reactions

Article
Requiem for the Rate-Determining Step in Complex
Heterogeneous Catalytic Reactions?
Dmitry Yu. Murzin
Process Chemistry Centre, Åbo Akademi University, 20500 Turku/Åbo, Finland; dmitry.murzin@abo.fi




Received: 1 September 2020; Accepted: 9 September 2020; Published: 10 September 2020


Abstract: The concept of the rate determining step, i.e., the step having the strongest influence on the
reaction rate or even being the only one present in the rate equation, is often used in heterogeneous
catalytic reactions. The utilization of this concept mainly stems from a need to reduce complexity
in deriving explicit rate equations or searching for a better catalyst based on the theoretical insight.
When the aim is to derive a rate equation with eventual kinetic modelling for single-route mechanisms
with linear sequences, the analytical rate expressions can be obtained based on the theory of complex
reactions. For such mechanisms, a single rate limiting step might not be present at all and the common
practice of introducing such steps is due mainly to the convenience of using simpler expressions.
For mechanisms with a combination of linear and nonlinear steps or those just comprising non-linear
steps, the reaction rates are influenced by several steps depending on reaction conditions, thus a
reduction in complexity to a single rate limiting step can lead to misinterpretations. More widespread
utilization of a microkinetic approach when the reaction rate constants can be computed with
reasonable accuracy based on the theoretical insight, and availability of software for kinetic modelling,
when a system of differential equations for reactants and products will be solved together with
differential equations for catalytic species and the algebraic conservation equation for the latter,
will eventually make the concept of the rate limiting step obsolete.

Keywords: rate determining step; linear steps; nonlinear steps

1. Introduction
The kinetics of heterogeneous catalytic reactions has been the focus of numerous studies because
of its theoretical and practical importance [1–10]. Kinetic analysis was applied for decades to assist
reactor design and scaling up of various reactions relevant for oil refining and synthesis of basis and
specialty chemicals. More recently, because of a widespread application of so-called flow chemistry
to streamline pharmaceutical research and products, kinetic analysis also started to be more widely
utilized in the field of fine chemicals [11–13]. It was argued [11] that the framework of a mechanistically
based rate equation combined with in situ experimental data is useful for the interpretation of complex
reaction networks. Increasing complexity of the catalytic reactions, either relevant for oil refining or
pharmaceutical synthesis, poses some restrictions regarding incorporation of such complex mechanisms
into tractable rate equations.
Thus, another trend is to simplify complex reaction networks and assume that there is a limiting step,
the rate of which is a good approximation of the reaction rate of the whole network [14,15]. This approach
of a rate-determining step (RDS) became very popular in chemical reaction engineering, allowing the
derivation of kinetic equations for reaction mechanisms of differing complexity. Such an assumption
of a rate-determining step makes the rate expressions more tractable, facilitating the kinetic modelling
of mainly steady-state kinetics even at the expense of losing important mechanistic information.
Moreover, in several instances, without a substantial reduction in complexity, kinetic modelling can be
computationally very demanding, especially when coupled with transport phenomena [16].

Reactions 2020, 1, 37–46; doi:10.3390/reactions1010004 www.mdpi.com/journal/reactions

Reactions 2020, 3, x FOR PEER REVIEW 2 of 11
Reactions 2020, 1 38
modelling can be computationally very demanding, especially when coupled with transport
phenomena [16].
On the
On the other
other hand,
hand, the the concept
concept of of RDS
RDS was was suggested
suggested to to give
give fruitful
fruitful ideas
ideas forfor modifying
modifying the the
reaction conditions or design the catalyst. Subsequently, there have
reaction conditions or design the catalyst. Subsequently, there have been many theoretical papers been many theoretical papers
addressing how
addressing how to to determine
determinethe thestep
stepwhich
whichisisthe therate
ratedetermining
determining [17,18].
[17,18]. The The most
most popular
popular is
is probably the degree of rate control proposed by Campbell, based
probably the degree of rate control proposed by Campbell, based on the general principles of on the general principles of
differential sensitivity
differential sensitivity analysis
analysis to to determine
determine sensitivity
sensitivity of of the
theoutput
outputto toone
oneinput
inputparameter
parameter[19–25].
[19–25].
It was
It was argued
argued [16]
[16] that
that an
an approach
approach analogous
analogous to to electrical
electrical networks
networks is is even
even better
better suited
suited for for the
the
identification of the key steps determining the reaction rate allowing the
identification of the key steps determining the reaction rate allowing the derivation of accurate rate derivation of accurate rate
expressions even
expressions even for
for mechanisms
mechanisms with with nonlinear
nonlinear steps.
steps. Such
Such nonlinear
nonlinear stepssteps areare present
present not not only
only in in
heterogeneous catalytic reactions, such as, for example, a water gas shift reaction
heterogeneous catalytic reactions, such as, for example, a water gas shift reaction [16], decomposition [16], decomposition
of ammonia
of ammonia [26,27]
[26,27]orormethanol
methanol [28], butbut
[28], alsoalso
in organometallic
in organometallic catalysis. In the In
catalysis. latter
thecase,
latterthecase,
reaction
the
order in catalysts deviates from unity [5]. The formation of dimeric catalytic
reaction order in catalysts deviates from unity [5]. The formation of dimeric catalytic species, on the species, on the contrary,
results in results
contrary, the reaction
in theorder
reaction being below
order beingone, which
below is rather
one, whichrare [29–31].
is rather rare [29–31].
Contrary to the case of linear (Christiansen) sequences
Contrary to the case of linear (Christiansen) sequences of a single-route of a single-route reaction
reaction [5,32,33]
[5,32,33] for for
single-route mechanisms
single-route mechanismswith withnonlinear
nonlinearsteps,
steps,a general
a general expression
expression forforthethereaction raterate
reaction in steady-state
in steady-
and quasi-steady-state conditions cannot be derived [34]. When such
state and quasi-steady-state conditions cannot be derived [34]. When such derivation is possible, derivation is possible, the rate
the
expressions
rate expressionsbecome rather
become complicated
rather complicated to handle [5,35–37].
to handle [5,35–37].
To overcome
To overcomedifficulties
difficulties in deriving
in derivingexplicit rate expressions,
explicit a semi-empirical
rate expressions, kinetic polynomial
a semi-empirical kinetic
was proposed [38] as a substitute of analytical rate equations.
polynomial was proposed [38] as a substitute of analytical rate equations.
However, in
However, incatalysis
catalysisbyby solids or organometallic
solids or organometallic complexes, quite often
complexes, quiteeither
oftenthere are there
either nonlinear are
steps involved or the rate equations for even single-route mechanisms
nonlinear steps involved or the rate equations for even single-route mechanisms and obviously multi and obviously multi route
reactions
route do notdo
reactions have
not rate
havelimiting steps [34].
rate limiting steps [34].
It was recognized a long time ago thatfor
It was recognized a long time ago that formulti-route
multi-route (or(or
composite)
composite) reactions,
reactions, thethe
concept
conceptof theof
rate-controlling steps is not required [34,39], while in other cases it should
the rate-controlling steps is not required [34,39], while in other cases it should be considered with be considered with care,
as misinterpretation
care, as misinterpretationis easily possible.
is easily possible.
In the current work, several
In the current work, several cases of cases of complex
complex single-
single- and and multi-route
multi-route heterogeneous
heterogeneous catalytic
catalytic
reactions will be presented, highlighting an apparent danger of falling
reactions will be presented, highlighting an apparent danger of falling into a trap of using the into a trap of using the rate
rate
determining step,
determining step, which
which leads
leads to to confusion
confusion rather
rather than
than clarification
clarification of of reaction
reaction mechanisms.
mechanisms.

2. Three Step Sequence

2. Three Step Sequence
Let us consider first a three-step linear sequence (Figure 1)
Let us consider first a three-step linear sequence (Figure 1)

Figure
Figure 1. 1. Potential
Potential energy
energy diagram
diagram using
using Gibbs
Gibbs energy
energy and
and Gibbs
Gibbs activation
activation energy
energy for
for the
the reaction
reaction
S->P.
S->P. TT11–T
–T33represent
representtransition
transition states,
states, and I11-I
–I22intermediates,
intermediates,II00isisthe
thefree
freeform
form of
of catalyst.
catalyst. Adapted
Adapted
from
from [40].
[40].

The general
The general equation
equation for
for this
this three-step
three-step sequence
sequence in the
the case
case of
of all
all reversible
reversible steps
steps can
can be
be written
written
in aa form
in form of
of frequencies
frequencies of steps [6]
ω+1 ω+2 ω+3 −ω−1 ω−2 ω−3
r= ω+2 ω+3 +ω−3 ω+2 +ω−3 ω−2 +ω+3 ω+1 + ω−1 ω+3 +ω−1 ω−3 +ω+1 ω+2 + ω−2 ω+1 +ω−2 ω−1 Ccat (1)
 Reactions 2020, 3, x FOR PEER REVIEW 3 of 11

ω+1ω+2ω+3 − ω−1ω−2ω−3
r= Ccat (1)
ω+2ω
Reactions 2020, 1
+3 + ω−3ω+2 + ω−3ω−2 + ω+3ω+1 + ω−1ω+3 + ω−1ω−3 + ω+1ω+2 + ω−2ω+1 + ω−2ω−1
39

where r is the reaction rate, ω+1 is the frequency of step 1, etc., and Ccat is the catalyst concentration.
Therfrequencies
where is the reaction rate, ωare
of steps +1 is the frequency
obtained of stepthe
by dividing 1, etc.,
rate and Ccat is theofcatalyst
expressions concentration.
a particular step by the
Theconcentration
frequencies ofofsteps catalytic species in that expression. For example, in the case of thebyreaction
are obtained by dividing the rate expressions of a particular step the
concentration
mechanismofpresented
catalytic species
in Figure in that
2, the expression.
general form For ofexample, in the case
the Equation of the[6]
(1) gives reaction mechanism
presented in Figure 2, the general form of the Equation (1) gives [6]
(k+1CH2 k+2CC2 H4 k+3 − k−1k−2 k−3CC2 H6 )Ccat
r= (k+1 CH2 k+2 CC2 H4 k+3 −k−1 k−2 k−3 CC2 H6 )Ccat (2)
r = k k+2kk+3++k k−C3CC2 H6kk+2++k k−C3CC2 H6kk−2++k k+3kk+1 CCH2 ++ kk−1kk+3++k k−k1k−3CCC2 H6++k k+1CCH2kk+2CCC2 H4 ++ kk−2kk+1C
CH2 + k−2 k−1 (2)
+k k
+2 +3 −3 C2 H6 +2 −3 C2 H6 −2 +3 +1 H2 −1 +3 −1 −3 C2 H6 +1 H2 +2 C2 H4 −2 +1 H2 −2 −1

Figure 2. Three-step direct ethylene hydrogenation mechanisms.

Figure 2. Three-step direct ethylene hydrogenation mechanisms.
Thus, the frequency of the first step in the forward direction is k+1 CH2 , while for the reverse step
it wouldThus, the
be just k−1frequency
. When allofsteps
the first step in the forward
are irreversible, Equationdirection k+1Csimplified,
(2) can beiseasily H 2 , while for the reverse
giving

step it would beωjust ω k ω −1 . When all steps are k+1irreversible,

CH k+2 CC H k+3Equation
Ccat (2) cank+be
1 CHeasily
C Csimplified, giving
2 C2 H4 cat
r = ω+2 ω+3 ++ω1+3+ω2+1++3 ω+1 ω+2 Ccat = k k +k k 2 C +2 k 4 C k C = k+1 k+1 (3)
+2 +3 +3 +1 H +1 H +2 C H
2 2 2 4 1+ CH2 + k CH2 CC2 H4
ω+1ω+2ω+3 k+1CH k+2CC H k+3Ccat k+1CH C
+2
C H Ccat
+3 k

r= Ccat = 2
= 2 4 2 2 4

Itωfollows
+2ω+3 + ω+3ω+1 + ω+1ω+2
from Equation (3) that on the values of partial kpressures
+3 + k+3k+1 CH + k+1CH k+2CC H
k+2kdepending k of, for example,(3)
2 1 + +1 C + +1 C C
H
2 2
H
4
C2 H4
hydrogen, the reaction order can change from unity at low pressures, to zero at k+2high2 hydrogen
k+3 2 pressures.
The relative contribution of the last term in the denominator of Equation (3) k+1 CH2 CC2 H4 /k+3 in
It follows
comparison with twofromotherEquation
terms(3) that depending
defines the reactionon the towards
order values ofethylene.
partial pressures of, for example,
hydrogen,
This examplethe illustrates
reaction order can change
an apparent dangerfrom unity at
of defining thelow
ratepressures, to zero
and even more at high
turnover hydrogen
frequency
through just one rate limiting step without taking into account kinetic regularities. To highlight the need (3)
pressures. The relative contribution of the last term in the denominator of Equation
k+1CH 2 Call
to consider / k+in3 ainlinear
steps
C2 H 4
comparison with
catalytic two other
sequence eventerms defines
further, let usthe reaction
consider theorder towards
apparent ethylene.
activation
energy for theexample
This three-step mechanism
illustrates an (Equation
apparent (3)). In what
danger follows, the
of defining the term
rate “apparent” corresponds
and even more turnover
to the observed activation energy of a complex multistep reaction in the kinetic regime, which
frequency through just one rate limiting step without taking into account kinetic regularities. To should
nothighlight
be confused
the with
need the case when
to consider all the observed
steps kinetics
in a linear is influenced
catalytic sequence by thefurther,
even transport
let phenomena.
us consider the
A more simple case of the two-step sequence was addressed in the literature
apparent activation energy for the three-step mechanism (Equation (3)). In what follows, [41] using
thethe
term
definition of the apparent activation energy
“apparent” corresponds to the observed activation energy of a complex multistep reaction in the
kinetic regime, which should not be confused with the case when the observed kinetics is influenced
∂ ln r
by the transport phenomena. Ea,app = −R (4)
∂(1/T )
A more simple case of the two-step sequence was addressed in the literature [41] using the
anddefinition
giving of the apparent activation energy
ω+2 ω+1
Ea,app = Ea,1 + E (5)
ω+1 + ω+2 ω+1 + ω+2 a,2
Reactions 2020, 1 40

As follows from Equation (5), the apparent activation energy depends not only on the step with
the highest activation energy, but also on the contribution of the other step with a lower activation
energy. For the three-step sequence using Equations (3) and (4), one gets

∂
Ea,app = RT2 ∂T (ln k+1 + ln CH2 + ln k+2 + ln CC2 H4 + ln k+3 + ln Ccat −
(6)
ln(k+2 k+3 + k+3 k+1 CH2 + k+1 CH2 k+2 CC2 H4 ))

Some terms in Equation (6) can be easily differentiated

∂ ∂ E+1
(ln k0 +1 exp(−E+1 /RT ) = (ln k0 +1 − E+1 /RT ) = (7)
∂T ∂T RT2
Taking Equation (7) into account and also using a standard approach for the differentiation of a
complex function
∂ ln U ∂ ln U ∂U 1 ∂U
= = (8)
∂T ∂U ∂T T ∂T
one gets the final expression for the activation energy of a three step sequence

ω+2 ω+3 Ea,1 + ω+1 ω+3 Ea,2 + ω+1 ω+2 Ea,3

Ea,app = (9)
ω+2 ω+3 + ω+3 ω+1 + ω+1 ω+2

It can be shown that in only exceptional cases the apparent activation energy of the overall reaction
is determined by the activation energy of only one rate-limiting step in a steady-state sequence.

3. Four Step Sequence

As an example of such a sequence, the liquid-phase hydrogenation of aromatic compounds will
be considered. The reaction kinetics was extensively investigated previously in [42–46]. The following
generic scheme for hydrogenation of an aromatic compound A to the product B was proposed

1.*A + H2 ⇔ *AH2
2.*AH2 + H2 ⇔ *AH4
3.*AH4 ⇒ *Y
(10)
3 .*Y + H2 ⇔ *B (fast)
0

4.*B + A Ξ *A + B
A + 3H2 = B

where Y is cyclohexene or its derivative, AH2 and AH4 are intermediate complexes, step 30 is fast
because hydrogenation of cycloalkenes is much faster than aromatic compounds and step 4 is at
quasi-equilibrium.
A general equation for the four step sequence is [6]

ω+1 ω+2 ω+3 ω+4 − ω−1 ω−2 ω−3 ω−4

r= Ccat (11)
D
where
D = ω+2 ω+3 ω+4 + ω−1 ω+3 ω+4 + ω−1 ω−2 ω+4 + ω−1 ω−2 ω−3 +
+ω+1 ω+2 ω+3 + ω−4 ω+2 ω+3 + ω−4 ω−1 ω+3 + ω−4 ω−1 ω−2 +
(12)
+ω+4 ω+1 ω+2 + ω−3 ω+1 ω+2 + ω−3 ω−4 ω+2 + ω−3 ω−4 ω−1 +
+ω+3 ω+4 ω+1 + ω−2 ω+4 ω+1 + ω−2 ω−3 ω+1 + ω−2 ω−3 ω−4
Because of irreversibility of step (3), Equations (11) and (12) can be simplified
ω+1 ω+2 ω+3 ω+4
r= Ccat (13)
D
Reactions 2020, 1 41

D = ω+2 ω+3 ω+4 + ω−1 ω+3 ω+4 + ω−1 ω−2 ω+4 + ω+1 ω+2 ω+3 + ω−4 ω+2 ω+3 + ω−4 ω−1 ω+3 + ω−4 ω−1 ω−2 +
(14)
+ω+4 ω+1 ω+2 + ω+3 ω+4 ω+1 + ω−2 ω+4 ω+1

Step 4 is at quasi-equilibrium, and therefore the rates are fast in both directions. Further
simplifications of Equation (13) are thus possible by dividing the numerator and the denominator by ω+4 ,
neglecting subsequently the terms ω+1 ω+2 ω+3 /ω+4 and ω−3 ω+1 ω+2 /ω+4 . Then the following holds
ω+1 ω+2 ω+3
r= Ccat (15)
(ω+2 ω+3 + ω−1 ω+3 + ω−1 ω−2 )(1 + ωω+−44 ) + ω+1 ω+2 + ω+3 ω+1 + ω−2 ω+1

Replacing frequencies in Equation (15) with the explicit expressions, one gets

k+1 CH2 k+2 CH2 k+3

r= CB
Ccat (16)
(k+2 CH2 k+3 + k−1 k+3 + k−1 k−2 )(1 + K4 CA ) + k+1 CH2 k+2 CH2 + k+3 k+1 CH2 + k−2 k+1 CH2

where K4 = k+4 /k−4 . For a binary mixture of the reactant and substrate, it is possible to use mole
fractions instead of concentrations. Moreover, quite often partial pressures of hydrogen are applied
instead of concentrations, resulting in another form of the rate equation

k0+1 PH2 k0+2 PH2 k+3

r= 1−NA Ccat (17)
(k0+2 PH2 k+3 + k−1 k+3 +k−1 k−2 )(1+ K )+k0+1 PH2 k0+2 PH2 +k+3 k0+1 PH2 + k−2 k0+1 PH2
4 NA

where NA is the mole fraction of the reactant. Equation (16) contains the modified rate constants
k0+1 ; k0+2 as instead of hydrogen concentration in the liquid phase, the pressure of hydrogen is used.
Equation (17) presented in a slightly different form
k0+1 k0+2 k+3
P N C
k+3 k0+1 +k−2 k0+1 +k0+2 k+3 H2 A cat
r= k−1 k+3 +k−1 k−2
−1
( k−1 k+3 +k−1 k−2 )(1−NA )
−1
k0+2 k+3 (1−NA ) k0+1 k0+2 (18)
N
k+3 k0+1 +k−2 k0+1 +k0+2 k+3 A
P +
H2 (k k0 +k k0 +k0 k )K ) P H2 (k k0 +k k0 +k0 k )K + k k0 +k k0 +k0 k
+ PH2 NA +NA
+3 +1 −2 +1 +2 +3 4 +3 +1 −2 +1 +2 +3 4 +3 +1 −2 +1 +2 +3

was derived in [43] using a more tedious procedure, namely applying directly the steady-state conditions

r+1 − r−1 = r+2 − r−2 = r+3 (19)

as well as the quasi-equilibrium for step 4 and finally the balance equation (i.e., the sum of all coverages
is equal to unity).
All steps in Equation (10) are needed to explain the observed kinetic regularities, because it was
demonstrated that at low hydrogen partial pressures, the reaction order in hydrogen can exceed unity,
which is possible when k−1 , 0, while at high pressures the reaction kinetics obeys frequently observed
zero orders in the substrate and hydrogen. In the latter case, the overall rate is determined by the
isomerization of the adsorbed AH4 species. The surface of the catalyst is completely covered with this
complex and the reaction rate ceases to depend on either hydrogen pressure or the concentration of
the substrate.
Apparently, the concept of a single rate-determining step is not able to account for a rich kinetic
behavior, observed experimentally in hydrogenation of aromatics.

4. Oxidative Dehydrogenation of Ethanol: A Multi-Route Mechanism with Nonlinear Steps

The mechanism and kinetics of oxidative dehydrogenation of ethanol over gold catalysts was
recently reported [47]. DFT calculations indicated that the activation of molecular oxygen is facilitated
in the presence of ethanol acting as a hydrogen donor. As a result of hydrogen abstraction from the
behavior, observed experimentally in hydrogenation of aromatics.

4. Oxidative Dehydrogenation of Ethanol: A Multi-Route Mechanism with Nonlinear Steps

The mechanism and kinetics of oxidative dehydrogenation of ethanol over gold catalysts was
Reactions 2020, 1 42
recently reported [47]. DFT calculations indicated that the activation of molecular oxygen is facilitated
in the presence of ethanol acting as a hydrogen donor. As a result of hydrogen abstraction from the
donor
donorleading
leadingto tothe
theformation
formationofofan
anOOH
OOHintermediate,
intermediate,the
thedioxygen
dioxygenundergoes
undergoesdissociation
dissociationon
onthe
the
catalyst
catalystsurface.
surface.The
Thescheme
schemeofofthe
thereaction
reactionmechanism
mechanismisisgiven
givenbelow
below

N(1a) N(1b) N(1c)

1. O2+*ΞO2* 1 1 1
2. EtOH+*ΞEtOH* 2 2 2
3. EtOH* + O2*↔EtO*+OOH* 2 1 2
4. OOH*+*→O*+OH* 2 1 1
5. O*+EtO*→AcH+*+OH* 2 2 2 (10)
(20)
6. 2OH*↔O*+H2O+* 2 2 2
7a. 2O*→O2*+* 1 0 0
7b. EtOH*+O*→EtO*+OH* 0 1 0
7c. O*+OOH*→O2*+OH* 0 0 1
N(1) 2EtOH+O2→2AcH+2H2O

In
In(20),
(20), on
on the
the right
right hand
hand sideside of
of the
the equations
equations for for the
the steps
steps (i.e.,
(i.e., 11 to
to 7c),
7c), the
the stoichiometric
stoichiometric
numbers (i.e., 0, 1, 2) along alternative routes N (1a) - N(1c) are given [32]. These numbers can be equal
numbers (i.e., 0, 1, 2) along alternative routes N(1a) - N(1c) are given [32]. These numbers can be equal
to
tozero,
zero,ififaaparticular
particularstepstepisisnot
notinvolved
involvedin inthe
thereaction
reaction mechanism.
mechanism. In InEquation
Equation(20), (20),EtOH
EtOHstands
stands
for ethanol, while AcH represents acetaldehyde and * denotes
for ethanol, while AcH represents acetaldehyde and * denotes a surface site. a surface site.
According
According to to the
the DFT
DFT calculations
calculations [47]
[47] illustrated
illustrated in in Figure
Figure 3,3, the
the largest
largest activation
activation barrier
barrier
corresponds
corresponds to step 3 in Equation (20), and thus superficially it can be considered inthe
to step 3 in Equation (20), and thus superficially it can be considered in theconventional
conventional
approaches
approachesas asthe
therate
ratelimiting
limitingstep.
step.However,
However,the theactivation
activationenergy
energyof ofthe
thesame
samestepstepininthe
thereverse
reverse
direction
direction is very
is very low and
lowPEER step
andREVIEW 3 can even be viewed to be close to the quasi-equilibrium.
step 3 can even be viewed to be close to the quasi-equilibrium.
Reactions 2020, 3, x FOR 7 of 11
From the considerations above on the apparent activation energy of the three-step sequence with
linear steps, it is clear that the apparent activation energy and the reaction rate depend on the
contribution of all steps in the mechanism, which could be treated using the steady-state
approximation. This approach is possible because of the specific features of the reaction mechanism
comprising only nonlinear steps and thus allowing derivation of an analytic rate expression. Such
derivation was done in [47] based on the DFT computed reaction energies assuming quasi-equilibria
for steps 1 and 2, irreversibility for steps 4 and 5 and reversibility for steps 3 and 6.

Figure
Figure 3. The minimum
3. The minimum energy path for ethanol (EtOH) dehydrogenation. The black and orange bars
correspond
correspond to minima
to minimaandandtransition
transitionstates,
states,respectively.
respectively.* denotes
* denotesadsorbed
adsorbedspecies,
species,while
while(g)(g)
refers to
refers
gas phase
to gas species.
phase Square
species. brackets
Square enclose
brackets a transition
enclose statestate
a transition structure where
structure ‘ - -’ marks
where the bond
‘ - -’ marks the being
bond
broken. Reproduced
being broken. with permission
Reproduced from [47].
with permission from [47].

From the viewpoint

From the considerationsof theabove
globalon the apparent
reaction kinetics,activation energy
not only steps 3-6ofare
the three-step
important butsequence
also the
with
final step in the mechanism, step 7, reflecting the fate of atomically adsorbed oxygen. Therefore,on
linear steps, it is clear that the apparent activation energy and the reaction rate depend the
three
contribution of all steps in the mechanism, which could be treated using the steady-state
options are possibly influencing the stoichiometric numbers of other steps. Step 7a in the route N(1a) approximation.
This approachtoisrecombination
corresponds possible because of the specific
of atomic oxygen,features of therecombination
while such reaction mechanismin stepcomprising
7c (route Nonly
(1c) )
nonlinear steps and thus allowing derivation of an analytic rate expression. Such derivation
involves a reaction with a peroxy species OOH. In the route N(1b), atomically adsorbed oxygen assists was done
in [47]abstraction
in the based on the DFT computed
of hydrogen from thereaction energies assuming quasi-equilibria for steps 1 and 2,
substrate.
irreversibility
Derivation of the rate expression (per molefor
for steps 4 and 5 and reversibility of steps
oxygen)3 and
for6.the route N(1b) was described in [47],
givingFrom the viewpoint of the global reaction kinetics, not only steps 3–6 are important but also
the final step in the mechanism, step 7, reflecting the fate of atomically adsorbed oxygen. Therefore,
k k KKC C +3 +4 1 2 O2 EtOH
three options are possibly influencing the stoichiometric k numbers of other steps. Step 7a in the route
(k+4 + k−3 +7 b
CEtOH )
(1b ) k+5
rN = (11)
2k+7 b K 2CEtOH k+3 k+4 K1CO2 2 k+3 k+4 K1 K 2CO2 CEtOH k−6 k+3 k+4 K1CO2 CH 2O k+3 K1 K 2CO2 CEtOH 2
(1 + K 2CEtOH + K1CO2 + + + ( + )+ )
k+5 k+7 b k k+7 b k+7 b k
k+7 b (k+4 + k−3 CEtOH ) + 6 k+4 + k−3 CEtOH k+7 b (k+4 + k−3 CEtOH ) k+4 + k−3 +7 b CEtOH
k +5 k +5 k+5 k +5

Just for illustration purposes, let us consider a case when step 3 is at quasi-equilibrium and step
6 is irreversible. Equation (21) is then transformed to
Reactions 2020, 1 43

N(1a) corresponds to recombination of atomic oxygen, while such recombination in step 7c (route N(1c) )
involves a reaction with a peroxy species OOH. In the route N(1b) , atomically adsorbed oxygen assists
in the abstraction of hydrogen from the substrate.
Derivation of the rate expression (per mole of oxygen) for the route N(1b) was described
in [47], giving
k+3 k+4 K1 K2 CO CEtOH
2
k
(1b) (k+4 +k−3 +7b CEtOH )
k+5
rN = v
u 2 (21)
2k+7b K2 CEtOH k+3 k+4 K1 CO t k+3 k+4 K1 K2 CO CEtOH k−6 k+3 k+4 K1 CO CH O k+3 K1 K2 CO CEtOH
(1+K2 CEtOH +K1 CO2 + k+5
+ k
2 + k2 ( k
2 + k
2 2 )+ k
2 )
k+7b (k+4 +k−3 +7b CEtOH ) +6 k+4 +k−3 +7b CEtOH k+7b (k+4 +k−3 +7b CEtOH ) k+4 +k−3 +7b CEtOH
k+5 k+5 k+5 k+5

Just for illustration purposes, let us consider a case when step 3 is at quasi-equilibrium and step 6
is irreversible. Equation (21) is then transformed to

(1b) K3 k+4 k+5 K1 K2 CO2 CEtOH /k7b

rN = r 2 (22)
2k+7b K2 CEtOH K3 k+4 k+5 K1 CO k k K K K C K3 K1 K2 k+5 CO CEtOH
(1+K2 CEtOH +K1 CO2 + + 2 + 2 ( +4 +5 1 2 3 O2 )+ 2 )
k+5 k2 +7b CEtOH k+6 k+7b k+7b

For two other options also considering the quasi-equilibria of the step 3, the rates are for the
routes N(1b)
r
2k+7c K3
k+4 k+5 /2k+7c k+5
K1 K2 CO2 CEtOH
(1c)
rN = r r 2 (23)
k 2k+7c K3 k+4 k+5 2k+7c K3 0.25
(1+K2 CEtOH +K1 CO2 + k +4 +(1+k+5 /2k+7c ) k+5
K1 K2 CO2 CEtOH + k+6 k+7c
( k K1 K2 CO2 CEtOH ) )
+7c +5

and N(1a) , respectively

2k k 2/3
k2 +5 /k+7a ( +27a +4 K1 K2 K3 CO2 CEtOH )
(1c) k +5
rN = r 1/6 1/3 2 (24)
2k+7a k+4 1/3 k k+4 k2 + 5 k2
(1+K2 CEtOH +K1 CO2 +( K1 K2 K3 CO2 CEtOH ) (1+ 2k+5 + ( ) )+( 2k +k5 ) (K1 K2 K3 CO2 CEtOH )2/3 )
k2 + 5 +7a k+6 2k+7a k+4 +7a +4

illustrating that the rate expression and even the kinetic regularities which follow from the corresponding
rate expressions are very sensitive to the chemistry of step 7 and the rate constant of this step.
The mechanism N(1a) is less probable compared to other alternatives considering a high activation
barrier anticipated for this step [47], while other options in principle are possible. For kinetic modelling
in [47], a feasible channel of atomically adsorbed oxygen consumption with a low activation energy
barrier was considered to be step 7b (Equation (20)).

5. Conclusions and Outlook

Apparently, the concept of the rate limiting will continue to be utilized in the future. This concept
is useful as a part of the education of future specialists in chemical reaction engineering and catalyst
development. For simple single-route reaction mechanisms, the application of the rate-determining
step along with the quasi-equilibria of other steps results in easily derived rate equations. For more
complex cases with several linear steps, the general approach based on the theory of complex reactions
of Horiuti–Temkin allows the derivation of the corresponding rate equations. Apparent difficulties in
doing this, as illustrated above for the four-step sequence, often result in a reductionistic approach
assuming a rate-determining step either based on chemical intuition or a more rigorous theoretical
analysis based on quantum chemical calculations.
There are cases when the rate equation for linear sequences with a small number of steps was
not derived and a system of differential equations was solved even if the rate equation for the steady
-state system can be readily derived. This was done, for example in [48], when a solver of differential
equations was used for a four step sequence of the Fujiwara–Moritani reaction (Figure 4), unfortunately
not reporting how the balance equation for catalytic species was taken into account,
theoretical analysis based on quantum chemical calculations.
There are cases when the rate equation for linear sequences with a small number of steps was
not derived and a system of differential equations was solved even if the rate equation for the steady
-state system can be readily derived. This was done, for example in [48], when a solver of differential
Reactions
equations 1
2020,was used for a four step sequence of the Fujiwara–Moritani reaction (Figure 4), 44

unfortunately not reporting how the balance equation for catalytic species was taken into account,

Figure 4.4.Reaction
Figure Reactionmechanism
mechanismforfor
thethe Fujiwara–Moritani
Fujiwara–Moritani reaction
reaction [48]. Published
[48]. Published by Theby TheSociety
Royal Royal
Society of Chemistry.
of Chemistry.

For a particular
For particular case
case of the mechanism
mechanism in Figure
Figure 4, 4, the rate equation
equation can be easily derived
derived as this
mechanismisisaaspecial
mechanism specialcase
caseofofEquations
Equations(11)
(11)and
and(12)
(12)with
withirreversible
irreversible steps
steps 2 and
2 and 3 simply
3 simply resulting
resulting in
in
ω+1 ω+2 ω+3 ω+4 Ccat
r=
ω2 ω3 ω4 + ω−1 ω3 ω4 + ω1 ω2 ω3 + ω+ω1ω−4+2ωω2+ω3ω
3+ +4C
ωcat
−4 ω−1 ω3 + +ω4 ω1 ω2 + ω3 ω4 ω1
(25)
r= (15)
ω2ω3ω4 + ωthe
Or, after introducing −1ω 3ω4 + ω
explicit 1ω2ω3 + ω−for
expressions 4ω2theω3 frequencies
+ ω−4ω−1ω3 of++ ω4ω1ω2 + ω3ω4ω1
steps
Or, after introducing the explicit expressions
k+ k+ k+ k+ C for
C the
C frequencies
C of steps
r=
1 2 3 4 ace tan ilide acrylate BQ cat
k+2 k+3 k+4 Cacrylate CBQ +k−1 k+3 k+4 Cacrylate CBQ +k+1 k+2 k+3 Cace tan ilide Cacrylate + k−4 k+2 k+3 Cacrylate +k−4 k−1 k+3 Cacrylate +k+1 k+2 k+4 Cace tan ilide CBQ + k+1 k+3 k+4 Cace tan ilide Cacrylate CBQ (26)

In a more general case, when the reaction mechanisms comprise linear and nonlinear steps
without any rate-limiting ones, derivation of an explicit rate equation can be too tedious. Instead,
a comparison between the experimental and calculations should be done in an implicit form using a
system of differential equations considering also an algebraic balance equation for the catalytic species.
Availability of computer programs with a customer written subroutine comprising a set of elementary
reactions will pave the way for eventual marginalization of the concept of the rate-determining step in
the kinetic modelling of complex heterogeneous catalytic reactions.

Funding: This research received no external funding.

Conflicts of Interest: The author declares no conflict of interest.

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