Applied Catalysis A: General 504 (2015) 220227

Contents lists available at ScienceDirect

Applied Catalysis A: General

journal homepage: www.elsevier.com/locate/apcata

Unraveling the mechanism of chemical reactions through

thermodynamic analyses: A short review
F.C. Meunier a, , J. Scalbert b , F. Thibault-Starzyk b
a
Universit Lyon 1, CNRS, UMR 5256, IRCELYON, Institut de recherches sur la catalyse et lenvironnement de Lyon, 2 avenue Albert Einstein, 69626
Villeurbanne, France
b
Laboratoire Catalyse et Spectrochimie, UMR 6506, CNRS-ENSICAEN, Universit de Caen, 6 Bd. Marechal Juin, 14050 Caen, France

a r t i c l e

i n f o

Article history:
Received 21 September 2014
Received in revised form
10 December 2014
Accepted 14 December 2014
Available online 23 December 2014
Keywords:
Reaction mechanism
Thermodynamics
Equilibrium constant
Reaction quotient
Approach to equilibrium

a b s t r a c t
Basic thermodynamic analyses can provide in-depth knowledge of the mechanism of chemical reactions.
This short review recalls rst the denitions of the approach-to-equilibrium , the reaction quotient Q
and the thermodynamic equilibrium constant K. Thereafter, four case studies specically dealing with
gas-phase heterogeneously catalyzed reactions are reviewed: (i) alkane hydroisomerization, (ii) NO oxidation during the selective catalytic reduction of NOx with propene, (iii) the steam reforming of methanol
and (iv) ethanol condensation to butanol. These examples illustrate in different manners how a reaction
mechanism can be supported or rejected based on rather simple analyses of the concentrations of reactants and products. While the examples used here are all referring to catalyzed reactions, it must be
emphasized that the method can be applied to non-catalytic systems.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Chemical processes can be made more efcient by better understanding the various reaction steps involved in the conversion of a
given feedstock into the desired products so that each step can be
(i) promoted by a suitable catalyst and/or (ii) carried out under
appropriate operating conditions as to push away the limiting conversion associated with the thermodynamics of the system. Insights
into reaction mechanisms can be obtained, for instance, via studying the nature (e.g. acid/base [1], redox [2]) and structure [3,4] of
the catalytic sites or by in situ and operando spectroscopy [58].
Thermodynamics is routinely used as a tool to determine favorable reaction conditions so that high yields of products can be
achieved. However, it is less common to use thermodynamics to
support or rule out a particular reaction step. The power of this
method is recalled here, showing how details of complex reaction
mechanisms can be unraveled. The method is based on the comparison of the proportions of reactants and products present in the
reactor efuent to various thermodynamic equilibrium constants
pertaining to the system.
This short review recalls rst the denitions of the reaction
quotient Q and the thermodynamic equilibrium constant K. The

calculation of these numbers will be detailed over a few examples, taken primarily from published work of the authors. The direct
comparison of these two numbers (or the value of the ratio Q/K = ,
so-called approach-to-equilibrium parameter) can be used to
support or reject the relevance of a reaction step in a complex
scheme.
It is important to stress that the method described here does not
involve the thermodynamics of adsorbed species and therefore no
inference can be made as to the nature and concentration of surface
intermediates. The examples used in the present paper are dealing
with gas-phase compounds and heterogeneous catalysis, but it is
crucial to realize that the method can be applied to non-catalytic
reactions and condensed systems, as long as activity coefcients
are available.
The insights obtained in each of the examples enabled to derive
better catalytic formulations or guide future catalyst development
and improved reaction conditions. Numerical examples of calculus
are given so that a reader not familiar with this topic should fully
understand the whole procedure. Most calculations can actually
be done on user-friendly commercially available thermodynamic
softwares such as HSC Chemistry .

2. Denitions
Part of the special issue of Applied Catalysis A: General dedicated to Prof J. Vedrine.
Corresponding author. Tel.: +33 472445468; fax: +33 472445365.
E-mail address: fcm@ircelyon.univ-lyon1.fr (F.C. Meunier).
http://dx.doi.org/10.1016/j.apcata.2014.12.028
0926-860X/ 2014 Elsevier B.V. All rights reserved.

The reaction quotient Q for a given reaction is the ratio between

the product of the (dimensionless) chemical activity of each of the

F.C. Meunier et al. / Applied Catalysis A: General 504 (2015) 220227

221

products to that of the reactants, each raised to the power of the

corresponding stoichiometric coefcient [9]. For reactions involving only gaseous compounds at moderate pressure, the chemical
activities can be approximated to the pressures of reactants normalized to the standard pressure P = 1 bar (i.e. ideal case for which
the gas fugacities are unity). Examples of expressions for Q are given
below for some of the reactions discussed here [Eqs. (1) (3)].
n butane  isobutane

Q1 =

Pisobutane
Pnbutane

n-butane  H2 + 1-butene

Q2 =

PH2 P1-butene

(1)

(Pn-butane P )

(2)

2 acetaldehyde + 2 H2  butanol + H2 O Q3

PH2 O Pbutanol P 2

Pacetaldehyde PH2

2

(3)

If no reaction product is present in the system (typically at the

start of the reaction in a batch reactor or at the front of the bed in a
plug ow reactor), the reaction quotient Q is equal to zero. If the system under study has reached the thermodynamic equilibrium the
value of the reaction quotient is equal, by denition, to the reaction
equilibrium constant K [Eq. (4)]. The value of K can be determined
through the knowledge of the standard Gibbs free energy of reaction r G at the temperature considered, which is tabulated for
common reactions and can be calculated in most thermodynamic
softwares.
Qequilibrium = K = exp

  G 
r

(4)

RT

The approach-to-equilibrium (noted ) is the ratio between Q

and K [Eq. (5)] and takes a maximum value of one as the system
reaches equilibrium. The approach-to-equilibrium is commonly
used as a means to obtain forward rates of reaction when the extent
of backward reaction becomes signicant [10]. The variation of
Gibbs free energy of reaction r G can be written as follows [Eq. (6)]:
=

Q
K

r G = r G + RT ln Q = RT ln

(5)
Q
= RT ln 
K

(6)

The change of the Gibbs free energy of reaction must remain

equal to or lower than zero at all stages of a spontaneous chemical
conversion of the system. Therefore, the value of the approach-toequilibrium  must remain lower or equal to unity, i.e.  = Q/K 1.
This is schematically represented in Fig. 1, in which the open circles
are associated with allowed evolutions of the system, while the
states in the red shaded zone are forbidden transformations.
The above paragraph recalls that the Gibbs free energy of the
system at any point of a spontaneous transformation cannot be
higher than its initial value. This is the realm of thermodynamics.
This statement is not contradictory with the fact that at any time
a minute fraction (determined by statistical thermodynamics) of
the molecules will have a sufciently high energy to overcome an
activation barrier to form the products. This fraction of molecules
that can react will be increased and so will be the reaction rate
if the activation barrier of the transformation can be lowered by
using a catalysts or a suitable solvent. This is the realm of kinetics.
The level of kinetic analysis used in the following examples is
basic, mostly consisting in measuring the concentrations of reactants and products. Detailed kinetic analyses (e.g. based on the
determination of reaction orders, primary and secondary reaction
products, microkinetic models) are also a powerful tool to unravel
reaction mechanism, but are not the point of the present contribution.

Fig. 1. Gibbs free energy of reaction as a function of the approach-to-equilibrium .

Only transformations associated with  1 are allowed.

3. Case studies
The calculation of  requires the determination of the reaction
quotient Q, which implies measuring the partial pressure (or concentration) of each of the species appearing in the stoichiometric
equation. If a reactant or product is in large excess, then the evolution of the reaction quotient can be satisfactorily monitored by
only considering the variation of the concentration of the other
compounds.
This is exemplied in the rst two case studies described below
dealing with alkane hydroisomerization and NOx oxidation, for
which the H2 and O2 concentrations, respectively, were considered to be constant. The thermodynamic analysis was there merely
reduced to comparing two-term ratios (i.e. [A]/[B]) of pairs of concentrations of reactant and/or products.
The third case study dealing with methanol steam reforming
shows how the thermodynamically relevant reaction pathway can
be readily determined from the comparison between the measured
molar fractions and those calculated at the thermodynamic equilibrium.
The nal case study dealing with ethanol condensation involves
the analysis of an intermediate reaction step based on the exact
determination of the reaction quotient Q. The utilization of equilibrium diagrams is shown to be a useful guide in the search of
possible reaction pathways and the rejection of forbidden routes.
3.1. Alkane hydroisomerization
Solids derived from tungsten and molybdenum carbides and
oxides can be alternative to noble metals to catalyze reactions
such as the reverse watergas shift and alkane hydroisomerization [1114]. The nature of the reaction mechanism of alkane
hydroisomerization over molybdenum oxide-based catalysts had
been a matter of debate. Katrib et al. [15] and Matsuda et al.
[16] had proposed that a traditional bifunctional mechanism
operated, involving alkenes as reaction intermediates. On the
contrary, Bouchy et al. [17] had proposed a metallacyclobutane
intermediate-based mechanism.
The hydroisomerization of n-butane to isobutane [Eq. (1)] over
reduced MoO3 provided a case study in which thermodynamics
enabled to positively determine both the reaction mechanism and
the rate-determining step (RDS) [18]. MoO3 is not active for this
reaction and the catalytically active phase (thought to be an oxyhydroxide of molybdenum [19]) is gradually formed under the
reaction stream at 350 C (Fig. 2). Note that the insertion of carbon

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F.C. Meunier et al. / Applied Catalysis A: General 504 (2015) 220227

Scheme 1. Reaction equilibria () and rate-determining step (RDS) relevant to

butane hydroisomerization over reduced MoO3 at 350 C. All the C4 molecules drawn
in the scheme refer to gas-phase species. (Adapted from Ref. [18].)

Fig. 2. Isobutane and butene yields during the reductive activation of MoO3 at
350 C. (a) isobutane, (b) trans-2-butene, (c) cis-2-butene, (d) 1-butene and (e)
isobutene. Feed: 7% n-butane in H2 , at ambient pressure. (Adapted from Ref. [18].)

in the catalyst structure (to form an oxicarbide) is detrimental to

the selectivity, leading to butane hydrogenolysis to methane [20].
The concentration of the various butenes, potential reaction
intermediates produced by dehydrogenation of n-butane [Eq. (2)
for the case of 1-butene], could be accurately measured at the reactor exit, despite being present at levels more than two and three
orders of magnitude lower than that of isobutane and n-butane,
respectively (Fig. 2). The catalytic experiments were carried out in
a large excess of dihydrogen, the concentration of which could be
considered as constant.
For the sake of brevity only the ratios of the hydrocarbon concentrations were considered and reported at various time on stream
in Table 1, since the concentration of H2 was essentially constant
throughout the experiment. The corresponding ratios at the thermodynamic equilibrium are reported in the last column of Table 1.
1-butene, cis-butene and trans-butene were quickly equilibrated
and are not discussed any further [18].
Steady-state experimental ratios (n-butane/1-butene) and
(isobutane/isobutene) were equal to those associated with the
dehydrogenation thermodynamic equilibria within the experimental error (Table 1). This indicates that the hydrogenation and
dehydrogenation reactions were fast and not rate-limiting, if the
bifunctional mechanism applied. The phase responsible for these
metal-like reactions has been proposed to be molybdenum dioxide
MoO2 , which exhibits a metallic band structure with delocalized
electrons [21].
On the contrary, the skeletal isomerization between butenes and
isobutene had not reached equilibrium (Table 1) and was proposed
as being the RDS. This assumption was subsequently conrmed by
the fact that the addition of an acidic microporous aluminophosphate (CoAlPO-11), a known catalyst for the selective isomerization
of alkenes [22], led to a large enhancement of the butane hydroisomerization activity when mechanically mixed with MoO3 [23].
It must be noted that CoAlPO-11 itself was not active for butane
hydroisomerization.
In conclusion, our approach enabled determining the main
reaction mechanism of n-butane hydroisomerization over reduced
molybdena, which is summarized in Scheme 1. It must be stressed
that no labeled compounds were used in this study, as is often the
case for mechanistic investigations on similar systems [24].
The cases of n-pentane and n-hexane were also investigated
[23]. The same bifunctional mechanism operated, with the main

difference being that the RDS was no longer the skeletal isomerization, but instead the dehydrogenation/hydrogenation steps were
determining the overall rate of the reaction [23].
3.2. Oxidation of NO to NO2 during the selective reduction of NOx
with propene
The selective catalytic reduction of NO with propene over alumina provided an example in which the long-thought-crucial direct
oxidation of NO with O2 to give NO2 [Eq. (7)] was actually found to
be irrelevant [25].
NO + 0.5 O2  NO2

(7)

The thermodynamic analysis was focused on the NO2 /NO ratio,

as O2 was in great excess and its concentration was essentially constant throughout the experiment. The NO2 /NO ratio above a certain
value of pseudo-contact time W/F (weight to ow ratio) was far
greater than that associated with the thermodynamics of the reaction described by [Eq. (7)] (Fig. 3). Such high NO2 /NO ratios are
thermodynamically forbidden, if the relevant route for NO2 formation were to be that described by the direct oxidation [Eq. (7)].
Several other catalysts based on alumina led to similar observations
[26,27].
Another mechanistic route enabling higher NO2 /NO ratios must
therefore exist. A possible pathway involves the formation and

Fig. 3. Selective catalytic reduction of NO using propene over alumina at 540 C

as a function of the W/F: NO2 to NO ratio (a) experimental and (b) at the thermodynamic equilibrium of the reaction NO + 1/2 O2  NO2 (). Feed: 500 ppm
NO + 500 ppm C3 H6 + 2.5% O2 in Ar. (Reprinted from Ref. [25].)

F.C. Meunier et al. / Applied Catalysis A: General 504 (2015) 220227

223

Table 1
Ratios of the concentrations of various C4 compounds observed during the activation of MoO3 under 7% n-butane + 93% H2 at 350 C and ambient pressure. (adapted from
Ref. [18]).
Molar ratios
Dehydrogenation
n-butane/1-butene
Isobutane/isobutene
Isomerization
Isobutene/1-butene
n-butane/isobutane
a
b

1h

6h

Steady-state at 350 Ca

Thermodynamic equilibrium ratio at 350 Cb

16000
0.045

7000
17

6000 800
500 80

6600
470

0.27
1.6 106

3.3
120

1.2 0.2
9.3 1

8.12
1.73

The average value for the three data points after 20 h is reported.
Calculated using the HSC software (version 4.1, Outokumpu Research Oy, Pori, Finland, A. Roine).

Fig. 4. Effect of the W/F on the C3 H6 -SCR of NO over Ag/Al2 O3 at 590 C: NO2 /NO
experimental ratio (o) and theoretical thermodynamic ratio (dotted line). Feed:
0.05% NO + 0.05% C3 H6 + 2.5% O2 /He. (Reprinted from Ref. [26].)

oxidation of organonitrogen compounds, which have often been

suggested as potential reaction intermediates [28]. The nature and
concentration of such compounds are yet unclear. Nitromethane
was selected as a model compound, since its thermodynamic
potentials are readily available to calculate the standard Gibbs free
energy of the reactions of interest [Eqs. (8) and (9)].
C3 H6 + 1.5O2 + 2NO  2CH3 NO2 + CO
CH3 NO2 + 1.75O2  NO2 + CO2 + 1.5H2 O

Fig. 5. The inuence of W/F on the product compositions at T = 300 C over

a CuZnZrAlO catalyst, m = equilibrium excluding CO from calculations,
n = equilibrium including CO in calculations (H2 O/CH3 OH = 1.3, P inert diluent = 55 kPa, Ptotal = 101 kPa). (Adapted from Ref. [31].)

The case studies described in Section 3.1 and 3.2 have underlined
how detailed mechanistic insights could be obtained by simply
considering the two-term ratios of the concentrations of a couple

r G (540 C) = 298 kJ mol1

r G (540 C) = 734 kJ mol

The thermodynamics of formation of nitromethane and its combustion to NO2 are largely favorable at the temperature of reaction
of 540 C, while the standard Gibbs free energy of the direct oxidation [Eq. (7)] at the same temperature is about + 4 kJ mol1 . The true
intermediates and reaction pathways are likely to be more complex, but these calculi show that organonitrogen-based routes can
afford high concentration of NO2 at high temperatures, contrary to
the case of the direct oxidation.
Some rational bases behind the thermodynamic relevance of
organonitrogen routes are that (i) the resulting intermediate is
much more stable than the highly energetic NO radicals [Eq. (8)], (ii)
the formation of highly stable water and CO2 provided an energy
(enthalpy) sink during oxidation [Eq. (9)] and (iii) the larger number
of molecules on the product side increased entropy [Eq. (9)].
Similar data collected over a silver-promoted alumina were
furthermore interesting because the level of conversion could be
varied to a larger extent when changing the pseudo-contact time
(Fig. 4). The NO2 /NO ratio rapidly and largely exceeded the thermodynamic limit associated with direct oxidation [Eq. (7)] with
increasing W/F. The NO2 /NO ratio then decreased and eventually
reached the value associated with the thermodynamic equilibrium
of the direct oxidation [Eq. (7)]. It was proposed that the NO2 rapidly
formed via the organonitrogen pathway [Eqs. (8) and (9)] and was
subsequently slowly decomposed to NO and O2 according to the
direct route [Eq. (7)], once propene had been fully consumed [26].

(8)
1

(9)

of reactant and/or products. The latter example even showed

that NO2 formation/decomposition occurred via two very different
routes depending on whether propene was present or not. It also
proved that a catalytic function able to oxidize directly NO to NO2
was not a pre-requisite to obtain an effective catalyst to reduce NO
with propene. On the contrary, such strong oxidizing centers lead
to unselective propene combustion.
3.3. Methanol steam reforming
The selectivity to CO2 is crucial during the steam reforming of
methanol to maximize the yield of H2 and limit the formation of CO,
which can poison fuel cell electrodes [29,30]. The steam reforming
of methanol [Eq. (10)] over CuZnZrAlO catalyst provided an
example of a system in which thermodynamics enabled discarding a reaction pathway [31]. A critical question was whether or
not CO was a primary reaction product, which would be formed
prior to CO2 [Eq. (11)] and would then be converted to CO2 via the
watergas shift reaction [Eq. (12)].
CH3 OH + H2 O CO2 + 3H2

(10)

CH3 OH CO + 2H2

(11)

CO + H2 O H2 + CO2

(12)

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F.C. Meunier et al. / Applied Catalysis A: General 504 (2015) 220227

Scheme 2. Ethanol condensation mechanism based on the self-aldolization of acetaldehyde. (Adapted from Ref. [37].)

CO was probably formed from CO2 as a result of a reverse watergas

shift reaction (reverse of Eq. (12)). This observation stressed that the
reverse watergas reaction should be suppressed to maximize H2
production.
3.4. Ethanol condensation to butanol

Fig. 6. Product composition at the thermodynamic equilibrium calculated at

T = 300 C in a system noted m containing methanol, H2 , CO2 and water and a system noted n containing the same components and CO. Calculus initial conditions:
water/methanol = 1.3, P inert diluent = 55 kPa, Ptotal = 101 kPa. Calculated using the
HSC software (version 4.1, Outokumpu Research Oy).

Fig. 5 represents the product compositions (left scale) and the

methanol conversion (right scale) as a function of the W/F. CO only
appeared after the other reaction products, H2 and CO2 , as the
W/F was increased and methanol conversion was complete. This
observation already strongly suggested that CO was not a primary
reaction product.
The expected proportions of methanol, water, H2 and CO2 at
the thermodynamic equilibrium of the direct reforming [Eq. (10)]
at 300 C were calculated for a system free of CO, referred to as
m (Fig. 6). The calculation shows that essentially full methanol
conversion can be expected at the equilibrium and that the molar
proportions of H2 and CO2 reach ca. 69% and 23%, respectively. The
molar proportions of H2 and CO2 decreased to ca. 66% and 20%,
respectively, when CO was included in the system, which is referred
to as n (Fig. 6).
The thermodynamic limits for each product associated with
the systems m and n are reported in Fig. 5 as dotted lines. The
experimental proportions of H2 and CO2 rst clearly matched the
thermodynamic composition associated with a CO-free system
(line m), being in excess of the proportion associated with a system
containing CO (line n). Therefore, these data unambiguously, and
surprisingly, proved that CO was not the precursor of CO2 . Instead,

Ethanol can be converted to higher molecular weight alcohols,

so-called Guerbet alcohols [32,33]. The traditional (partlyhomogeneous) synthesis of Guerbet alcohols is thought to
proceed via several consecutive steps [34,35]. Aldehyde formation by alcohol dehydrogenation and its self-aldolization is a
well-accepted reaction pathway in the case of the reaction catalyzed by alkali metal hydroxides in the presence of a metallic
catalyst.
Scheme 2 illustrates this pathway in the case of the ethanol
conversion to butanol. The metal carries out the ethanol dehydrogenation to acetaldehyde, as well as the hydrogenation of reaction
intermediates to butanol (Steps 1, 3 and 4 in Scheme 2). The
homogeneous base is responsible for acetaldehyde self-aldolization
to 3-hydroxybutyraldehyde, which is then dehydrated to crotonaldehyde. Crotonaldehyde hydrogenation eventually leads to
butanol.
Interestingly, metal-free basic oxides were shown to be active
and selective, albeit at higher temperatures, typically between
300 and 450 C [3639]. The nature of the reaction mechanism
of the metal-free systems has been widely debated and alternative mechanisms have been proposed. Yang and Meng [36]
proposed a direct route with no identiable reaction intermediates (Scheme 3.A) and a semi-direct pathway involving ethanol
condensation with acetaldehyde, which was formed from ethanol
dehydrogenation (Scheme 3.B). Other authors have proposed that
the direct pathway (Scheme 3.A) could be taking place simultaneously with the acetaldehyde self-aldolization route (Scheme 2)
[38].
We have recently reported thermodynamic-based investigations of the high temperature condensation of ethanol to butanol
over a hydroxyapatite Ca3 (PO4 )2 Ca(OH)2 , noted HAP, one of the
best known catalysts for this reaction [40,41]. The formation of
acetaldehyde was of particular interest, since this compound was
often proposed as being a crucial reaction intermediate, through

F.C. Meunier et al. / Applied Catalysis A: General 504 (2015) 220227

Scheme 3. Alternative ethanol condensation mechanisms: (A) direct dimerization

and (B) semi-direct dimerization. (Adapted from Ref. [36].)

225

Fig. 8. Composition at the thermodynamic equilibrium of a system containing

ethanol, butanol, acetaldehyde, crotonaldehyde, butanal, 2-buten-1-ol, H2 and
water as a function of temperature. Total pressure is 1 bar and the initial state of
the system corresponds to an equivalent 11 mol.% of ethanol (balanced by Ar). The
molar fractions of ethanol and 2-buten-1-ol were always lower than ca. 0.01 mol
and cannot be seen on the graph (Reprinted from Ref. [41].)
Table 2
Ratio between the reaction quotient Q and the equilibrium constant K for Eq. (3),
obtained under various reaction conditions.

Fig. 7. Yields of the main reaction products during ethanol reaction over
the hydroxyapatite as a function of temperature. Feed: Ethanol = 15.2% in Ar,
WHSV = 14 h1 . (Reprinted from Ref. [40].)

its self-aldolization (Scheme 2) and condensation with ethanol

(Scheme 3.B) [38,39,4244].
1-Butanol (noted here butanol) was the main product and
acetaldehyde the main by-product (Fig. 7). Butadiene and ethylene
were also formed, the latter probably by ethanol dehydration on
residual acid sites [39]. Minute concentrations of butenol, butanal
and crotonaldehyde were also observed. The selectivity to butanol
was highest at around 400 C.
Equilibrium composition diagrams were drawn as a means
to comprehend the global thermodynamics of systems of interest. The thermodynamic equilibrium of a system containing most
of the species present in Scheme 2 was calculated over the
100500 C temperature range (Fig. 8). The thermodynamic data
of 3-hydroxybutyraldehyde were not available and this molecule
was therefore omitted from the system. Its equilibrium concentration is yet expected to be very low and should not change the values
associated with other species.
The striking feature of the data reported in Fig. 8 is that
the equilibrium concentration of butanol drops dramatically with
increasing temperature and becomes negligible above 300 C.
Butanol is replaced by butanal (and H2 ) and then acetaldehyde and
crotonaldehyde. The equilibrium distribution of products above
350 C (Fig. 8) is clearly at odds with the catalytic data collected in
the 350440 C temperature range reported in Fig. 7. Butanol was
clearly the main reaction product obtained over our HAP catalyst.

Temperature ( C)

Ethanol inlet concentration (%)

WHSV (h1 )

 = Q/K

350
400
440
400
400
400

15.2
15.2
15.2
7.6
7.6
7.6

28
28
28
1.4
7.0
14

623
2430
2730
8440
4560
4430

This combination of kinetic (Fig. 7) and thermodynamic (Fig. 8)

data suggests that the reaction scheme as proposed above
(Scheme 2) is likely to be irrelevant. In simple terms, if butanal
and acetaldehyde were to be reaction intermediates in the formation of butanol, then the concentration of these compounds should
remain higher than that of butanol when operating above ca. 350 C,
because those are more favored thermodynamically.
A precise quantitative comparison of reaction quotient (Q) and
equilibrium constant (K) is yet required to be able to draw a
denitive conclusion on the relevance of the pathway described
in Scheme 2, since there are many other by-products (e.g., butadiene, ethene, H2 ) which affect various reaction equilibria. The
simplest system based on acetaldehyde self-aldolization that can be
computed (i.e. having intermediates of accurately measurable concentrations and available thermochemical data) is given by reaction
[Eq. (3)]:
2 acetaldehyde + 2 H2  butanol + H2 O Q3

PH2 O Pbutanol P 2

Pacetaldehyde PH2

2

(3)

It must be stressed that the water and the H2 concentrations

needed to quantitatively measured, alongside those of butanol and
acetaldehyde. The ratios between the reaction quotient Q and the
equilibrium constant K were calculated at various temperatures
and for different experimental conditions (Table 2). Practical examples of calculus are detailed elsewhere [40,41].
Since the reaction quotient would be higher than the equilibrium constant, in fact, Q  K (Table 2), the reaction given by Eq.
(3) is irrelevant to describe the mechanism of butanol formation

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F.C. Meunier et al. / Applied Catalysis A: General 504 (2015) 220227

Scheme 4. The ethanol condensation mechanism prevailing at high temperatures over metal-free catalysts (left) is different from that occurring at low temperatures on
metal-containing systems (right).

taking place over our metal-free HAP between 350 and 440 C. In
other words, the condensation of ethanol to butanol did not proceed
via acetaldehyde self-aldolization in the present case.
This observation is in contrast with the low temperature catalytic systems, which typically include a metallic phase, and which
were shown to operate through aldol self-condensation (Scheme 4)
[34]. The metallic phase is crucial for the low-temperature system
to enable (i) alcohol dehydrogenation and (ii) the hydrogenation of
reaction intermediates.
Alcohol dehydrogenation is facile on basic oxides and isopropanol dehydrogenation is actually routinely used as a probe
reaction to measure oxide basicity. Yet, the absence of a metallic phase would make very difcult the activation of molecular
hydrogen needed to hydrogenate unsaturated intermediates.
Other reaction pathways must be considered in the case of
our HAP at temperatures above 350 C, which are discussed elsewhere [40]. In brief, the main pathway would be the direct route
(Scheme 3.A) and a minor parallel pathway would be similar to
the indirect route (Scheme 3.B), but in which the hydrogenation
of unsaturated intermediates proceeds via hydrogen-transfer from
sacricial ethanol molecules and not from molecular hydrogen [40].
4. Conclusions
The approach-to-equilibrium ratio should always remain lower
or equal to one for a thermodynamically feasible reaction. Reaction pathways that breach this rule can be ruled out and
several examples have been detailed here. An advantage of this
thermodynamic-based method is that it is uses steady-state kinetic
data obtained under operating conditions and does not require the
use of transient methods or labeled compounds. It is yet necessary
to have the thermochemical data of the compounds appearing in
the stoichiometric equation and the corresponding concentrations
(and possibly the activity coefcient, if not under ideal conditions).
The method may unambiguously discard a reaction pathway or may
determine the relevance of others routes.
Acknowledgements
F.C.M. thanks Prof J.R.H. Ross and Dr J.P. Breen for fruitful discussions on some of the methods described here while at the
University of Limerick.

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