relationships. Experimental results that are not given here confirm
the proportionality of r'') and r(') to PH,.
Scheme (254) does not predict explicitly any dependence of reaction rates
r('), d2), and r'3)on the concentration of H,SO, and product salts. It is
24.4 M. I. TEMKIN
a catalyst (82-84); this was a guarantee that the reaction proceeded in the
kinetic region. The reaction on a commercial type catalyst (i.e., nickel
supported on porous alumina) proceeds in the internal diffusion region
(85). Here we shall discuss only the kinetics of the reaction not complicated
by diffusion.
At 900C the rate of the reaction as measured by the amount of CH,
consumed, r, is satisfactorily described by a simple first-order equation (82) :
r = k,Pc,,. (274)
Here k, is the rate constant of the irreversible first-stage high temperatures.
The stage occurs at impacts of a gas-phase CH, molecule on a catalyst sur-
face that is supposed to be practically free.
In the range of temperatures and pressures where the reaction is sub-
stantially reversible, the kinetics is much more complicated. There is no
grounds to consider chemical changes described by (272) and (273) as inde-
pendent, not interconnected, reactions. Conversely, if processes (272) and
(273) occur on the same surface sites, then free sites will act as intermediates
of both processes. Thus one must use the general approach, treating (272)
and (273) as overall equations of a certain single reaction mechanism. But
if a reaction is described by two overall equations, its mechanism should
include at least two basic routes; hence, the concept of reaction rate in the
forward and reverse directions can be inapplicable in this case. However,
experiments show that water-gas equilibrium (273) is maintained with suffi-
cient accuracy in the course of the reaction. Let us suppose that the number
of basic routes of the reaction is 2; then, as it has been explained in Section
VIII, since one of the routes is at equilibrium, the other route, viz., the route
with (272) as overall equation, can be described in terms of forward, r + , and
reverse, r - , reaction rates. The observed reaction rate is then the difference
of these
r = r+ - r- (275)
and the first problem in the kinetic studies is the determination of the
average stoichiometric number of the reaction, 5. According to (83),
where g(pH,, pH,,) and h(PH,,pHzo) are some, not yet disclosed, functions
Of pH, and PHI,. Equation (277) is valid at PCH4 < 0.2 atm and (278) holds
at pco, < 0.1 atm (total pressure is 1 atm).
It follows from (277) and (278) that r - / r + cc P& since r + a PCH4 and
r - does not depend on PCH4. According to (276), this means that ij = 1.
Equations (277) and (278) also show that r - / r + a P,, since r - a P,, and
r+ is independent of P,,. Again, it follows from this result and (276) that
ij = 1.
For a further verification of this conclusion, we determined equilibrium
constant, K , by combining the results of kinetic measurements in the region
of r + > r - and in the region of r+ < r - , having assumed that J = 1. The
agreement of the obtained value with the value known from thermodynamic
data ( K = 0.0364 atm at 530C) has confirmed that B = 1. This result
means that stoichiometric numbers of all nonequilibrium stages of the
reaction equal unity.
After this preliminary study, we measured the rates of methane reaction
with steam (i.e., r values in the r + > r - region), and the rates of carbon
monoxide hydrogenation [i.e., ( - r ) values in the r+ < r- region] at 470,
530, 600, and 700C (84). In these experiments the PCH4and Pc, values
did not exceed 0.2 and 0.1 atm, respectively ; therefore, (277) and (278) were
applicable. Variations in catalytic activity were taken into account on the
basis of control experiments.
It was found in all experiments that the ratio P ~ ~ , P ~ , / P in ~the~ P ~ , ~
exit gas mixture was near to the equilibrium constant of (273) at the reac-
tion temperature.
The data obtained can be interpreted with the following reaction mech-
anism :
jq) E J ( 2 )
1. +
CH4 Z @ ZCH, H, + 1 0
2. ZCH, +
H2O Ft ZCHOH H, + 1 0
3. ZCHOH Ft ZCO HZ + 1 0
(279)
4. zco Ft z co + 1 0
5. +
Z HzO ZO H, + 0 1
6. ZO + CO = Z + CO, 0 1
Basic route N ( ' ) is a block (i.e., has with basic route N(') no common stages);
therefore, (71) may serve for the derivation of the kinetic equation, with
only the stages of the block included.
The rates of corresponding elementary reactions are expressed as follows :
rl = k1PCH4rZ1 r - l = k-lP~,[ZCH2]
r2 = k2PHzo[ZCH2] 1-, = k-,PHZ[ZCHOH]
r3 = k,[ZCHOH] r _ 3 = k-3PH,[ZCO] (283)
r4 = k4[ZCO] r - 4 = k-,Pc0[Z].
r+ =
+
k l k2k3k4PCH,PH20
(k2k3k4P,20 k-lk3k4PH2+ k- lk-2k4P& + k-lk-2k-3PA2)
. (284)
c1 + KS(PH20/PHz)I
L1 + KS(PH,dPH2)I
1, = k - , k _ 2 / k 2 k J
l3 = k-lk-2k-3/k2k3k4.
Then (284) and (286) are transformed into the following
At this the reaction rate, r, is the amount of CH, reacted per square meter
of the apparent surface of nickel per hour, measured in cubic centimeters
reduced to 0C and 760 mm Hg; R is the gas constant in cal K-' mol-'.
Kinetic equation (290) is in satisfactory agreement with experiments
both at r > 0 and r < 0. Equation (290) can be obtained not only from
mechanism (279). Some authors have developed a carbide theory of catalytic
syntheses of hydrocarbons from CO and H2 (88,89).In terms of this theory,
the following mechanism involving carbon chemisorbed on nickel as an
intermediate should be accepted instead of mechanism (279).
"1'
1. CH4 Z + G ZCH2 + H2 1 0
2. ZCH2 # ZC + H2 1 0
3. ZC + H,O F? ZCO + Hz 1 0
4. zco # z + co 1 0 (292)
5. Z H2O + ZO + H2 0 1
6. ZO CO + = Z + C02 0 1
Equations (287)are again used for the definition of 11, 12, and l3 in this equa-
tion via rate constants of elementary reactions of scheme (292). At l , = 0,
(293) becomes (290). This corresponds to stage 2 of scheme (292), being at
equilibrium. Thus the reaction kinetics does not provide a possibility for
giving preference to the Eidus-Zelinskii theory or the carbide theory.
The notions of the reaction mechanism presented here are in better agree-
ment with the results of kinetic measurements if the simplifying assumption
250 M. 1. TEMKIN
of the surface being uniform is not made and instead the surface is assumed
to be evenly nonuniform [see Chap. 10 of the contribution by Snagovskii
and Ostrovskii (2)].
N2 + 3H2 = 2NH3
INDUSTRIAL HETEROGENEOUS CATALYTIC REACTIONS 25 1
where
and
PkH3/PN2Pi2 = (306)
252 M. I. TEMKIN
in accordance with the mass action law for equilibrium. Since k - and k ,
are bound by (303) and K values for different temperatures are well known,
only two constants in (305) are to be determined for a given catalyst from
experiments, viz., m and one of the values, k , or k - ; then other constants
can be calculated by means of (303) and (304).
In the original derivation of (305), it was supposed (40) that the nitrogen
adsorption equilibrium on the catalyst follows the logarithmic isotherms
(i.e., that the surface is evenly nonuniform). In this case y = 0 and, according
to (143) and (164), m = a, n = /?.Experiments with iron catalyst promoted
with A1,03 and KzOgave m = 0.5. This was interpreted as a = 0.5 (93).
It was later demonstrated that if the reaction mechanism corresponds to
scheme (295) and the linear relation between standard Gibbs energy of
adsorption and Gibbs activation energy of adsorption is obeyed [see (91)],
then the kinetic (305) corresponds in general to the exponential nonuni-
formity of the surface with even nonuniformity included as a particular
case (44). In the general case the exponent m is not equal to transfer coeffi-
cient a, but is connected with it according to (143).
A study of adsorption-chemical equilibrium
ZNZ + 3Hz = Z i-
2NH3, (307)
which corresponds to stage 2 of mechanism (295), done with iron catalyst
promoted with A1,0, and K,O (49) showed that the logarithmic isotherm
was followed. Thus the original approach was correct as applied to this
catalyst. In ammonia synthesis on cobalt (95, 96) and nickel (96) catalysts,
m equals 0.2 and 0.3, respectively. A study of equilibrium (307) showed that
on cobalt and nickel catalysts the Freundlich isotherm with y = 0.3 for
cobalt and 0.2 for nickel was valid. Thus, in both cases a = m + y = 0.5 as
for iron (94). This result is in agreement with the natural assumption that
the differences in m values for catalysts should result from differences in
surface nonuniformity, but not in the transfer coefficienta.
We note that the very possibility of observing the equilibrium (307) sup-
ports the notion that the reaction rate is determined by stage 1 of mechanism
(295). At temperatures somewhat lower than that of ammonia synthesis,
the reaction rate of this stage becomes negligible, but the equilibrium of
stage 2 still is established sufficiently rapidly.
The concepts underlying the derivation of (305) were also confirmed in the
extensive study by Scholten (97). This author used a balance of special design
that permitted following the weight changes of the ammonia synthesis
catalyst in the course of the reaction and in the process of nitrogen adsorp-
This proof has been quoted by the author in his paper for the 5th International Congress on
Catalysis. Unfortunately, during the preparation of the proceedings of the Congress, the
corresponding pages were lost and are absent from the published text (94).
INDUSTRIAL HETEROGENEOUS CATALYTIC REACTIONS 253
In a number of works the dependence of the type k a T-' exp ( - A / R T ) was used. A and
E- do not differ greatly. E - = A - RT, where T, is the average temperature (101).
254 M. I. TEMKIN
fractions of NH, in the gas mixture at the reactor inlet and outlet, respect-
ively, and
~ ( -i z p 5 d z
J(z) =
(1 + Z)Z[L2(1 - z)4 - Z Z ] .
(319)
J ( z ) x -i(1 - z ) , . ~In
At z values small as compared to z,, (322) differs but little from the following:
J(z) x +(Z/L)2. (323)
Originally (93),because of an inaccuracy, an equation was obtained (for
z1 = 0) where the denominator of the integrand corresponding to that
+ +
given in (319) contained not (1 z), but (1 z). This inaccuracy was de-
tected by Emmett and Kummer (113), but these authors did not perform
the calculations rigorously either and obtained the factor (1 + z),, which
was used in subsequznt articles (107,114,115) until the correct value was
obtained; i.e., (1 + z ) ~(98). These differences are minor since z is small
compared to unity.
At high pressures the effects that are not taken into account in (305) are
manifested, viz. the deviations from the laws of ideal gases and the effect of
pressure on the reaction rate depending on the volume change at activation.
The equation that is strictly applicable at high pressure (114) contains, in
contradistinction to (305), not partial pressures, but fugacities of gaseous
participants of the reaction. The right-hand side of the equation includes,
moreover, a factor exp[ -( Vg - a V,,,)P/RT] where V, is the partial molar
volume of the activated complex of nitrogen adsorption, VZN2is the partial
molar volume of adsorbed nitrogen, P is total pressure (the equation was
derived for m = a). When k value is calculated from the simple (305) its
INDUSTRIAL HETEROGENEOUS CATALYTIC REACTIONS 257
where k is a constant.
The second possibility is that at small PNHsthe equilibrium of stage 2 is
not established during the reaction. Therefore, the reaction rate is deter-
mined not only by the rate of the adsorption of nitrogen, but also by the
rate of hydrogenation of adsorbed nitrogen. In this case the reaction pro-
ceeds in the region of medium surface coverages with nitrogen, but the
degree of covering corresponds not to the equilibrium but to a steady state
with equality of the rates of adsorption and hydrogenation of nitrogen. Then
the reaction rate should depend not only on PN,, but also on PH2.
An experimental study of kinetics of ammonia synthesis on iron ( l o ] ) ,
cobalt, and nickel (96) catalysts, at ammonia concentrations much lower
than that at equilibrium, showed that at pressures of the order of 1 atm the
second of these possibilities is realized. When far from equilibrium, the
The first possibility can become realistic at high pressures since at high partial pressures of
hydrogen the rate of hydrogenation is large.
INDUSTRIAL HETEROGENEOUS CATALYTIC REACTIONS 259
reaction rate on any of the three metals is described by equations of the fol-
lowing form :
r z k'P;,P',;"', (325)
where n' is a constant satisfying the inequalities 0 < n' < 1, instead of (324)
that can actually be formally considered as a particular case of (325) at
n' = 1. Equation (325) results from (217) if A, is identified with N, and A,
is identified with H, . This means that at small concentrations of NH, the
reaction rate is determined by two slow irreversible stages, as in a two-stage
scheme (53); they are followed by equilibrium stages that may be united
into one complex stage:
1. Z + N2 + ZN, 1
2a. ZN, + H, -P ZN,H, 1 (326)
2b. ZN2H2 + 2H2 = Z + 2NH3 1
N2 + 3H2 = 2NH3
Stages 2a and 2b together comprise stage 2 of mechanism (295). To have
the change in the rate of stage 2a at passing from one surface site to another
dependent only on the energy of adsorption of N, and independent of the
energy of adsorption of the diimide radical N,H,, one must accept that the
latter energy is the same on all sites. It seems that in general the smaller the
energy of adsorption, the smaller its change at passing from one site to an-
other. The variations in energy of adsorption can be supposed equal only for
substances that are adsorbed with approximately equal strengths.
From this interpretation of (325), it follows that m' = m where m' = 1 - n'
and m is the exponent in (305) found for the same catalyst from the reaction
rate in the region where (305) applies.
This conclusion was verified by studies of kinetics on each of the above-
mentioned metals of the iron group at very low and near to equilibrium
concentrations of ammonia. It was completely confirmed that for an iron
catalyst m = 0.5 and m' = 0.5 (101), for cobalt m = 0.2 and m' = 0.2 (96),
for nickel m = 0.3 and m' = 0.3 (96).
Schemes (295) and (326) can be united into one general scheme of the
mechanism. It is sufficient to regard stages 1 and 2a as reversible:
1. Z + N, ZN, 1
2a. ZN, +
Hz # ZN2Hz
2b. ZNzH2 + 2H2 = Z + 2NH3
1
1
(327)
N, + 3H, = 2NH3
260 M. I. TEMKIN
The constant k, has the same meaning as in Section XV; i.e., it is related
to k+ by (301); the constant I is determined by the equation
1 = u-o/u;, (33 1)
so that the term l / P H 2 is the ratio of rates of desorption and hydrogenation
of adsorbed nitrogen.
We note that although, according to scheme (327), the reaction includes
two slow stages, 1 and 2a, so that the concept of the rate-determining stage
is inapplicable to this case, (330) still corresponds to
r - / r + = (1/K)(piH3/pN2pi2)-
In compliance with the treatment given in Section VIII, this is explained
by the stoichiometric numbers of both slow stages being equal to 1 so that
the average stoichiometric number 5 = 1.
Let us make, instead of a supposition used in deriving (305) that stage 1
is rate-determining, a more general assumption that almost all adsorbed
nitrogen molecules react with hydrogen and only a small portion of these
molecules are desorbed. This means that
l/PH2 4 1. (332)
INDUSTRIAL HETEROGENEOUS CATALYTIC REACTIONS 26 1
1. 2 + NZeZN2 1
2. ZNZ + 3H2 =2NH, +Z 1 (336)
3. ZO t H, = Z t H,O 0
We need to find the rate of adsorption of nitrogen by the surface that, apart
from nitrogen, contains oxygen in comparable amounts. We shall use
Assumption 3 formulated in Section IX; i.e., we shall assume that the change
in AG,' at passing from one surface site to another is the same for N2 and
0. Then we may apply (180) substituting for P the pressure of nitrogen,
P,, , and for p and p' the fugacities of adsorbed nitrogen, pN2,and oxygen,
p o , as determined by the equilibria of stages 2 and 3; i.e.,
PN2 = (1/Q(piH3/pAz) (337)
and
Po = (1/K0)(pH20/p"2) (338)
where KO is the equilibrium constant of the reaction
0 + HZ = H 2 0 . (339)
Thus we find that
The reaction
CO + H 2 0 = CO, + H, (342)
called carbon monoxide conversion or water-gas shift reaction is used on
a large scale for production of hydrogen in ammonia plants. In this pro-
cess carbon monoxide obtained by natural gas reforming is used (Section
XIV). The process comprises two steps. The main amount of CO is con-
verted at 400-500C on a so-called high-temperature catalyst. But at these
temperatures, as follows from the conditions of equilibrium of reaction
(342), a sufficiently complete CO conversion cannot be achieved. A supple-
mentary conversion is effected at 200-250C on a so-called low-temperature
catalyst.
The high-temperature catalyst is prepared in the form of ferric oxide,
Fe,O3, to which some chromium oxide, Cr,03, is added to prevent the
thermal sintering of the catalyst in operation. Prior to the reaction ferric
oxide is reduced to Fe304 with hydrogen or carbon monoxide (in the pres-
ence of steam in excess). When reaction (342) occurs on the high-temperature
catalyst, the catalyst contains iron in the form of magnetite, Fe,O,, as an
x-ray phase analysis showed (124).
Our first study of reaction (342) kinetics (124) was done in a flow system
under atmospheric pressure at 400, 450, and 500C on a Fe,O, catalyst
without any additions and also on a mixed oxide catalyst of the nitrogen
type, the active component of which is Fe,O, .
In this work the following reaction mechanism was proposed :
1. Z+H,O#ZO+ H2 1
2. zo + co P Z + co, 1 (343)
CO + H 2 0 = C02 + H,
264 M. I. TEMKIN
was 1.37 g/cm3, the size of catalyst grains in the experiments was from
0.5 to 1 mm. The determination of the effective diffusion coefficient made
it possible to ascertain that at this size of the grains the reaction occurred
in the kinetic region. The measurements were done in a flow circulation
system under atmospheric pressure and at 390,420,450, and 483C. It was
assumed in compliance with scheme (343) that the average stoichiometric
number, 7, equals unity, and on the basis of (85) and the observed reaction
rate, r, the forward reaction rate, r+ , was calculated from the equation
(347)
r= k(PH20PC0 - K- 1pC02pH2)
(349)
APH20 + pC02
Such an equation was proposed earlier than our work (129, but later a
more complex one was substituted (128). Later other authors advanced
an equation practically equivalent to (349) (Z29).
A comparison between scheme (343) with a general two-stage scheme
(53) shows the following correspondence :
Scheme(53) A, B1 A2 B, I
Scheme(343) H20 H2 CO CO, 0
Experimental results of this work (124) were found to agree with (352) at
n = 0.5. Since according to the data on adsorption-chemical equilibrium
(3441, the logarithmic isotherm is valid; i.e., y = 0, (158) gives n = p. There-
fore, as usual, a = p = 1/2.
The difference between the results obtained in the first (124) and the
subsequent (126) works consists not only in the region of surface coverages
to which the kinetic equation corresponds, but also in the order of magnitude
of the constant A . It has been explained in Section XI that A is the ratio of
rate constants of adsorption directions of the first and the second stages.
According to (350), A -= 1 in the temperature range of 400-500C; whereas
for the deduction of (352) it must be assumed that A % 1.
The source of this discrepancy is unknown to us. Equation (349) is, un-
doubtedly, adequate for the description of the reaction kinetics on an iron-
chromium oxide catalyst. The fact that in one of the works (124) magnetite
without the addition of chromium oxide served as a catalyst can hardly be
of consequence since a study of adsorption-chemical equilibrium (344) on
an iron-chromium oxide catalyst (7% Cr,O,) (52) led to the value of the
average energy of liberation of a surface oxygen atom that practically coin-
cides with that found earlier (50) for an iron oxide catalyst with no chromium
oxide. It may be suspected that in the first work (124) the catalyst was poi-
soned with sulfur of H,S that possibly was contained in unpurified COz
INDUSTRIAL HETEROGENEOUS CATALYTIC REACTIONS 267
The reaction
HDO + H, = HD + H20 (356)
or the reverse finds its application in the production of heavy water.
The commercial catalyst is nickel on a support, but reaction (356) can
also occur on surfaces of a number of other catalysts. Its kinetics was studied
268 M. I. TEMKIN
on Ni, Co, Pd, Cu, Ag, Au, Pt, and Fe,04 (131, 132). Experiments were
done in a flow (131)and a circulation-flow (132) systems under atmospheric
pressure. Hydrogen was saturated at various temperatures with water vapor
containing from 2.2 to 4.5 at.% D. Depending on the activity of a catalyst,
the temperature range of experiments was chosen within the limits of 200-
500C. Measurements were conducted in the kinetic region.
In the theoretical discussion of the kinetics we shall suppose that contents
of D in water vapor and hydrogen are small (as it was in our experiments).
Then the gas mixture contains practically no D 2 0 and D2molecules and
only reaction (356) occurs.
The results of kinetic studies conform with the notion of a reaction pro-
ceeding on a evenly or exponentially nonuniform surface in the region of
medium coverages as described by the following mechanism :
1. Z + H D O # Z O + H D 1
2. Z O + H, e Z +HzO 1
(357)
HDO + Hz = H D + H z 0
Scheme(l88) A, B1 uz A, b, B, I
Scheme(357) HDO HD 1 Hz 1 HzO 0
Catalyst Ni Co Pd Cu Fe,O, Ag
m 0.5 0.5 0.3 0.3 1.0 0.8
pressure, P,with time, t. The following formula was used in the calculations :
co + CI, = COCI,
272 M. I. TEMKIN
Scheme(53) A, A, B, Bz I
Scheme(371) CO C1, - co co
Since B, is absent, I coincides with A,.
At first sight, scheme (371) does not agree with the results of our adsorp-
tion experiments; these experiments showed that activated charcoal does
not chemisorb CO at 100C. It should, however, be taken into consideration
that the surface of charcoal subjected to activation or even simply after
storage in contact with air is covered with chemisorbed oxygen. The studies
of the reactions of carbon with C 0 2 and steam (see Section XX) have demon-
strated that oxygen chemisorbed on carbon is indistinguishable from chemi-
sorbed carbon monoxide. So it may be reckoned that activated charcoal is
already covered with carbon monoxide before the contact with this gas.
Desorption of CO from the surface of such charcoal occurs only at tem-
peratures much higher than those employed in phosgene catalytic synthesis;
therefore, stage 1 of scheme (371) is irreversible under the usual conditions
of the reaction. Kinetic measurements show that the reaction is retarded
by its product, phosgene. To account for this in terms of scheme (371),
stage 2 must be considered as reversible. In such a case (214) is directly
applicable. After the substitution specified above we obtain
r = k P c o [ ~ c , , / ( A P c+
o ~coc~,)lm. (372)
Experimental data gave m = 1/4 at the three temperatures (i.e., 70, 100, and
130C).
According to (99) and (143),
m = u - (T/O) (373)
where a and 0 are temperature-independent; therefore, if m # u, m depends
on T. However, this dependence is hardly noticeable. Let us, for instance,
accept for the transfer coefficient a the most usual value, 0.5, and assume that
m = 0.25 at 100C. Then we find that 0 = 1490K; hence, at 70"C, m = 0.27
and at 130"C, m = 0.23. The deviation of m from the average value 0.25,
by k0.02 is difficult to detect.
Taking m = 0.25, we found numerical values of constants in (372) from
experimental data for activated charcoal Bayer. These constants are de-
scribed by the equations
logA = -1900/T + 3.40 (374)
log k = - 1875/T + 3.80. (375)
INDUSTRIAL HETEROGENEOUS CATALYTIC REACTIONS 273
Values of k from (375) give the phosgene formation rate, in moles per second
per gram (200 m2) of charcoal at pressures expressed in atmospheres.
According to (379, the apparent activation energy, E = 8.6 kcal/mol.
Equation (372) with rn = 0.25 and A found from (374) agrees well with
experiments not only for the charcoal Bayer, but also for the Soviet activated
charcoal AR-3.
In the temperature range covered by the experiments by Potter and Baron
(139)one may have A = 0 as follows from (374). This means that stage 2 of
scheme (37 1) is virtually at equilibrium under these conditions. Then,
instead of (372), we have the following equation corresponding to (21 5) :
r = kPc,(Pc,,/Pc,,,,)". (376)
Experimental results of the referenced work agree with (376) ;namely, points
fall into straight lines being plotted in the log(r/Pco) vs. log(PcI2/Pc~~,)
coordinates. Slopes of the lines for most of experimental series give m values
near to 1/4.
substances are added. Here we will consider only the reactions of pure carbon
with carbon dioxide and steam. The kinetics of these reactions is closely
related to the kinetics of some of the reactions discussed above.
As a result of their investigations of reaction (377), Frank-Kamenetskii
and Semechkova (142, 143) advanced a mechanism that can be presented
as follows :
1. z c + c o 2 # z c o +co 1
2. zco # z + co 1 (379)
c + co, = 2CO
Scheme(53) A, B, A, B, I
Scheme(379) C02 CO - co co
In deriving a kinetic equation for mechanism (379), Frank-Kamenetskii
assumed the surface to be uniform. The kinetic equation answering to this
assumption is obtained immediately from (61):
where I,, I,, and I, are constants. An equation of the form of (383) was
proposed after the works by Frank-Kamenetskii also by Gadsby et al.
( 1 4 4 , who derived it from notions about the mechanism of the reaction
somewhat different from those of Frank-Kamenetskii, but still assuming
the surface to be uniform.
Equation (383) is in qualitative agreement with the experiment. Reaction
(377) is indeed retarded by its product, carbon monoxide, even when the
concentration of the product is smaller than equilibrium concentration to
such an extent that the reverse reaction is virtually absent. This was verified
also by our experiments described below. According to the meaning of
(381), the retardation of the reaction by its product results from the reversi-
bility of stage 1 ; (382) implies that the reaction is retarded by adsorption of
the product. The correct choice can be made by the comparison of the reac-
tion rate and the rate of exchange of Oi8 between CO, and CO, since of the
two reaction stages in scheme (379), only the stage 1 (when it proceeds for-
ward and backward) results in this isotopic exchange.
Our investigation of the kinetics of reaction (377) (145) was done on a
practically ash-free carbon sample. The carbon was obtained by kilning
Bakelite prepared from chemically pure phenol and formaldehyde with
subsequent activation with carbon dioxide. Specific surface area of the car-
bon measured by adsorption of methylene blue was 2.2 mz/g for the initial
sample and 3.7 m2/g for the sample that reacted with COz for 155 hours.
Surface area measurements by low-temperature adsorption of nitrogen
showed a much greater increase in specific surface with the burning off of
carbon; namely, from 24 m2/g for fresh carbon to 300 m2/g for carbon
after 155 hours of reaction with CO, ,presumably, as a result of the opening
of the orifices of micropores. Kinetic experiments demonstrated that the
rate of the reaction (377) is proportional to the specific surface measured
by adsorption of methylene blue. This means that the reaction occurs mainly
on the surface of wide pores accessible to the molecules of methylene blue
and that the surface of micropores takes virtually no part in the reaction.
The experiments were conducted in the temperature range of 700-780C.
The degree of CO, conversion in these experiments did not exceed 3%; CO
concentration at the outlet comprised only 5-6% of its equilibrium content
under the conditions of the experiment. Therefore, in discussing the results,
the reaction could be considered irreversible.
276 M. 1. TEMKIN
The size of carbon grains in the kinetic experiments was 1-2 mm. Pre-
liminary tests with grains of different sizes had shown that this size range
ensured the reaction course in the kinetic region.
The same carbon that was used for reaction (377) was employed in the
measurements of the rates of the reactions
COO'S + co = coo + C0'8 (384)
and
coo + CO'8 = coo'8+ co (385)
in the temperature range of 550-570C. The concentrations of carbon mon-
oxide and carbon dioxide corresponded in this case to equilibrium with
respect to reaction (377). The measurements were conducted in a closed
circulation system.
The rate of isotopic exchange is proportional to the difference of contents
of labeled atoms in the exchanging molecules. The factor of proportionality
was proposed (145) to be named the "total rate of exchange" since it is equal
to the rate of the continuous exchange of atoms that cannot be detected
unless the atoms are labeled. The rate of isotopic exchange would be equal
to the total rate of exchange if all atoms of an element in one of the species
were labeled and those in the other species were normal.
Total rates of oxygen exchange between CO, and CO calculated from the
rates of reactions (384) and (385) were compared to the forward rate of
reaction (377) in the equilibrium state found by extrapolation of measured
rates by means of an empirical kinetic'equation. It turned out that at 750C
the total rate of exchange exceeds the rate of reaction by a factor of 50 and
at 700C more than of 100. The difference in rates is so large that it cannot
depend on the inexactness of measurement of the rates of isotopic exchange
or on the uncertainty associated with the extrapolation of the reaction rate
to equilibrium. It follows that stage 1 of scheme (379) is much faster than
stage 2. Therefore, if one of the reaction stages becomes irreversible as a
result of going away from equilibrium, it is stage 2 and not stage 1. This
means that (381), but not (382), is qualitatively correct.
The comparison of our measurements of the rate of reaction (377) with
(383) showed that this equation is not obeyed quantitatively. The disagree-
ment of (383) with experimentation already noted in preceding works can
be explained by the nonuniformity of the surface not being taken into
account. To describe the rate on a nonuniform surface under the conditions
of practical irreversibility of the reaction, (214) can be applied. It should,
however, be remembered that this equation corresponds to the mechanism
with the irreversible first stage, and in our case it is the second stage that is
irreversible. Therefore, in order to make use of (214), the numbering of
INDUSTRIAL HETEROGENEOUS CATALYTIC REACTIONS 277
where k = [ k ] A m .
Equation (387) at rn = 0.5 agrees quantitatively with experimentation
(145). Constants in (387) are described as functions of temperature by the
equations
k = 3.25 x 105e-48*000/RT (388)
A = 5.3 10-11eS8.S00/RT
(389)
Here the rate of reaction, r, is expressed in units (mole CO,)/mZ hr (specific
surface area of carbon being measured by adsorption of methylene blue);
pressures are in atmospheres.
A number of authors (246-150) who studied the reaction (378) concluded
that the kinetics of reaction (378) follows the equation
r(l, = 'lPH20
1 + i2PH2+ i3PHzO (390)
where r(') is the rate of entering of carbon into the reaction; i , , i, , and i,
are constants. This equation is analogous to (383). As in (383), it corresponds
to the assumption that the surface is uniform.
It is natural to assume on the basis of mechanism (379) of the reaction of
carbon with carbon dioxide and the mechanism of carbon monoxide con-
version, (343), that the reaction of carbon with steam occurs as follows:
Arc') "2'
1. ZC + H 2 0 + H2
P ZCO 1 1
2. zco ?3z + co 1. 0 (391)
3. z c o + c o * c o 2 +zc 0 1
MI); C + H 2 0 = CO + H2
N'"; CO + H 2 0 = C 0 2 + H,
Stage 1 of this mechanism is analogous to stage 1 of mechanism (379),
stage 2 of both mechanisms are identical, and stage 3 coincides with stage
1 of mechanism (379) written in the reverse direction. On the other hand,
stages 1 and 3 conform with the mechanism of carbon monoxide conversion
(343). Such a mechanism of reaction (378) was proposed by Key (15Z).
278 M. I. TEMKIN
The reaction is described by two basic routes; in (391) they are chosen
so that carbon enters the reaction only in route Mi), and route N)results
in the conversion of a part of CO formed in route N()into CO, . With such
a choice of the basis of routes, r(l), the rate of the reaction along route N()is
the rate of carbon gasification; i.e., corresponds to symbol r(l) in (390).
Our study of the kinetics of the reaction of carbon with steam (152) was
conducted by the circulation flow method under atmospheric pressure in
the temperature range of 900- 1000C. Dilution with helium was employed
to vary the sum of partial pressures of the reaction participants. The experi-
ments were carried out with nonporous graphite of high purity (the content
of admixtures did not exceed lo-%). The roughness factor of graphite was
found to be 2-2.5 (from electrochemical measurements). Equation (390)
proved not to be obeyed quantitatively; the results of the variation of PH2
in a broad range by addition of H, to the gas mixture at the inlet do not form
a straight line in the plot l/r( vs. P,, .
Experimental data answer the equation
r( = k(1)(PH20/PH2)m (392)
with rn = 0.5.
In order to obtain (392) from the scheme of mechanism (391), the surface
of carbon should be regarded as nonuniform, as in the derivation of (387)
for reaction (377). Besides that, it should I& assumed that stage 1 of mech-
anism (391) is at equilibrium (ie., occurs much faster than stages 2 and 3).
In this case stage 3 virtually does not change the surface coverage with
oxygen, the coverage being determined by the equilibrium of stage 1. Since,
on the other hand, carbon does not participate in stage 3, this stage may be
ignored in determining r(. Thus, we have a simple two-stage reaction con-.
sisting of stages 1 and 2, stage 1 being at equilibrium. In scheme (188) stage
2 is at equilibrium. Hence, to apply the kinetic equation of this scheme, the
numbering of stages should be altered. Then we obtain (392) from (196).
According to the results of experiments at 950, 1000, 1050, and 1110C
k(1) = 4.2 1014e-76.800/RT (393)
Reaction rate is expressed here in units cm3 (CO + CO,)NTP/hr m2.
The rate of formation of C 0 2 , r), is found in a similar manner. Since
stage 1 is at equilibrium, stage 2 does not change the surface coverage and
it is sufficient to take into account only stages 1 and 3 in determining r(2).
Thus we obtain mechanism (343), only stage 2 of this mechanism is now
designated as stage 3. Since stage 1 is at equilibrium, we have the mechanism
of type (188), stages 3 and 1 of mechanism (391) corresponding to stages 1
INDUSTRIAL HETEROGENEOUS CATALYTIC REACTIONS 279
where k(') is a constant and K")is the equilibrium constant of route N").
It follows from (392) and (394) that (153)
P)/r(') = k(z)/k(l)[l- (I/@ z, )(pco2pH2/pcopH20)I. (395)
Equation (395) is confirmed by experimental data (154).
Constants k(') and k(') are related to constants k and A in (386); it can be
shown that A = k(2)/k(') and [k]= k(')[fi2)]-". Therefore the measurements
of the rates of formation of CO and COz in steam gasification of carbon
give the possibility of calculating theoretically the rate of gasification of
the same carbon with COz . The comparison of the results of such a calcula-
tion with the direct measurement of the rate of reaction (377) on pyrographite
at 1050C demonstrated a good agreement (154). It shows that the homo-
geneous reaction
CO + H20= COz + Hz (396)
did not play any essential role under the conditions of these experiments.
It can be explained by the homogeneous reaction (396) being a chain one
with large chain length (155). On the surface of carbon the chains terminate
and reaction (396) is strongly retarded.
under atmospheric pressure (150, A = 4.2 for cylindrical pellets with the
diameter of base, 1, equal to the height, and A = 2.5 for spherical pellets
with the diameter 1. These A values refer to the downward stream of the gas
mixture usually employed in the reactors with the nonplatinum catalyst.
Taking a co/cl ratio such that there would be practically no diffusion of
ammonia, e.g., co/cl = lo4, we obtain from (400) the required thickness of
the bed of pellets.
Let us consider now the effect on the process of passage from atmospheric
pressure to a higher pressure P, with load, w ,and the size of catalyst pellets,
I, unchanged. The Sherwood number, Sh = l / h D , is determined by the
Reynolds, Re = ul/v, and the Schmidt, Sc = v/D, numbers. The value of
w being given, v, D, and u values are inversely proportional to pressure, P.
Therefore, 6, is independent of P at constant w and 1. Since u and D are
inversely proportional to P, the increase in the time of contact of the gas
mixture with the catalyst by a factor of P as a result of passage from 1 atm
to P atm is compensated by the P times diminition of the diffusion coefficient,
and the fraction of ammonia reacted remains unchanged. We conclude that
(398) and (400) may also be used without any modification in the case of
reaction under pressures differing from atmospheric.
In ammonia oxidation, under elevated pressures higher loads are used
than under atmospheric pressure, possibly because there is no difficulty
in overcoming the resistance to the flow. For instance, at 7 atm the load is
5000 m3NH, (NTP)/hr m2 and the number of gauzes is 16. Although the
load is 25 times higher than the above-mentioned load for the atmospheric
pressure reactors, the number of gauzes is only 5.3 times larger. Therefore,
the productivity of gauzes in the reactors under elevated pressure is much
higher. It would be a mistake to think that this increase in productivity re-
sults from the increase in pressure; it results from the increase of load making
the diffusion layer thinner.
The possibility of such increase in productivity is restricted by the value
of limiting load, but for platinum gauzes this value is very high. Experiments
with gauzes characterized above (wire thickness 0.09 mm) done without
preheating of the ammonia-air mixture under atmospheric pressure and
at 10% NH, gave a limiting load about 30000 1 mixture (NTP)/hrcm2
(157). The limiting loads for nonplatinum catalysts are smaller than that for
platinum. The largest value was found for Co,O, (158). Pertinent data will
be given and discussed below.
To observe ammonia oxidation on platinum in the kinetic region, the reac-
tion must be carried out at low pressures since the decrease in pressure in-
creases the diffusion coefficient and slows down the reaction, both factors
favoring the transition to the kinetic region.
We studied the reaction under pressures about mm Hg in a static
INDUSTRIAL HETEROGENEOUS CATALYTIC REACTIONS 285
REFZRENCE.9
77. Savodnik, N. V., Kulkova, N. V., Dokholov, D. M., Lopatin, V. L., and Temkin, M. I.,
Kinet. Katal. 13, 1520 (1972).
78. Brian, P. L. T., Hales, H. B., and Sherwood, T. K., AIChE J. 15, 727 (1969).
79. Horiuti, J., and Toya, T., Solid State Surf Sci. 1 (1969).
80. Shlygin, A. I., and Frumkin, A. N., Acta Physicochim. URSS 3,791 (1935); 4,911 (1936).
81. Temkin, M. I., Vopr. Khim. Kinet., Katal. Reakt. Sposobn., Dokl. Vses. Soveshch., 1955
p. 484 (1955).
82. Bodrov, I. M., Apelbaum, L. O., and Temkin, M. I., Kinet. Katal. 5, 696 (1964).
83. Khomenko, A. A,, Apelbaum, L. O., Shub, F. S., andTemkin, M. I., Kinet. Katal. 11,1480
(1970).
84. Khomenko, A. A., Apelbaum, L. O., Shub, F. S., Snagovskii, Yu. S., and Temkin, M. I.,
Kinet. Katal. 12,423 (1971); Temkin, M. I., Shub, F. S., Khomenko, A. A., and Apelbaum,
L. O., Nauchn. O m . Katal. Konvers. Uglevodorodov, 1977. p. 3 (1977).
85. Bodrov, I. M., Apelbaum, L. O., and Temkin, M. I., Kinet. Katal. 8,821 (1967).
86. Eidus, Ya. T., and Zelinskii, N. D., Izu. Akad. Nauk SSSR, Ser. Khim p. 289 (1940).
87. Eidus, Ya. T., Izv. Akad. Nauk SSSR, Ser. Khim. p 65 (1943).
88. Fisher, F., and Tropsch, H., Brennst.-Chem. 7,97 (1926).
89. Craxford, S. R., and Rideal, E. K., J . Chem. Sor. p. 1604 (1939).
90. Emmett, P. H., ed., Catalysis, 3, pp. 171 and 265. New York, 1955.
91. Nielsen, A,, An Investigation on Promoted Iron Catalysts for the Synthesis of Ammonia,
3rd ed. Giellerups, Copenhagen, 1968.
92. Malina, I. K., Razvitie issledovanii v.oblasti sinteza ammiaka. Nauka, Moscow, 1973.
93. Temkin, M., and Pyzhev, V., Zh. Fir. Khim. 13,851 (1939); Acta Physicochim. URSS 12,
327 (1940).
94. Temkin, M. I., in Catalysis, Proc. Int. Congr. 5th, 1972, (J. W. Hightower, ed.), Vol. 1,
p. F-I 13. North-Holland Publ., Amsterdam, 1973.
95. Morozov, N. M., Lukyanova, L. I., and Temkin, M. I., Kinet. Katal. 6, 82 (1965).
96. Morozov, N. M., Shapatina, E. N., Lukyanova, L. I., and Temkin, M. I., Kinet. Katal. 7,
688 (1966).
97. Scholten, J. J. F., Chemosorption of Nitrogen on Iron Catalists in Connection with
Ammonia Synthesis. Croniger, Amsterdam, 1959.
98. Temkin, M. I., Khim. Nauka Promst. 2, 219 (1957).
99. Shishkova, V. V., Sidorov, I. P., and Temkin, M. I., Tr. GIAP 7, 62 (1957).
100. Sokolova, D. F., Morozov, N. M., and Temkin, M. I., Zh. Fiz. Khim. 33,471 (1959).
101. Temkin, M. I., Morozov, N. M., and Shapatina, E. N., Kinet. Katal. 4,260 and 565 (1963).
102. Smirnov, I. A., Morozov, N. M., and Temkin, M. I., Dokl. Akad. Nauk SSSR 153, 386
(1963).
103. Smirnov, I. A,, Morozov, N. M., and Temkin, M. I., Kinet. Katal. 6, 351 (1965).
104. Nielsen, A,, Kjer, J., and Hansen, B., J. Catal. 3, 68 (19642.
105. Kiperman, S., and Temkin, M., Zh. Fiz. Khim. 20,369 (1946).
106. Kiperman, S., and Temkin, M., Zh. Fiz. Khim. 20,623 (1946).
107. Kiperman, S. L., and Temkin, M. I., Zh. Fiz. Khim. 21,927 (1947).
108. Ozaki, A., Taylor, H., and Boudart, M., Proc. R. Soc. London, Ser. A 258,47 (1960).
109. Schulz, G., and Schaefer, H., Ber, Bunsenges. Phys. Chem. 70,21 (1966).
110. Shapatina, E. N., Kuchaev, V. L., and Temkin, M. I., Kinet. Katal. 12, 1476 (1971).
I l l . Boreskova, E. G., Kuchaev, V. L., Penkovoi, B. E., and Temkin, M. I., Kinet. Katal. 13,
358 (1972).
112. Igranova, E. G.,Ostrovskii, V. E., and Temkin, M. I., Kinet.-2, Vtor. Vses. Konf. Kinet.
Katal. Reakts., Vol. 1, p. 135 (1975).
113. Emmett, P. H., and Kummer, J., Ind. Eng. Chem. 35, 677 (1943).
290 M. I. TEMKIN
154. Cherednik, E. M., Temkin, M. I., and Apelbaum, L. O., Kinet. Katal. 9,824 (1968).
155. Shub, F. S., Apelbaum, L. O., and Temkin, M. I., Kinet. Katal. 11,566 and 11 19 (1970).
156. Apelbaum, L. O., and Temkin, M., Zh. Fiz. Khim. 22, 179 and 195 (1948).
157. Temkin, M. I., Morozov, N. M., Pyshev, V. M., Apelbaum, L. O., Lukyanova, L. I., and
Demidkin, V. A,, Probl. Fiz. Khim. 2, 14 (1959).
158. Morozov, N. M., Lukyanova, L. I., and Temkin, M. I., Kinet. Katal. 7, 172 (1966).
159. Apelbaum, L. O., and Temkin, M., Dokl. Akad. Nauk SSSR 74,963 (1950).
160. Apelbaum, L. O., and Temkin, M. I., Zh. Fiz. Khim. 33,2697 (1959).
161. Bodenstein, M., and Biittner, G., Z. Angew. Chem. 47, 364 (1934).
162. Bodenstein, M., Z . Angew. Chem. 48,327 (1935); Trans. Electrochem. SOC. 71,353 (1937);
Z.,Elektrochem. 47, 501 (1941); Z . Phys. Chem., Abt. B 50, 333 (1941).
163. Krauss, W . , Z . Phys. Chem., Abt. B 39,83 (1938).
164. Krauss, W . , and Schuleit, H., Z. Phys. Chem., Abt. B 45, 1. (1940).
165. Temkin, M., and Pyzhev, V., Acta Physicochim. URSS 1, 177 (1934); 2,473 (1935).
166. Shub, F. S., Khomenko, A. A., Apelbaum, L. O., and Temkin, M. I., Kinet.-2, Vtor.
Vses. Konf. Kinet. Katal. Reakts., Vol. 2, p. 13 (1975).
167. Shub, F. S., Khomenko, A. A., Apelbaum, L. O., andTemkin, M. I., Kinet. Katal. 17,1586
(1976).
168. Bulatnikova, Yu. I., Apelbaum, L. O., and Temkin, M. I., Zh. Fiz. Khim. 32,2717 (1958).