70 Ind. Eng. Chem. Fundam.

1986, 25, 70-75

Some Applications of the Generalized De Donder Equation to

Industrial Reactions

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.

Introduction powerful links between the kinetic of elementary steps and

Thousands of rate constants are tabulated for elemen-
tary reactions involving free radicals (Kondrat’ev, 1970).
Many more can be estimated (Benson, 1976). Thus, rates
of chain reactions proceeding singly or in networks can be
calculated or estimated from kinetic information on ele-
mentary steps, Le., a microkinetic database. In this way
macrokinetic behavior of many free radical chain reactions
can be described from microkinetic information. Many
examples can be found in pyrolysis of hydrocarbons
(Baronnet and Niclause, 1985), vinyl polymerization
(North, 1966), oxidation (Van Tiggelen, 1968), combustion
(Glassman, 1977), and chemistry of the troposphere
(Hampton, 1973) or the stratosphere (Boudart and
DjBga-Mariadasou, 1984). Progress in the numerical so-
lution of stiff differential equations now makes the qua-
si-steady-state approximation unnecessary in the kinetic
analysis of these reactions (Allara and Edelson, 1975). The
interplay of micro- and macrokinetics in free radical re-
actions provides a prime example of the feedback loop
between industrial chemistry dealing with, e.g., steam
cracking and academic chemical kinetics dealing with rate
constants of elementary steps, e.g., of free radical reactions.
By contrast, in the case of catalytic kinetics, the old
tradition of inferring microkinetic information from ma-
crokinetic observation continues tQ flourish in spite of the
well-known ambiguities of mechanisms derived from ki-
netics, the so-called kinetic mechanisms (Boudart and
DjBga-Mariadassou,1984). The reason is clear. Until very
recently, there was very little known about the microki-
netics of catalytic reactions. The situation is now changing
in the case of homogeneous catalysis (Hjortkjaer, 1982).
As to heterogeneous catalysis, recent advances in surface
science have made available a small but rapidly increasing
number of rate constants of elementary steps on so-called
well-defined surfaces, mostly metallic single crystals
(Madix, 1979). Such data are now available for adsorption,
surface reaction, and desorption (Boudart and DjBga-
Mariadassou, 1984). As these data accumulate, it seems
opportune to review the available relations linking micro-
and macrokinetics and to examine the general kinetic
structure of catalytic cycles. In particular, some special
kinetic features of cycles in heterogeneous catalysis will
be discussed. Indeed, it is hoped that the kinetic
knowledge made available by studies on single crystals will
quickly find its application in the mainstream of catalytic
research as a result of a keener awareness of the links
between micro- and macrokinetics. It is also hoped that
this review may stimulate the discovery of new, more
0 1986 American Chemical Society
the rate of catalytic cycles. In turn, this would accelerate
the transfer of data from industrial catalysis to surface
science, and vice versa. Let us now present the main useful
relations connecting micro- and macrokinetics or kinetics
and mechanism.
The Quasi-Steady-State Approximation
Any catalytic cycle consists of a sequence of elementary
processes. Each one proceeds at a net rate:
V i = Ci - gi
Steps must be written as they are believed to occur at the
molecular level. Thus, for dissociative chemisorption of
N2 on a catalytic site denoted by *, one may write two
successive steps
+
Nz * -i N*N
N*N + * & 2N*
or perhaps in a single step
N2 + 2* s 2N*
but certainly not
1/2N2+ * e N*
If the stoichiometric equations for each step in a catalytic
sequence are summed up side by side, the sum reproduces
the stoichiometric equation for the overall reaction, pro-
vided that each step is taken u, times where ui is the
stoichiometric number of that step. The value of cri de-
pends on the arbitrary way in which the stoichiometric
equation for the overall reaction has been written, e.g.
N2 + 3H2 = 2NH, or 1/2N2+ 3/2H2= NH,
The quasi-steady-state approximation (QSSA), in the
form first clearly enunciated by Christiansen (1953), states
that at the kinetic steady state
UiU = u’i - fii
(1)
for all steps in the cycle proceeding at a net overall rate:
v=v‘-v’
If the rate, u, is referred to the number of catalytic sites,
it becomes the turnover rate, ut. The inverse of ut is a time,
the turnover time, T. It seems intuitively clear that the
kinetic steady state will not be established before a re-
laxation time of the order of T. In any event, a substance
is not a catalyst unless it turns over more than once. An
example of relaxation time (Figure 1)to reach the steady
 Ind. Eng. Chem. Fundam., Vol. 25, No. 1, 1986 71

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

Substitution of the De Donder relation (5) into Temkin’s I I I

3
product rule (3) followed by the use of definition (6) leads
to the generalized De Donder relation
i3/C = exp(A/@Rn (7) 2

which expresses the kinetic irreversibility of the overall

reaction proceeding at a net rate
- 1
Im
u=u’-6 (8) c

N
L
in terms of its thermodynamic driving force. The affinity -0
is modified by the average stoichiometric number of the
reaction.
.
$
>
0

Rearranging (7) with the use of (8) gives simply

-I
u = u’[l - exp(-A/@RT)] (9)
Thus, the net rate of a reaction is given by its forward rate
multiplied by a thermodynamic potential (Happel, 1972) -2
given by the expression between brackets in (9).
Linear Relation between Rate and Affinity near -0 4 0 04 08
Equilibrium A IRT

Sufficiently near equilibrium, where AIaRT << 1so that
the exponential in (9) can be expanded in series with only
the first term retained in the expansion, eq 9 becomes
u = u’(A/sRT) (10)
Further, when AIaRT tends to zero, ?I tends to u,, the rate
at equilibrium or the exchange rate (Wagner, 1970)
u = u,(A/@RT) (11)
The linear relation (11)between rate and affinity was first
formulated by Horiuti (1953). It was then used by Horiuti
and Nakamura (1967) in the case of ammonia synthesis
Nz + 3H2 = 2NH3 (12)
with the idea of obtaining the stoichiometric number, g d ,
of the rate-determining step (rds) of that reaction. The
existence of an rds predicates that the affinity of all steps
is zero (or essentially zero) except that of the rds. In such
a case, it follows from (6) that
?? = g d (13)
Thus, if there exists an rds, (11)becomes
u = u,(A/gdRT) (14)
Thus, it is possible to determine g d by measuring the
net rate, u , near equilibrium and the exchange rate, u,, at
equilibrium by means of a suitable tracer. It was first
reported (Horiuti and Nakamura, 1967) that g d = 2 for
ammonia synthesis when the reaction is written as in (12).
However, later work suggested that g d = 1 (Mars et al.,
1960). If the latter value is correct, it follows from any
dissociative mechanism of catalytic ammonia synthesis
that the rds is the chemisorption of N2 at the surface of
the catalyst. By the words “dissociative mechanism” is
meant one in which both N2 and H2 first dissociate at the
surface; then successive recombination steps take place
between adsorbed species until NH, is released from the
surface (Boudart, 1981).
This example is just one of the many nice illustrations
of the fact that work on ammonia synthesis, the epitome
of an industrial catalytic reaction, has fed back many new
general concepts to fundamental catalysis science. This
point has been discussed in detail elsewhere (Boudart,
1978; Timm, 1974).
Validity and Further Use of the Linear Relation
between v and A
Since u’, a variable in (IO), can be replaced by u,, a
constant in ( l l ) , only when the affinity tends to zero, it
Figure 2. Linear relation between net rate u and affinity A for the
reaction CsHl2 = CsHs + 3Hz on both sides of equilibrium. Data are
from Prigogine et al. (1948), and the least-squares line is from Bou-
dart et al. (1985).
is not evident that the linear relation (11)will be obeyed
except perhaps so near equilibrium that the h e a r law may
be a trivial one (Garfinkle, 1983). It is therefore interesting
that linearity between u and A was established experi-
mentally by Prigogine et al. (1948) on both sides of the
equilibrium of the reaction
CCH12 = C&6 + 3H2 (15)
taking place on a nickel catalyst. In fact, it has been
noticed (Boudart et al., 1985) that the small standard
deviation of the data from the best least-squares straight
line (Figure 2) suggests, as follows from (ll),a rather high
value of a, equal to at least 3. Let us assume that it is 3
and that there exists an rds. As suggested by Herbo (1942),
the rds involved is the dehydrogenation of cyclohexane
(C6H12)to cyclohexene (C6H10):
Then, if the reaction proceeds further by the equilibrated
disproportionation of C6H10
3C6HIO C6H6 t 2C6HIZ (17)
where the symbol =8= denotes zero net rate, or an
equilibrated reaction. This reaction proceeds very rapidly
on nickel. The value of ad should be equal to 3 since the
rds implied in (16) followed by (17) must take place three
times for reaction 15 to turn over once. This conclusion
is supported by the excellent fit of the data up to high
values of A. Details are given in Boudart et al. (1985).
Thus, not only is the linear relationship (11)of Horiuti
valid near equilibrium but it can provide useful mecha-
nistic information without the need of rate measurements
at equilibrium.
Virtual Pressure [N,],in Ammonia
Decomposition
This is another interesting application of the De Donder
relation. The overall reaction with equilibrium constant
K is
K
2NH3 = N2 + 3H2
On many catalysts, at not too high temperatures and not

too low pressures, the accepted mechanism is
2NH3 + 2" -9- 2N" + 3H2
2N* 2" + N,
x2
where the first reaction is equilibrated and the second is
the rds on a surface where N is the most abundant reaction
intermediate.
Define a virtual pressure [N2], as the value of [N,] re-
quired to obtain at virtual equilibrium the value [N],,
pertaining to the steady state of the reaction
v'2 = Ldd(aN*,ss) = 62 = k'ja(a*,ss)[Nzle
where we have carefully used a thermodynamic activity,
a, for the surface species and have not specified the form
of the functions, fa and fd, that depend on surface activity
at the steady state, uN*,,,. Thus, in all generality, we can
write with the help of (18)
Applying the De Donder relation and noting that A2 = A,
since step 2 is the rds, and expressing A in terms of K and
steady-state values of gaseous concentrations or fugacities,
we get from (19)
"
- =-= exp(A,/RT) = exp(A/RT) =
fi2 [N21,,
~~NH31,,2/[N2lss~H21ss3
Finally, for example
[N2Ie= K[NH3],,2/[H2],s3 N 6400 bar at 673 K
with ammonia and dihydrogen at 1 bar each.
The concept of virtual pressure, presented here as a
consequence of the De Donder relation, originated with
Temkin and Pyzhev (1940), who introduced the related
concept of fugacity of adsorbed species. The concept of
virtual pressure was further developed by Kemball(l966).
Although it is yet another concept that came about as a
result of fundamental studies of ammonia synthesis, it is
general and useful.
Thus, by using ammonia as a nitriding agent, it is pos-
sible to form iron nitride at low pressure and at the high
temperatures required so that diffusion of nitrogen into
the bulk of the metal proceeds at reasonable speed. Yet,
without the high virtual pressure of nitrogen, the nitride
would not be stable at those high temperatures. Another
consequence of eq 19 is that the irreversibility of the as-
-
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
steady-state concentration of surface nitrogen must be
considerably larger than the concentration of surface ni-
trogen that would be in equilibrium with the steady-state
concentration of gaseous dinitrogen. This conclusion was
checked experimentally in the case of decomposition of
ammonia on a molybdenum foil at high temperatures but
low pressures, at which the steady-state concentration of
surface nitrogen could be monitored by Auger electron
spectroscopy (Boudart et al., 1982). Another consequence
of the irreversibility of the desorption step in ammonia
decomposition is that the rate is not inhibited by nitrogen
as might be the case if the desorption step was limited by
equilibrium. We will return to this point later.
Ind. Eng. Chem. Fundam., Vol. 25, No. 1, 1986 73
Kinetic Coupling of Elementary Steps in a
Catalytic Sequence
To drive a thermodynamically unfavorable step, (Aio <
0), two possibilities exist: either the concentration of a
reactant should be made large enough, as was the case
above in ammonia decomposition, or a product must be
kept at a sufficiently low concentration level by removing
it is a subsequent step faster than it can return to the
original reactants. This can be done by kinetic coupling
(Boudart, 1976). Let us explain briefly the nature of this
kinetic coupling in the free radical reaction, H2 Br2 = +
2HBr, that takes place according to the classical mecha-
nism following an equilibrium between Br and Br,, which,
by the way, does not take place through an elementary step
(18)
v2Br2 =& Br
+ -
kI
+
1
Br H, HBr H (k,/k-,=K,)
T
propagation
H -I- Br,
&
2 HBr + Br
The first step in the propagation sequence should be se-
verely limited by equilibrium since it is sizably endo-
thermic and essentially isentropic. At equilibrium the
concentration of hydrogen, [HI,, is obtained easily by
noting that
Kl[Br], = K1K[Br2]1/2= Ko[Br2]1/2
where KOis the equilibrium constant of
'/2Br2 + H, HBr + H
so that
[HI, = Ko[Br2]1/2
Now, if we start from a stoichiometric mixture, we have
at half-reaction [H,] = [Br,] = [HBr]. The De Donder
relation gives, at half-reaction
Cl/Cl = exp(Al/RT) = [H],/[H],, = 1 + k z / k l (20)
since
[HI,, = k,[BrI,/(k-, + k2)
as readily obtained from the steady-state condition (1)
u = v'l - v'l = v'p
The meaning of eq 20 is that the thermodynamically un-
favorable step proceeds forward with a decided irrevers-
ibility even at half-reaction, since
kZ/k-1 10 N v'l/C1
because, at steady state, H atoms are "pumped down" from
H + Br, HBr + Br -
their equilibrium concentration by the subsequent step
As a result, the affmity for the difficult step at steady state,
Al,,,, is positive although the standard affinity, AlO,is
negative. Thus, in calculations of the standard affinity,
Ai', of steps in a catalytic cycle (Goddard, 1985), the oc-
currence of negative values for Aio should not prevent the
cycle from turning over at an acceptable rate, if kinetic
coupling is favorable.
Yet, in the above example, because k 2 / k - , is known to
be only -10, the step Br + H2 F? HBr + H is nonetheless
reversible and HBr is an inhibitor of the overall rate, al-
though the overall reaction itself is not limited by equi-
librium. The inhibiting effect of the product HBr on the
rate of a reaction which is run under irreversible conditions
was indeed a formidable puzzle for Bodenstein and Lind
74 Ind. Eng. Chem. Fundam., Vol. 25, No. 1, 1986
(1907), who first observed it but did not know the mech-
anism of the reaction. Let us now return to the inhibition
or lack of inhibition of the rate of a catalytic reaction by
a reaction product.
Mechanistic Information Obtainable from the
Presence or Absence of Product Inhibition
In a catalytic reaction, the desorption step or steps that
release products are moderately or strongly endothermic.
Although desorption proceeds with an increase in standard
entropy, a desorption step is normally expected to be lim-
ited by equilibrium. Thus, it is likely that, at the steady
state, the desorption steps will be in quasi-equilibrium. If
the surface species that desorbs occupies a significant
fraction of the catalytic sites, it follows that the product
of desorption will inhibit the rate of the overall reaction.
This is the case of ammonia synthesis on iron that is in-
hibited by ammonia (Ozaki and Aika, 1981), of oxidation
of sulfur dioxide on vanadium oxide that is inhibited by
sulfur trioxide (Bodenstein and Fink, 19071, and of the
hydrodesulfurization of sulfur-containing hydrocarbons on
cobalt-molybdenum sulfide that is inhibited by hydrogen
sulfide (Satterfield and Roberts, 1968).
When a reaction product is not an inhibitor, three ex-
planations are possible. The first is that the surface species
that desorbs occupies a kinetically insignificant fraction
of the catalytic sites. This is true for ammonia decom-
position at low pressures and high temperatures (Boudart
et al., 1982) or at high pressures and low temperatures
(Emmett, 1962), where dihydrogen goes not inhibit the rate
of ammonia decomposition. Correspondingly, nitrogen is
the most abundant reactive intermediate and hydrogen
does not compete effectively for catalytic sites.
A second explanation applies to dinitrogen in ammonia
decomposition. In this case, dinitrogen is not an inhibitor
of the rate. As noted above, this is attributed to the fact
that, as a result of the high virtual pressure of nitrogen,
the surface concentration of adsorbed nitrogen consider-
ably exceeds the equilibrium value corresponding to the
steady-state pressure of dinitrogen. Hence, the desorption
of nitrogen proceeds essentially irreversibly and no in-
hibition by nitrogen is observed.
A similar situation applks to the dehydrogenation of
methylcyclohexane, M, to toluene, T, on a platinum-re-
forming catalyst (Sinfelt et al., 1960). I t is found that
toluene does not inhibit the rate. The preferred mecha-
nism (Sinfelt et al., 1960) is one in which M adsorbs ir-
reversibly in an opening step and T*, the most abundant
reactive intermediate, desorbs irreversibly in a final step.
Again, why is the desorption step essentially irreversible?
Our explanation is that, at the steady state, the surface
concentration of toluene is substantially greater than that
corresponding to the equilibrium concentration that could
be reached at equilibrium between the surface and toluene
at the steady-state pressure of the reaction. In other words,
the virtual pressure of toluene resulting from kinetic
coupling is much higher than its steady-state pressure.
This explains clearly why addition of benzene to the feed
(Sinfelt et al., 1960) hardly inhibited the rate of M * T
+ 3Hz. To compete effectivelywith toluene for the surface
benzene should be added at a pressure corresponding to
the virtual pressure of toluene, not its real pressure. These
remarks are qualitative but could be quantified by
measuring the steady-state and equilibrium concentrations
of adsorbed toluene. Then the irreversibility of the de-
sorption step could be calculated. But even without this
knowledge, the mechanistic information inferred from the
mere lack of inhibition of the rate of reaction by the
product issuing from the most abundant reactive inter-
mediate is quite valuable. Note that the lack of inhibition
of the reaction rate by the other reaction product, di-
hydrogen, follows ipso facto from its inability to compete
with the abundant reactive intermediate.
In yet another example, when an order of reaction is zero
with respect to a certain component, the lack of inhibition
of the rate by the product issuing from the species related
to the zero-order component is not unexpected. Thus, for
ethylene hydrogenation on platinum (Emmett, 1962),the
zero order with respect to ethane appears related to the
zero order with respect to ethylene. Although the nature
of the surface species that saturates the catalytic sites is
not known (de Boer, 1957; Cimino et al., 1954),there is no
doubt that such a species exists.
A third explanation of the lack of inhibition of the
forward rate of reaction by a product is that the desorption
of the product from the surface of the catalyst is indeed
exothermic. This implies, of course, that adsorption of that
species would be endothermic and therefore very unfa-
vorable (Aio< 0) since adsorption is normally accompanied
by a loss of entropy (de Boer, 1957). This explanation
suggests itself in the case of the hydrogenolysis of ethane
(Cimino et al., 1954)
CZH, + Hz = 2CH4
and the methanation reaction (Vannice, 1982)
CO + 3Hz = CH4 + HzO
on transition metals. In both cases, methane is not an
inhibitor of the rate. That adsorption of methane on
metals is endothermic is not surprising in view of the
known difficulty of methane activation. It may be noted
that methane activation is not assessed correctly by
methane-deuterium exchange.
Thus, mere inspection of a rudimentary rate equation
or even the elementary knowledge whether a product in-
hibits the rate or not contains nontrivial mechanistic in-
formation. Ultimately, the qualitative or quantitative
meaning of this information is contained in the De Donder
relation that measures the irreversibility of a step.
Conclusions
The De Donder relation for an elementary step and its
generalization for a catalystic or chain sequence contain
useful mechanistic information. Thus, the relation pro-
vides a useful bridge between macro- and microkinetics.
Its measure of irreversibility, far from or near equilibrium,
can be used to understand or determine kinetic coupling,
virtual pressure, the difference between equilibrium and
steady-state concentrations, the inhibition of a catalytic
reaction by a reaction product or the lack of it, and the
stoichiometric number of the rate-determining step, if
there is one. The De Donder relation is obviously a useful
bridge between thermodynamics and kinetics. The present
paper underscores its usefulness in building bridges be-
tween macro- and microkinetics, i.e., between the rates of
the overall reaction and the rates of its component steps,
or finally, between industrial data and fundamental in-
vestigations.
Acknowledgment
This work was carried out as part of a continuing NSF
program, currently under Grant NSF-CBT 8219066.
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Received f o r review June 21, 1985
Accepted October 17, 1985
This paper was presented at the National Meeting of the American
Chemical Society, Miami, April 1985.

GENERAL ARTICLES

Cubic Chain-of-Rotators Equation of State

Hwayong Kim,+ Ho-Mu Lln, and Kwang-Chu Chao’
School of Chemical Engineering, Purdue lJnivers& West Lafayette, Indiana 47907

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.

Introduction equation of state to include Carnahan and Starling’s re-

Equations of state are useful for the calculation of fluid
thermodynamic properties. This usefulness has prompted
a continual development of new equations. The pertur-
bation type of approach is noteworthy for being productive
of some very useful equations of which the cubic equations
have received much attention. Equations such as Red-
lich-Kwong (1949), Soave (1972), and Peng-Robinson
(1976) are in wide use due to their simplicity and generality
combined with reasonable accuracy. AU of these equations
contain van der Waals excluded-volume expression for the
repulsive pressure RT/(u - b). The excluded-volume
concept is valid for a dilute gas but breaks down at high
densities such as those of liquids (Vera and Prausnitz,
1972; Gubbins, 1973; Abbott, 1979; Henderson, 1979).
In place of van der Waals form, Carnahan and Starling
(1969, 1972) obtained an expression for the repulsive
pressure based on molecular dynamics calculations. Do-
nohue and Prausnitz (1978) developed a perturbation
‘Department of Chemical Engineering, University of Delaware,
Newark. DE.
0196-4313/86/1025-0075$01.50/0
pulsive pressure and, additionally, to account for the ro-
tational motion of polyatomic molecules in terms of
equivalent translational degrees of freedom. Chien et al.
(1983) obtained an expression for the rotational pressure
from Boublik’s (1975) equation for hard dumbbell mole-
cules. The chain-of-rotators (COR) equation of state that
Chien et al. developed using the Carnahan and Starling
repulsive pressure expression and their new rotational
pressure expression appears to be accurate, but complex.
In this work we develop a cubic equation as a simplified
form of the COR equation of Chien et al. in order to
provide the computational ease of cubic equations while
retaining the structure of the COR equation. The repulsive
and rotational pressure contributions are simulated with
simpler functions. The attractive pressure expression is
also simplified. The equation is then fitted to the vapor
pressure and saturated liquid density at subcritical tem-
peratures and the pu isotherms at supercritical tempera-
tures.
The CCOR equation requires the three constants T,,p,,
and o for the substance to be described. These constants
are known for a large number of substances, in contrast
0 1986 American Chemical Society