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Mlchel Boudart
Department of Chemlcal Engineering, Stanford Unlversify, Stanford, California 94305
The generalized De Donder equation relates the ratio of forward and reverse reaction rates to the exponential of
the thermodynamic driving force for reaction. The latter is the affinity divided by 8RT where 8 is the average
stoichiometric number for the reaction, equal to the stoichiometric number for the rate-determining step, if there
is one, and always equal to unity for an elementary step. I n the latter case,the equation provides useful i n f m t l o n
on the kinetic coupling between steps in a chain or catalytic sequence. I f there exists a rate-determining step,
the equation may help in revealing its identity.
6
that, for any elementary process, the rate constants, and
ki,are related to the equilibrium constant, K ; ,by means
of the relation
&/Ei = Ki (4)
As is well-known, this relation was anticipated by Ar-
rhenius and others, in less fundamental terms. Relation
4 is very useful as it gives access to a rate constant that
w
o
0.6 t- 1 may be difficult to measure, provided that the rate con-
stant for the step in the reverse direction is available to-
$ 2
gether with the equilibrium constant. The unexpected
51
lJ?k validity of (4) over 40 orders of magnitude of rate was
u. 3 0.4
8 pointed out by Johnston (1968) for an elementary process
Zk!
O W O,+M+ O + O + M
6a u6 O.* which may not seem amenable at first glance to the for-
[L
LL
malism of transition-state theory.
o 20 40 60 ao 100 120
TIME/S The De Donder Irreversibility Relation
Figure 1. Relaxation to the steady-state decomposition of ammonia De Donder's concern with irreversibility and affinity, A,
(pressure 2.4 X Pa) on a molybdenum foil at 1060 K (Boudart which is identical with -AG, the Gibbs free energy of re-
et al., 1982): upper curve, rate vs. time; lower curve, fraction of action with the minus sign, led him (De Donder, 1927) to
surface covered with nitrogen vs. time. a very useful relation that is similar in form to Eyring's
relation above.
state relates to the decomposition of ammonia at low
pressure (-lo+ Pa) and high temperature on a molyb- Ci/Ci = exp(Ai/Rr) (5)
denum foil in an ultrahigh-vacuum chamber used as a Indeed, to obtain Eyring's relation (4) from the relation
continuous stirred tank reactor (Boudart et al., 1982). The of De Donder (5), all that is necessary is to specify
reaction is run at the steady state. Then, the foil is standard-state conditions for which rates of elementary
"flashed" and N* leaves the foil. The upper curve shows process become equal to rate constants and affinities be-
the return to the steady-state rate as measured by a mass come standard affinities so that exp(Aio/RT) = Ki with
spectrometer. The relaxation time is of the same order the superscript denoting standard state. In actual fact,
as the value of the turnover time at the steady state. As it is ( 5 ) which is obtained most simply from Eyring's re-
the steady state is approached, the fraction of surface lation (4) and transition-state theory (Boudart and
covered with nitrogen, as measured by Auger electron DjBga-Mariadassou, 1984). The De Donder relation ex-
spectroscopy, also reaches its steady-state value (lower presses the kinetic irreversibility of reaction in terms of
curve of Figure 1)with the same relaxation time as that its thermodynamic driving force. In the form of eq 5, it
for the rate of reaction. is valid only for elementary steps.
The Product Rule A relation similar to (5)-relat$s forward and reverse
Following Temkin (Horiuti, 1973),the following identity currents for an electrode, i and i, to the overvoltage, 7
t -
can always be written for some or for all of the steps in i / i = exp(aq/FRT)
a catalytic sequence
where F is the Faraday constant and a is an empirical
(ij1 - v'l)i;2v'3...v', +
v'1(4 - ii,)v'3 ...v', + ... +
coefficient. This expression gives a measure of the irre-
v'&73*..(v'n - fin) = hi- hi(2)
Pl i=l
versibility of the electrode reaction in terms of its driving
force. It was first derived by Volmer and Butler (Bockris
Substitution of (1) for each step into (2) yields and Reddy, 1970).
Let us note a simple application of De Donder's relation.
u= [fi& - fiCi]/D Since in the expression (1) of the QSSA Ci > Si as long as
i=l i=l the reaction moves forward with u > 0, it follows from (5)
that, for a sequence of elementary steps at the steady state,
+
where D = 1 ~ ~ 4 v ' ~ . . . vv'l~2v'3...Cn
'~ + ... +
4C2&.,~,,. If the the affinity, Ai, is positive for all steps. This statement
catalytic sequence consists of n steps, u = v' - u is its net may sound evident, but it is useful to stress it (Boudart,
rate and, from the above 1983) as a result of statements in the literature in which
no distinction is made between Ai and its standard value,
Ai". Of course, a negative value of Aio does not prevent
a step from proceeding forward until it reaches its unfa-
Hence vorable equilibrium. We shall return to this point later
as we talk about kinetic coupling of catalytic cycles.
The Generalized De Donder Irreversibility
(3) Relation
For any catalytic chain sequence, let us introduce Tem-
kin's (Temkin, 1971) average stoichiometric number, 8,
This product rule will be used in what follows. defined as
Arrhenius' Relation between Rate Constants and 5 = CaiAi/ZAi = A / C A i (6)
i i i
the Equilibrium Constant
It is a straightforward consequence of Eyring's ther- where the summation extends to all steps and A is the
modynamic formulation of reaction rates (Eyring, 1935) affinity of the overall reaction.
72 Ind. Eng. Chem. Fundam., Vol. 25, No. 1, 1986
N
L
in terms of its thermodynamic driving force. The affinity -0
is modified by the average stoichiometric number of the
reaction.
.
$
>
0
Sufficiently near equilibrium, where AIaRT << 1so that Figure 2. Linear relation between net rate u and affinity A for the
the exponential in (9) can be expanded in series with only reaction CsHl2 = CsHs + 3Hz on both sides of equilibrium. Data are
from Prigogine et al. (1948), and the least-squares line is from Bou-
the first term retained in the expansion, eq 9 becomes dart et al. (1985).
u = u’(A/sRT) (10)
is not evident that the linear relation (11)will be obeyed
Further, when AIaRT tends to zero, ?I tends to u,, the rate except perhaps so near equilibrium that the h e a r law may
at equilibrium or the exchange rate (Wagner, 1970) be a trivial one (Garfinkle, 1983). It is therefore interesting
u = u,(A/@RT) (11) that linearity between u and A was established experi-
mentally by Prigogine et al. (1948) on both sides of the
The linear relation (11)between rate and affinity was first equilibrium of the reaction
formulated by Horiuti (1953). It was then used by Horiuti
and Nakamura (1967) in the case of ammonia synthesis CCH12 = C&6 + 3H2 (15)
Nz + 3H2 = 2NH3 (12) taking place on a nickel catalyst. In fact, it has been
with the idea of obtaining the stoichiometric number, g d , noticed (Boudart et al., 1985) that the small standard
of the rate-determining step (rds) of that reaction. The deviation of the data from the best least-squares straight
existence of an rds predicates that the affinity of all steps line (Figure 2) suggests, as follows from (ll),a rather high
is zero (or essentially zero) except that of the rds. In such value of a, equal to at least 3. Let us assume that it is 3
a case, it follows from (6) that and that there exists an rds. As suggested by Herbo (1942),
the rds involved is the dehydrogenation of cyclohexane
?? = g d (13) (C6H12)to cyclohexene (C6H10):
Thus, if there exists an rds, (11)becomes
u = u,(A/gdRT) (14)
Then, if the reaction proceeds further by the equilibrated
Thus, it is possible to determine g d by measuring the disproportionation of C6H10
net rate, u , near equilibrium and the exchange rate, u,, at
equilibrium by means of a suitable tracer. It was first 3C6HIO C6H6 t 2C6HIZ (17)
reported (Horiuti and Nakamura, 1967) that g d = 2 for
ammonia synthesis when the reaction is written as in (12). where the symbol =8= denotes zero net rate, or an
However, later work suggested that g d = 1 (Mars et al., equilibrated reaction. This reaction proceeds very rapidly
1960). If the latter value is correct, it follows from any on nickel. The value of ad should be equal to 3 since the
dissociative mechanism of catalytic ammonia synthesis rds implied in (16) followed by (17) must take place three
that the rds is the chemisorption of N2 at the surface of times for reaction 15 to turn over once. This conclusion
the catalyst. By the words “dissociative mechanism” is is supported by the excellent fit of the data up to high
meant one in which both N2 and H2 first dissociate at the values of A. Details are given in Boudart et al. (1985).
surface; then successive recombination steps take place Thus, not only is the linear relationship (11)of Horiuti
between adsorbed species until NH, is released from the valid near equilibrium but it can provide useful mecha-
surface (Boudart, 1981). nistic information without the need of rate measurements
This example is just one of the many nice illustrations at equilibrium.
of the fact that work on ammonia synthesis, the epitome Virtual Pressure [N,],in Ammonia
of an industrial catalytic reaction, has fed back many new Decomposition
general concepts to fundamental catalysis science. This
point has been discussed in detail elsewhere (Boudart, This is another interesting application of the De Donder
1978; Timm, 1974). relation. The overall reaction with equilibrium constant
K is
Validity and Further Use of the Linear Relation
K
between v and A 2NH3 = N2 + 3H2
Since u’, a variable in (IO), can be replaced by u,, a
constant in ( l l ) , only when the affinity tends to zero, it On many catalysts, at not too high temperatures and not
Ind. Eng. Chem. Fundam., Vol. 25, No. 1, 1986 73
too low pressures, the accepted mechanism is Kinetic Coupling of Elementary Steps in a
Catalytic Sequence
2NH3 + 2" -9- 2N" + 3H2
To drive a thermodynamically unfavorable step, (Aio <
0), two possibilities exist: either the concentration of a
2N* 2" + N,
reactant should be made large enough, as was the case
above in ammonia decomposition, or a product must be
x2
kept at a sufficiently low concentration level by removing
where the first reaction is equilibrated and the second is it is a subsequent step faster than it can return to the
the rds on a surface where N is the most abundant reaction original reactants. This can be done by kinetic coupling
intermediate. (Boudart, 1976). Let us explain briefly the nature of this
Define a virtual pressure [N2], as the value of [N,] re- kinetic coupling in the free radical reaction, H2 Br2 = +
quired to obtain at virtual equilibrium the value [N],, 2HBr, that takes place according to the classical mecha-
pertaining to the steady state of the reaction nism following an equilibrium between Br and Br,, which,
by the way, does not take place through an elementary step
v'2 = Ldd(aN*,ss) = 62 = k'ja(a*,ss)[Nzle (18)
where we have carefully used a thermodynamic activity, v2Br2 =& Br
a, for the surface species and have not specified the form
+ -
kI
+
1
of the functions, fa and fd, that depend on surface activity Br H, HBr H (k,/k-,=K,)
T
at the steady state, uN*,,,. Thus, in all generality, we can propagation
write with the help of (18) H -I- Br,
&
2 HBr + Br
~~NH31,,2/[N2lss~H21ss3
so that
Finally, for example
[HI, = Ko[Br2]1/2
[N2Ie= K[NH3],,2/[H2],s3 N 6400 bar at 673 K
Now, if we start from a stoichiometric mixture, we have
with ammonia and dihydrogen at 1 bar each. at half-reaction [H,] = [Br,] = [HBr]. The De Donder
The concept of virtual pressure, presented here as a relation gives, at half-reaction
consequence of the De Donder relation, originated with Cl/Cl = exp(Al/RT) = [H],/[H],, = 1 + k z / k l (20)
Temkin and Pyzhev (1940), who introduced the related
concept of fugacity of adsorbed species. The concept of since
virtual pressure was further developed by Kemball(l966).
Although it is yet another concept that came about as a [HI,, = k,[BrI,/(k-, + k2)
result of fundamental studies of ammonia synthesis, it is as readily obtained from the steady-state condition (1)
general and useful. u = v'l - v'l = v'p
Thus, by using ammonia as a nitriding agent, it is pos-
sible to form iron nitride at low pressure and at the high The meaning of eq 20 is that the thermodynamically un-
temperatures required so that diffusion of nitrogen into favorable step proceeds forward with a decided irrevers-
the bulk of the metal proceeds at reasonable speed. Yet, ibility even at half-reaction, since
without the high virtual pressure of nitrogen, the nitride kZ/k-1 10 N v'l/C1
would not be stable at those high temperatures. Another
consequence of eq 19 is that the irreversibility of the as- because, at steady state, H atoms are "pumped down" from
-
sociative desorption of nitrogen is very large under the
conditions specified, since 4/17, 6400 during the
steady-state decomposition of ammonia. This marked
irreversibility of the desorption step means that the
H + Br, HBr + Br -
their equilibrium concentration by the subsequent step
(1907), who first observed it but did not know the mech- mediate is quite valuable. Note that the lack of inhibition
anism of the reaction. Let us now return to the inhibition of the reaction rate by the other reaction product, di-
or lack of inhibition of the rate of a catalytic reaction by hydrogen, follows ipso facto from its inability to compete
a reaction product. with the abundant reactive intermediate.
In yet another example, when an order of reaction is zero
Mechanistic Information Obtainable from the with respect to a certain component, the lack of inhibition
Presence or Absence of Product Inhibition of the rate by the product issuing from the species related
In a catalytic reaction, the desorption step or steps that to the zero-order component is not unexpected. Thus, for
release products are moderately or strongly endothermic. ethylene hydrogenation on platinum (Emmett, 1962),the
Although desorption proceeds with an increase in standard zero order with respect to ethane appears related to the
entropy, a desorption step is normally expected to be lim- zero order with respect to ethylene. Although the nature
ited by equilibrium. Thus, it is likely that, at the steady of the surface species that saturates the catalytic sites is
state, the desorption steps will be in quasi-equilibrium. If not known (de Boer, 1957; Cimino et al., 1954),there is no
the surface species that desorbs occupies a significant doubt that such a species exists.
fraction of the catalytic sites, it follows that the product A third explanation of the lack of inhibition of the
of desorption will inhibit the rate of the overall reaction. forward rate of reaction by a product is that the desorption
This is the case of ammonia synthesis on iron that is in- of the product from the surface of the catalyst is indeed
hibited by ammonia (Ozaki and Aika, 1981), of oxidation exothermic. This implies, of course, that adsorption of that
of sulfur dioxide on vanadium oxide that is inhibited by species would be endothermic and therefore very unfa-
sulfur trioxide (Bodenstein and Fink, 19071, and of the vorable (Aio< 0) since adsorption is normally accompanied
hydrodesulfurization of sulfur-containing hydrocarbons on by a loss of entropy (de Boer, 1957). This explanation
cobalt-molybdenum sulfide that is inhibited by hydrogen suggests itself in the case of the hydrogenolysis of ethane
sulfide (Satterfield and Roberts, 1968). (Cimino et al., 1954)
When a reaction product is not an inhibitor, three ex-
CZH, + Hz = 2CH4
planations are possible. The first is that the surface species
that desorbs occupies a kinetically insignificant fraction and the methanation reaction (Vannice, 1982)
of the catalytic sites. This is true for ammonia decom- CO + 3Hz = CH4 + HzO
position at low pressures and high temperatures (Boudart
et al., 1982) or at high pressures and low temperatures on transition metals. In both cases, methane is not an
(Emmett, 1962), where dihydrogen goes not inhibit the rate inhibitor of the rate. That adsorption of methane on
of ammonia decomposition. Correspondingly, nitrogen is metals is endothermic is not surprising in view of the
the most abundant reactive intermediate and hydrogen known difficulty of methane activation. It may be noted
does not compete effectively for catalytic sites. that methane activation is not assessed correctly by
A second explanation applies to dinitrogen in ammonia methane-deuterium exchange.
decomposition. In this case, dinitrogen is not an inhibitor Thus, mere inspection of a rudimentary rate equation
of the rate. As noted above, this is attributed to the fact or even the elementary knowledge whether a product in-
that, as a result of the high virtual pressure of nitrogen, hibits the rate or not contains nontrivial mechanistic in-
the surface concentration of adsorbed nitrogen consider- formation. Ultimately, the qualitative or quantitative
ably exceeds the equilibrium value corresponding to the meaning of this information is contained in the De Donder
steady-state pressure of dinitrogen. Hence, the desorption relation that measures the irreversibility of a step.
of nitrogen proceeds essentially irreversibly and no in- Conclusions
hibition by nitrogen is observed. The De Donder relation for an elementary step and its
A similar situation applks to the dehydrogenation of generalization for a catalystic or chain sequence contain
methylcyclohexane, M, to toluene, T, on a platinum-re- useful mechanistic information. Thus, the relation pro-
forming catalyst (Sinfelt et al., 1960). I t is found that vides a useful bridge between macro- and microkinetics.
toluene does not inhibit the rate. The preferred mecha- Its measure of irreversibility, far from or near equilibrium,
nism (Sinfelt et al., 1960) is one in which M adsorbs ir- can be used to understand or determine kinetic coupling,
reversibly in an opening step and T*, the most abundant virtual pressure, the difference between equilibrium and
reactive intermediate, desorbs irreversibly in a final step. steady-state concentrations, the inhibition of a catalytic
Again, why is the desorption step essentially irreversible? reaction by a reaction product or the lack of it, and the
Our explanation is that, at the steady state, the surface stoichiometric number of the rate-determining step, if
concentration of toluene is substantially greater than that there is one. The De Donder relation is obviously a useful
corresponding to the equilibrium concentration that could bridge between thermodynamics and kinetics. The present
be reached at equilibrium between the surface and toluene paper underscores its usefulness in building bridges be-
at the steady-state pressure of the reaction. In other words, tween macro- and microkinetics, i.e., between the rates of
the virtual pressure of toluene resulting from kinetic the overall reaction and the rates of its component steps,
coupling is much higher than its steady-state pressure. or finally, between industrial data and fundamental in-
This explains clearly why addition of benzene to the feed vestigations.
(Sinfelt et al., 1960) hardly inhibited the rate of M * T
+ 3Hz. To compete effectivelywith toluene for the surface Acknowledgment
benzene should be added at a pressure corresponding to This work was carried out as part of a continuing NSF
the virtual pressure of toluene, not its real pressure. These program, currently under Grant NSF-CBT 8219066.
remarks are qualitative but could be quantified by
measuring the steady-state and equilibrium concentrations Literature Cited
of adsorbed toluene. Then the irreversibility of the de- A k a , D. L.; Edelson, D. Int. J . Chem. Kinet. 1975, 7, 479.
Baronnet, F.; Niclause, M. Ind. fng. Chem. Fundam.. this issue.
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knowledge, the mechanistic information inferred from the Bockris, J. O.'M.; Reddy, A. K. N. "Modern Electrochemistry"; Plenum Press:
New York, 1970; Voi. 2, Chapter 8.
mere lack of inhibition of the rate of reaction by the Bodenstein, M.; Fink, C. G. 2.fhys. Chem. 1907, 60, 1.
product issuing from the most abundant reactive inter- Bodenstein, M.; Lind. S. C. Z .fhys. Chem. 1907, 57, 168.
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GENERAL ARTICLES
A cubic equation of the perturbation type is developed to express pressure as being made up of contributions due
to repulsive, rotational, and attractive forces. Use of the equation requires p,, T,, and w of a substance to be
known. Calculated pvT, vapor pressure, and enthalpy are compared with data and with the Soave equation and
the Peng-Robinson equation for a variety of substances over wide ranges of temperature and pressure. The
equation is extended to mixtures by using van der Waals one-fluid mixing rules for the equation parameters.
Gas-liquid equillbria of fluid mixtures are calculated for low-pressure symmetric mixtures as well as for highpressure
asymmetric mixtures of a heavy solvent with a light gas such as hydrogen, methane, carbon dioxide, and nitrogen.
Calculated pvT of mixtures is illustrated with two binary systems for gas and liquid states%p to the critical point.