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INVITED ARTICLE www.rsc.org/pccp | Physical Chemistry Chemical Physics

Kinetic measurements of hydrocarbon conversion reactions on model

metal surfacesw
Jarod Wilson, Hansheng Guo, Ricardo Morales, Egor Podgornov, Ilkeun Lee and
Francisco Zaera*
Published on 29 May 2007. Downloaded by Universidad Autonoma de Nuevo Leon on 25/01/2017 13:32:34.

Received 20th February 2007, Accepted 23rd April 2007

First published as an Advance Article on the web 29th May 2007
DOI: 10.1039/b702652h

Examples from recent studies in our laboratory are presented to illustrate the main tools available
to surface scientists for the determination of the kinetics of surface reactions. Emphasis is given
here to hydrocarbon conversions and studies that rely on the use of model systems, typically
single crystals and controlled (ultrahigh vacuum) environments. A detailed discussion is provided
on the use of temperature-programmed desorption for the determination of activation energies as
well as for product identification and yield estimations. Isothermal kinetic measurements are
addressed next by focusing on studies under vacuum using molecular beams and surface-sensitive
spectroscopies. That is followed by a review of the usefulness of high-pressure cells and other
reactor designs for the emulation of realistic catalytic conditions. Finally, an analysis of the power
of isotope labeling and chemical substitutions in mechanistic research on surface reactions is
presented.

1. Introduction tant role in heterogeneous catalysis. Early in the 20th century,

Surface reactions feature prominently in many industrial
processes, including those involving catalysis, microelectronics
fabrication, tribology, and electrochemistry.13 Because many
of those processes rely on the formation of metastable pro-
ducts, their kinetics often define their viability. In catalysis in
particular, the increase in complexity that has accompanied
new developments in modern times has changed the paradigm
so that catalysts need to be chosen not only because of their
ability to promote reactions but also because of their eec-
tiveness in promoting the desirable reactions selectively over
all possible pathways.411 This means that, in terms of transi-
tion state theory, what matters is not so much the absolute
height of the activation barrier for the reaction of interest, but
its relative energy in relation to those of other potential
competing reactions.12,13 The dierences among those barriers
may be small, but still sucient to steer the catalytic conver-
sion down a specific pathway. In general, dierences in
activation energies on the order of 510% of their absolute
value are sucient to ensure close to 100% selectivity toward
one specific product.
The subtleties associated with issues of selectivity have led to
an increased interest in the determination of accurate kinetic
parameters for surface chemical reactions. Much work has
been performed to address this issue in catalysis by using
supported catalysts,1420 Indeed, since Langmuir advanced a
simple theory of chemisorption and showed how it could be
used to formulate rate laws for reactions occurring on sur-
faces,21,22 studies on surface chemistry have played an impor-
Department of Chemistry, University of California, Riverside, CA
92521, USA. E-mail: zaera@ucr.edu
w The HTML version of this article has been enhanced with colour
images.
simple studies on adsorption by catalysts led to the develop-
ment of viable methods for the determination of the surface
areas of the porous structures often used as catalytic materials,
and also to the advancement of the concept of activated
adsorption. Later, the application of various spectroscopic
and structural probes made it possible to investigate catalyst
surfaces at a more microscopic level.2325 Those studies were
able to provide some direct information on the rates of
elementary reactions of well-defined surface species. However,
the ill-defined nature of the catalytic samples used limited the
conclusions reached from that work.
A number of modern surface-science techniques and meth-
odologies have been incorporated in studies on model surface
systems to better understand not only the kinetics but also the
mechanisms of such conversions on solid interfaces.1,2629 We
have been working on this problem for quite some time, with
the specific goal to better understand reactions involving
hydrocarbons on metals.3035 In this review we oer a personal
perspective of the state of the art in this field. The emphasis
here will be on the methods available for measuring kinetic
parameters on small flat surfaces, typically single crystals,
foils, or thin films. Examples from our laboratory will be
provided to highlight some of the general conclusions that
have arisen from these studies regarding the surface chemistry
of organic molecules. This is not intended to be a comprehen-
sive review, but rather a personal and critical discussion with
emphasis on recent work from our own laboratory.
2. Temperature programmed desorption
Although developed several decades ago, temperature pro-
grammed desorption (TPD, sometimes also called thermal
desorption spectroscopy, TDS, or temperature programmed
reaction, TPR) is still by far the most widely used technique to

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determine kinetic parameters of reactions on model sur-
faces.29,3638 The majority of TPD experiments are carried
out on single-crystal surfaces and performed under ultrahigh
vacuum (UHV) conditions, although similar experiments are
also performed routinely on supported high-surface-area cat-
alysts.16,25,29,39 In a typical TPD experiment, specific amounts
of one or more gaseous chemicals are dosed onto the solid
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surface at a set (low) temperature, and the surface is then
heated rapidly while the desorbing species are monitored by
using mass spectrometry.40,41 TPD experiments belong to the
family of techniques where kinetic information is extracted
from experiments carried out under conditions of variable
temperature, and provide rich information not only on the
kinetics of the surface reactions that occur upon thermal
activation, but also on the identity, yield, and stoichiometry
of the desorbing products. Below, we expand on each of these
features of TPD experiments.
2.1 Kinetics of surface reactions
One of the most common pieces of information extracted from
TPD experiments is the activation energy of the reaction
leading to the formation of the desorbing products. By using
a well-defined heating program, typically a linear heating
ramp, a direct correlation can be established between the time
elapsed in the TPD experiment and the temperature of the
surface. With that information, an Arrhenius or transition-
state rate analysis can be used to determine the evolution of
the concentrations of the species involved as a function of
either temperature or time. Unfortunately, the resulting equa-
tion is not simple to manipulate and compare with the experi-
mental data. As a consequence, a number of simplified
analytical protocols have been developed over the years to
extract kinetic parameters from experimental TPD traces
based on the use of only a few pieces of information from
the whole data set.4246 To discuss the most common of those,
here we analyze the TPD traces obtained in our laboratory for
the molecular desorption of a series of alkanes from Rh(111)
single-crystal surfaces (Fig. 1).47 This represents one of the
simplest cases in kinetics of surface processes, because alkanes
are quite dicult to activate and rather desorb molecularly
following simple first-order kinetics.4850 All the data in Fig. 1
were obtained by starting with saturation coverages of the
alkanes at 100 K.
A simple TPD peak is seen for each alkane in the left panel
of Fig. 1, centered at increasingly higher temperatures as the
molecular weight of the alkane is increased. The shape of those
peaks is asymmetric, with a slow rise to the maximum and a
sharper trailing edge, as expected for first-order kinetics.44 To
illustrate the performance of the dierent analytical proce-
dures mentioned above, the experimental trace obtained for
n-butane is contrasted in the right panel of Fig. 1 against
calculated desorption profiles using the most common four.
Briefly, the following comments can be made about each of
these:
(1) Redhead:42 This is the oldest and simplest of the
proposed procedures, and only requires measuring the tem-
perature at which the reaction rate reaches its maximum
(Tmax). By assuming linear heating and making a few other
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Fig. 1 Molecular temperature programmed desorption (TPD) spec-
tra from dierent alkanes adsorbed on a Rh(111) single-crystal sur-
face. All traces correspond to saturated monolayers, and were
obtained with linear heating rates of 10 K s#1. Left: TPD traces for
ethane, propane, n-butane, n-pentane, and n-hexane. A progressively
higher peak desorption temperature is seen with increasing molecular
weight, as expected and reported previously for similar systems. The
peaks also show the asymmetric shape expected from first-order
kinetics. Right: detailed analysis of the data for the case of n-butane.
The experimental data (dots) are contrasted with traces calculated by
using Redheads (short dashed line)42 and Weinbergs (long dashed)44
procedures, by a leading-edge analysis (mixed shortlong dashes),45
and by integration of a first-order law with an Arrhenius-type reaction
rate constant (solid line).40 The best fits are obtained with the
Weinbergs analysis and full simulation. However, since those require
well dierentiated TPD peaks and do not account for a number of
complications arising from intermolecular interactions on the surface,
a better compromise may be to use the simpler Redhead analysis and
accept the B10% error margin associated with it.
approximations, a very simple equation can be derived to
relate the activation energy of the desorption to the logarithm
of Tmax. This analysis does need to assume a reaction order
(typically first order), and also a pre-exponential factor (typi-
cally 1 " 1012 s#1, but sometimes higher, about 1 " 1015 s#1
for molecular desorptions such as those in this example). Fig. 1
shows that in our case the Redhead fit (short dashed trace)
estimates a TPD feature peaking at lower temperatures and
higher desorption rates than those observed experimentally. A
better fit could be obtained using lower pre-exponential fac-
tors, but then the results would be physically unreasonable.
(2) Leading edge:45 In this approach it is assumed that the
changes in the surface concentrations of the reactants at the
beginning (leading edge) of the TPD peak are negligible, and
that the desorption rate in that temperature region can there-
fore be fitted to a simple exponential Arrhenius expression.
This method does not involve any assumptions in terms of
reaction orders or pre-exponential factors, but relies on an
analysis of the segment of the TPD trace where the signal is the
weakest and the experimental artifacts the most severe. In
particular, any inhomogeneous heating across the surface
tends to smear the leading edge of the TPD peak, and usually
leads to an underestimation of the activation energy. Fig. 1
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shows how a leading edge fit to the first B30 K of our
n-butane desorption trace (shortlong dashed line) follows
the data quite closely. However, the activation energy
estimated in this way is lower than those obtained with
other methods.
(3) Weinberg:44 This is in principle a better procedure than
the other two because it uses two pieces of information from
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the experimental data (Tmax and the full peak width at either
half or 3/4 of its maximum, Dw1/2 or Dw3/4) rather than the one
(Tmax) employed in the Redhead approach. On the other hand,
it is a bit more involved, and requires a better peak definition
(to get the peak width). It also requires the a priori assumption
of a particular reaction order for the surface reaction. In our
example, this analysis actually fits the experimental peak
reasonably well over the whole temperature range (long
dashed line), even though it predicts an earlier trailing edge
and an overall sharper TPD peak.
(4) Peak simulation:40 This is the best approach from a
theoretical point of view, since it is based on the fit of the
whole peak to an Arrhenius-type equation. However, it is
significantly more demanding from both the experimental and
analytical points of view, because it can only be performed in
fully isolated and low-noise peaks, and because it involves a
minimum square fit to all data points. Moreover, this proce-
dure still assumes a specific rate law with a specific rate order,
and ultimately produces parameters close to those obtained
with the Weinberg method. The fit to the data in our example
is excellent (solid line), but perhaps not sucient to justify the
extra work.
A summary of the kinetic parameters obtained for the
desorption of all the alkanes reported in the left panel of
Fig. 1 using these four methods is provided in Table 1. They
typify the spread in activation energies obtained using this
type of analysis. One additional way of extracting kinetic
parameters from TPD data is by performing sets of experi-
ments using various heating rates.43 The stated goal of that
approach is to extract reaction orders without having to make
any a priori suppositions, but the problems here are that the
method requires the performance of many experiments and
often suers from the limited range of heating rates available
within a given experimental setup.
Much discussion has been reported in the past on the
relative merits of all these methods in terms of their mathe-
matical accuracy in reproducing ideal desorption traces. For
instance, Niemantsverdriet et al. have published a detailed
study of the deviations of the predictions of each method from
simulated TPD spectra.46 However, it is our belief that it is
more relevant to consider the limitations imposed on these
analyses by both the nature of the system being studied and
Table 1 Kinetic parameters for the desorption of alkanes from Rh(111) single-crystal surfaces, estimated from the TPD data reported in Fig. 1
Redhead42 Leading edge45
Ea/kcal mol#1 Log[A s] Ea/kcal mol#1
Ethane 6.0 12.0 5.5
Propane 8.6 12.0 5.1
n-Butane 10.7 12.0 8.3
n-Pentane 11.9 12.0 7.2
n-Hexane 12.9 12.0 8.7
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the experimental setup used. In terms of the nature of the
system, for instance, the kinetics of even the simplest mole-
cular desorptions often deviate from first-order beha-
vior:13,51,52 it has been extensively documented that
molecules such as CO can interact strongly with each other
on the surface, and that those interactions aect their de-
sorption activation barrier.5355 Modified equations have been
developed to address this issue, typically by assuming that
activation energies depend linearly on surface coverages, but
their success has been limited by the fact that any inhomo-
geneity in the distribution of adsorbates on the surface renders
mean-field equations inadequate to describe such kinetics.56,57
Furthermore, significant intermolecular interaction changes
can sometimes occur abruptly at one given coverage, as with
many aromatic molecules on metals, which switch from tilted
to flat-lying adsorption as soon as sucient space is available
on the surface for the latter. That occasionally results in the
development of two desorption regimes in TPD experi-
ments,58,59 and in extreme cases to autocatalytic or explo-
sion kinetics.6062 Then there is the possible existence of
dierent adsorption sites with dierent energetics even on
the simplest of surfaces.63,64 In hydrocarbon chemistry, all
this is accompanied by fairly complex chemistry involving
several surface species and many competing reaction path-
ways. That alone is sucient to lead to fairly elaborate TPD
traces with many overlapping peaks of ill-defined shape.8,33,65
In such cases, perhaps the best approach to the analysis of
TPD traces remains the use of the Redhead equation assuming
pseudo-first-order kinetics, with the understanding that the
estimated activation barriers obtained in this way are not to be
trusted to better than B10% of their values. In the example in
Fig. 1, that is sucient to describe the most important trends
that derive from the data, in particular the approximately
linear increase in adsorption energy with molecular weight
typically seen for alkanes.49,50 It should also be said that
kinetic comparisons across two or more competing reactions
can better be performed by directly contrasting the rates
measured from the TPD traces at a given temperature, as in
the example provided in Section 5.2 in connection with the
production of neopentane via the thermal conversion of
neopentyl iodide on a Pt(111) surface (Fig. 12).
2.2 Yields
In addition to kinetics, TPD data also provides much infor-
mation about the mechanisms of the reactions been studied.
Under the high-pumping speeds typically used in UHV sys-
tems, the partial pressures of the desorbing gases measured in
the TPDs are directly proportional, and may be converted
Weinberg44 Simulation40
Log[A s] Ea/kcal mol#1 Log[A s] Ea/kcal mol#1 Log[A s]
10.4 6.0 12.4 5.7 11.0
6.8 7.0 9.7 7.1 9.8
8.9 8.8 9.7 9.0 9.8
6.8 11.1 11.5 11.9 11.8
7.8 12.7 11.7 12.8 11.8
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after appropriate calibration, to their desorption rates.37,41
Consequently, the integrals of the areas under the TPD peaks,
when plotted versus time, provide a measure of the yields for
those products. This is quite useful in determining selectivities
among dierent competing reactions. It should be kept in
mind, though, that TPDs are carried out under highly irrever-
sible conditions, where reactions with high rates at low
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temperatures under the UHV conditions used in TPD experi-
ments. This behavior is the most pronounced at low surface
coverages, in which case only hydrogen desorption is ob-
served. However, the dehydrogenation steps are typically
inhibited at higher coverages, for which hydrogenation pro-
ducts are commonly detected. This change in selectivity with
coverage has been explained by a switch in adsorption geo-

temperatures are favored over those with higher activation
energies. Once the adsorbate is consumed by the first viable
reaction during the heating process, it is no longer available
for other reactions even if those are feasible at higher tem-
peratures. Because of this, dierent product distributions, and
even the appearance of new products, are sometimes seen in
TPD experiments if the reactants are dosed at higher tempera-
tures. One consequence of this kinetic limitation is that the
yields calculated from TPD experiments may bear little rela-
tion with selectivities in steady-state processes such as those
encountered in catalysis. Nevertheless, TPD yields can be
useful in determining trends as a function of, for instance,
surface coverages.
An example of this is illustrated by the data for the thermal
activation of 1-iodobutane on Pt(111) single-crystal surfaces as
a function of initial coverage shown in Fig. 2.66 By relying on
the lability of carbonhalogen bonds (especially of carbon
iodine bonds), haloalkanes have been often used to prepare
alkyl surface intermediates on surfaces;30,31,6771 alkyl surface
species are the initial intermediates during both the activation
of alkanes31,7274 and the hydrogenation of alkenes.31,75,76 The
data in Fig. 2, which address the case of n-butyl moieties on
Pt(111), are quite representative of the surface chemistry of
alkyls adsorbed on transition metal surfaces.31,32,69,70,7781
Most hydrocarbon surface species adsorbed on those surfaces
dehydrogenate and decompose to surface carbon at low
metry with increasing crowding of the surface, from flat-lying
to tilted in the case of alkyls,8286 or by a change in bonding
mode from di-s to p with alkenes and other unsaturated
molecules.3,31,75 In the example of Fig. 2, total dehydrogena-
tion and H2 desorption are seen exclusively for doses up to 1.0
L, but significant alkene (from b-hydride elimination)8,35 and
alkane (from reductive elimination with coadsorbed hydro-
gen)31,76,80 production is observed at coverages close to mono-
layer saturation. It should also be said that the detection of
even minority products in TPD experiments may be sucient
to speculate on possible catalytic processes provided that the
proper reaction conditions are identified.81,8789 In this exam-
ple, the yields for the production of the alkane (n-butane) may
be quite low, but still indicative of the potential self-hydro-
genation of alkyl groups via the incorporation of hydrogen
atoms produced by the b-hydride elimination step that leads to
the production of the alkene.66,77,80,90
TPD yield calculations are also used to estimate average
stoichiometries in surface species. This is particularly common
in studies with hydrocarbons, since their dehydrogenation
often occurs in a stepwise manner and leads to H2 TPD traces
with several distinct features. It can be argued that each peak
corresponds to a particular dehydrogenation step leading to a
new, more dehydrogenated, surface species, and that the
carbon-to-hydrogen ratio of the intermediate species may be
estimated from the relative areas of the dierent H2 TPD

Fig. 2 TPD data from 1-iodobutane adsorbed on a Pt(111) single-crystal surface at 100 K as a function of initial exposure.66 Shown are the
desorption traces for hydrogen (left panel), butene (second from left) and butane (third from left), and the yields of all products as a function of
exposure. Gradual but significant changes are seen in the TPD traces as the exposure is increased, mostly involving the growth of new peaks and/or
the shift of old ones to higher temperatures. Those trends exemplify the general behavior seen with adsorbed hydrocarbons, namely, a transition
from almost exclusive deep dehydrogenation and H2 production at low exposures to the desorption of significant amounts of hydrocarbons, butene
and butane in this case, at saturation. Note also the several distinct peaks seen in the H2 and C4H8 TPD traces, an observation that indicates the
occurrence of several reactions as the surface temperature is increased.

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peaks. In Fig. 2, dehydrogenation clearly occurs in at least
four distinguishable temperature regimes, and leads to the
formation of a minimum of three partially-hydrogenated
species, at approximately 380, 500, and 800 K, respectively.
However, these species show dierent average stoichiometries
at dierent coverages. Indeed, starting with n-butyl (C4H9)
fragments, it is estimated that in the 0.6 to 1.0 L exposure
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range surface species with C4H5 and C4H2 average composi-
tion form at 380 and 500 K, respectively (the relative areas in
the H2 TPD features in the 100380, 380500, and 500800 K and atomic hydrogen, the kinetics may not only depend on the
temperature ranges follow ratios of approximately 4 : 3 : 2).
On the other hand, the average stoichiometries for those
intermediates are C4H6 and C4H3 at the intermediate 1.2 to
1.6 L exposures, and C4H7 and C4H3 at saturation. It is
important to keep in mind that stoichiometry values estimated
from this type of analysis represent averages over all species
present on the surface, and do not preclude the possible
simultaneous formation of two or more intermediates with
dierent stoichiometries. It should also be pointed out here
that there is a complication arising from the fact that, as
mentioned above, one single reaction can produce more than
one TPD peak because of potential variations in the inter-
molecular interactions on the surface as the coverages of the
adsorbates evolve upon desorption of some of the products.
Conversely, because of the poor temperature resolution of
TPD spectra, one TPD peak may correspond to more than
one reaction step. One more issue to consider is that de-
hydrogenation reactions on adsorbed hydrocarbons occur
via the deposition of hydrogen atoms on the surface followed
by recombination of those to form molecular H2, which then
desorbs into the gas phase. Above room temperature the rate-
limiting step for that sequence is the hydrogen abstraction
itself, but at lower temperatures it is the hydrogen recombina-
tion that controls the kinetics of the overall process, which
means that facile dehydrogenation kinetics can most often not
be measured by this type of TPD experiment.
Finally, it is worth mentioning in this section that in many
instances cooperative eects are seen among dierent compet-
ing steps in the kinetics of complex reactions. This is in fact
quite common in hydrocarbon surface chemistry on metals,
where multiple reactions often display the same or similar
threshold temperatures. One example of this is the dispropor-
tionation of alkyl groups into alkenes and alkanes,8,31,66,77,80
which is believed to take place via an initial rate-limiting b-H
elimination step from one alkyl fragment to form the corre-
sponding alkene followed by the immediate incorporation of
the hydrogen atom released to the surface into a second alkyl
moiety to produce the alkane. In this case, the detection of
multiple products is due to the non-elementary nature of the
reaction: one rate-limiting step is followed by other, faster
conversions. This particular type of mechanism accounts for
the similarity in peak shapes and positions for the production
of butene and butane from n-butyl surface species seen in
Fig. 2. Another possibility is for the conversion and desorption
of one adsorbate to liberate surface sites for the adjacent
adsorbates to react. This may be what takes place during the
dehydrogenation and conversion of alkenes to alkylidynes;
scanning tunneling microscopy experiments have indicated
preferential reactivity at the interface between domains of
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the two surface species.91 A third option for cooperative eects
in surface kinetics is that associated with reaction dynamics, as
would be the case in, for instance, the generation of local heat
by one reaction triggering another more activated step. In-
deed, direct evidence has been reported for the non-adiabatic
nature of the dissociation of molecular oxygen on metals.92
and there is no reason to believe that this is not a general
phenomena on surfaces. Finally, in binary reactions such as in
hydrogenation steps between hydrocarbon surface fragments
surface concentration of the two reactants, but also on their
spatial distribution and/or their surface mobility. Reactions
with non-homogeneous mixtures of reactants are common on
surfaces, but can also be found in other systems, such as in
reactions in solid-state93,94 or poorly stirred liquid mix-
tures.9597 All these issues aect both the kinetics and the
yields of the reactions involved.
2.3 Product identification
Another direct piece of information arising from the analysis
of TPD data is the identification of reaction products. This is
quite helpful in determining reaction mechanisms. In principle,
each product displays a unique mass spectrum and can there-
fore be dierentiated from the others and followed kinetically
in TPD experiments if data are acquired for the appropriate
masses simultaneously. The optimum approach is to select one
unique mass for each potential product with high sensitivity
for that molecule and little interference from all others. In
practice, however, this is often not easy to accomplish in
studies with hydrocarbons, because those typically display
complex and overlapping cracking patterns in their mass
spectra. Although it is still desirable to identify and use the
most representative, intense, and minimally interfering masses
possible for each product, additional deconvolution of the
data may be required. A useful approach for this is a matricial
analysis based on the following steps:
(1) The building of a square matrix S = [Sij] summarizing
the mass spectrometer sensitivity factors Sij of all compounds i
and masses j to be recorded in the TPD experiment.
(2) The construction of a vector I(T) = [Ij(T)] for every
temperature point T in the TPD data with the mass spectro-
metry signal intensities Ij measured for each mass j.
(3) The calculation, on the basis that the partial pressures of
each compound at the given temperature Pi(T) can be grouped
into a vector P(T) = [Pi(T)] so that I(T) = P(T) $ S, of those
partial pressures by the matrix product P(T) = I(T) $ S#1,
where S#1 is the inverse of the sensitivity matrix S.
(4) The repetition of the operation in Step (3) for each vector
I(T) = [Ij(T)] obtained for each temperature point in the TPD.
The result is a matrix M = [PiT] consisting of a set of vectors
P(T) = [Pi(T)], one for each temperature point.
(5) The plotting of each of these vectors P(i) as a function of
temperature, taking into consideration that the matrix men-
tioned in Step (4) can also be viewed as a collection of vectors
P(i) = [PT(i)], that is, as MTranspose = [PTi]. One TPD trace is
obtained this way for each product i.
An example of how this procedure works is provided in
Fig. 3 for the thermal chemistry of ethyl iodide on a Ni(110)
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Fig. 3 TPD data from 3.0 L of ethyl iodide adsorbed on a Ni(110)
single-crystal surface at 100 K. The signal from twelve selected masses
were recorded simultaneously in order to be able to identify the
desorbing products. Left: raw data for the twelve masses chosen.
Right: desorption profiles obtained after deconvolution of the raw
data using available cracking patterns. Notice that only three species
were detected in this experiment, namely, ethylene and ethane from
disproportionation of ethyl surface groups, and propylene. It should
also be noted that changes are possible in the shape of the peaks
obtained after deconvolution, as, for instance, in the case of the
27 amu signal versus that for ethylene desorption.
single-crystal surface.98 Twelve masses were recorded simulta-
neously in that study in order to be able to unequivocally
identify all the desorbing products of this conversion. It should
be noted here that although features are seen in the raw traces
for almost all masses, these correspond to only three hydro-
carbon species. The main product is ethylene, which results
from b-hydride elimination34,99 from the ethyl surface species
produced by an early CI bond scission step.30,100 As men-
tioned above, this reaction is facile and common on metal
surfaces,3,31 and has previously been reported on other nickel
facets77,88,101,102 as well as on other metals.66,80,83,84,90,103,104
Note, however, that the final TPD trace for ethylene obtained
after data deconvolution displays a somewhat dierent shape
to that of the original raw spectrum for 27 amu from which
most of that information comes from: the main feature at
195 K with an unresolved shoulder seen in the raw trace was
converted into two distinct peaks at 192 and 250 K upon data
deconvolution. This is because the 27 amu signal also includes
some intensity from ethane, which is produced at B207 K via
the reductive elimination of some of the ethyl surface moieties
with the surface hydrogen from ethyl dehydrogenation, an-
other common reaction in these systems.66,81,88,105110 Inter-
estingly, a third product, propene, was identified at 190 K by
the deconvolution of the traces of Fig. 3. Such a product has
not been observed on other surfaces and its origin is not yet
fully understood, but what is clear is that it is not accompanied
by the production of any other hydrocarbon products. In
terms of the deconvolution analysis being discussed in this
section, it is worth pointing out that the system in Fig. 3 is
over-defined, since twelve masses were followed to identify
only eight products. The accuracy of the method could there-
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fore be checked by calculating the residual signals for the
traces of the four redundant masses, 14, 15, 29, and 39 amu.
The fact that these are fairly flat attests to the reliability of the
deconvolution performed.
Note that for this type of deconvolution of TPD data
cracking patterns are required for all the products detected.
Ideally, those should be obtained independently using the
same mass spectrometer and conditions employed to acquire
the TPD data (because cracking patterns are highly dependent
on the details of the mass spectrometer and the conditions
used). When this is not possible, published data, or even
estimated patterns based on data for similar compounds or
reports on cracking mechanisms, may be used as a starting
point. In those cases further minor adjustments to the initial
values may be required, something that can be carried out
interactively, preferably by using large sets of data (for
instance, sets of TPDs versus coverage) and by fitting the same
set of cracking pattern parameters to all the data. To decide on
the goodness of the final values, one useful criterion is to avoid
physically unreasonable results such as negative TPD peaks.
Also, a comparison of peak shapes can help decide what
results from the deconvolution process are credible. On the
one hand, it is clear that if the raw traces of two or more
masses display dierent shapes or dierent trends as a function
of exposure, they must include signals from at least two
dierent species. Conversely, traces that can always be super-
imposed on each other after proper scaling are likely to
correspond to the same compound. Finally, the deconvolution
process does add noise to the results, more as the traces and
compounds treated simultaneously increase. Therefore, it is a
good idea to separate the analysis by groups of compounds
with non-overlapping sets of mass spectra to the maximum
extent possible.
3. Isothermal kinetic measurements
One of the main kinetic limitations of TPD experiments is that
their temperature and time are directly correlated and cannot
be controlled independently. This means that the surface
concentrations vary in a complex way with the reaction time,
making the extraction of detailed kinetic data quite dicult if
not impossible. This is a problem common to all kinetic
measurement techniques involving variable tempera-
tures.111,112 The appropriate response to this problem is to
decouple time and temperature by carrying out kinetic mea-
surements isothermally. Under vacuum, this is often accom-
plished by using molecular beams.
3.1 Molecular beams
In the past, molecular beams have been used mainly for the
characterization of physical properties of surfaces113115 and
for investigation of the dynamics of surface processes.116,117
Nevertheless, there has also been some pioneering molecular
beam work reported on studies of simple reactions on single-
crystal surfaces. For instance, the use of modulation and lock-
in detection has been used to determine the dynamics of a
number of surface reactions.118,119 Time-resolved molecular
beam experiments have also helped in dierentiating between
LangmuirHinshelwood and EleyRideal mechanisms,120 and
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in separating mass transport from chemical conversion
steps.121 Molecular beams in conjunction with isotope labeling
has been used to determine the role of steps in catalysis.122
Most of that work, however, has focused on the kinetics of
simple high-probability reactions such as carbon monoxide
oxidation, and have relied on the use of supersonic beams.
This brings into question their relevance to the study of
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catalytic reactions, which typically involve less energetic
molecules.
Because of the issue of the energy of the reactants low-
energy or eusive beams are typically more appropriate for the
emulation of catalytic processes,123 but one noticeable exemp-
tion to this is the case of alkane activation. Studies using
supersonic beams have indicated that the dissociation of the
saturated CH bonds may take place either directly upon
collision of the incoming gas molecule with the surface or
via the formation of a weakly adsorbed intermediate trapped
on the surface.31,73 Thanks to the control that supersonic
beams oer on the energies of the individual molecular degrees
of freedom, it has been possible to determine that alkane
dissociation relies mostly on energy transfer from the transla-
tional and internal degrees of freedom of the gas molecules to
the particular CH bond to be broken; the energy stored by
the surface seems to be of little importance for this pro-
cess.124126 It has been suggested that while direct activation
of alkanes takes place via a tunneling mechanism, the trap-
ping-mediated activation process may proceed via a three-
center two-electron intermediate instead.127
For more reactive systems, isothermal kinetic studies can
certainly be carried out under vacuum using eusive beams as
long as the reaction probabilities are high enough for the
products to be detectable above the noise level of the mass
spectrometer employed. Rates of conversion can be measured
under both transient and steady-state conditions by using a
variation of the so-called King and Wells method,123,128,129 as
shown in the various studies already reported on the kinetics
of CO oxidation55,56,130,131 and NO reduction.132137 There
have also been a few reports of molecular beam kinetic
investigations on hydrocarbon reactions, in particular on the
hydrogenation of ethylene138141 and on the conversions of
methanol,142,143 formic acid,144 and acetic acid.145 Molecular
beams have also been employed recently to study hydrocarbon
conversion kinetics on supported nanometal particles,146,147
but that work is still in its infancy.
The challenge here is that many hydrocarbons, saturated
alkanes in particular, display relatively low reaction probabil-
ities, often dependent not only on the composition of the gas in
the beam but also on its total flux. Because of this, new designs
are required to be able to work with high molecular
fluxes.148,149 However, alkane activation is still possible with
conventional beam arrangements at high temperatures, under
conditions resembling short contact-time catalysis.150 An ex-
ample of a molecular beam study of the oxidative dehydro-
genation of alkanes under such conditions is provided in
Fig. 4.151 There, the steady-state catalytic conversion of iso-
butane with oxygen was followed on a Rh(111) single-crystal
surface held at a temperature of 1150 K. Shown are the traces
obtained for the rates of oxygen and isobutane consumption
as well as those for the production of molecular hydrogen,
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Fig. 4 Isothermal kinetic data for the conversion of a 1 : 1 isobutane
+ O2 mixture on a Rh(111) single-crystal surface at 1150 K, acquired
by using an eusive molecular beam in a setup similar to that used for
sticking coecient measurements.123 Here, the evolution of the partial
pressures of the reactants (oxygen and isobutane) and products
(hydrogen, carbon monoxide, water, and carbon dioxide) are shown
as a function of time under steady-state catalytic conditions. The
impinging gas beam was interrupted periodically as indicated by the
arrows in the plot to directly determine the reaction rates over the
background signals. These data helped identify the products that form
in this system (H2, CO, and H2O, but not CO2), and provided, after
appropriate calibration, absolute reaction rates and stoichiometries.
Additional information was aorded by the transient behavior that
takes place immediately after blocking and unblocking of the beam.
Note in particular the slow evolution of the water signal, an observa-
tion that suggests a secondary reaction on the surface.
carbon monoxide, carbon dioxide, and water. The beam was
interrupted periodically to achieve better estimates of the rate
dierentials corresponding to the conversion of the reaction
mixture from the beam impinging directly on the surface.123
Several observations are worth highlighting from these data:
(1) Steady-state alkane conversion can be clearly reached for
this system;
(2) The stoichiometry measured from the data suggests the
following as the primary reaction: i-C4H10 + 2 O2 - 4 CO +
5 H2 .
(3) A competing minority channel is also indicated by the
production of a small amount of water. However, the absence
of any CO2 production argues against the expected water-shift
reaction.152
(4) The slow transient measured for the formation of water
highlights the secondary nature of the surface reaction respon-
sible for its production.
(5) The mirroring spikes in the O2 and H2 traces seen
immediately after blocking and unblocking of the beam point
to the formation of other transient species on the surface.
All these conclusions illustrate the power of the molecular
beam approach for the measurement of reaction kinetics on
solid surfaces. Additional information can also be extracted by
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post-mortem analysis of the surface, either by using surface-
sensitive spectroscopies or indirectly by titrating adsorbed
species using appropriate probe molecules (CO for oxygen,
O2 for carbon) in TPD experiments.123
Clearly, its isothermal nature, combined with its ability to
probe both transient and steady-state conditions, makes the
molecular beam approach much more powerful from the
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kinetic point of view than the use of TPD so commonly seen
in surface-science laboratories. Unfortunately, only a handful
of researchers have embarked in the type of molecular beam
work described here. Perhaps the general perception is that
these require complex and expensive instrumentation, even
though in reality simple eusive beams can be set up in most
ultrahigh vacuum (UHV) chambers by using regular dosing
hardware and a small capillary array.123,153 On the other hand,
one needs to be aware of the limitations of molecular beam
kinetic measurements, which include the need to detect deso-
rbing products, as in TPD experiments, and the lack of
sensitivity for low-probability reactions. The latter point is
critical, because even so-called facile catalytic reactions such as
olefin hydrogenations typically exhibit reaction probabilities
on the order of one conversion per million collisions or
less.86,154,155 Furthermore, the rates of olefin catalytic conver-
sion depend not only on the composition of the reaction
mixture, namely, the ratio of hydrogen (or deuterium) to the
hydrocarbon, but also on the total pressure at which the
reaction is carried out. Under catalytic conditions, the positive
(usually close to unity) order of the rates on the pressure of
hydrogen and the negative (B0 to #0.5) order on the pressure
of the hydrocarbon (HC) means that, for a given fixed H2 : HC
mixture ratio, hydrogenation is favored over dehydrogenation
only at relatively high pressures.156159 Perhaps because of
this, there are not, to date, any published reports of steady-
state olefin catalytic conversions under vacuum, not even in
molecular beam experiments with hydrogen-rich mix-
tures.123,139,146,160 This is soon to change since we have re-
cently been able to sustain the catalytic cistrans isomerization
of butenes on a supported palladium model catalyst,147 but the
main argument remains: regular molecular beam arrange-
ments are not well suited to kinetic studies of hydrocarbon
catalytic reactions.
3.2 High-pressure cells
It derives from the discussion above that, in order to be able to
sustain low-probability reactions under steady-state condi-
tions, high flows (impinging frequencies) of reactants on the
surface are required, much higher than those possible with
traditional molecular beams. Yet, it is still desirable to carry
out kinetic measurements on model surfaces such as those of
single crystals in order to exert some control on the nature of
the active sites probed. This dilemma, a manifestation of what
has come to be known as the pressure gap in surface science
circles,1,3,86 has been traditionally addressed by using a so-
called high pressure cell setup, where the solid sample is mixture collected at the end of the kinetic run, obtained by mass
characterized under UHV but then transferred to a small
reactor for catalytic kinetic measurements.161165
Much kinetic data have been acquired by this type of study,
typically to extract appropriate kinetic parameters and pro-
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pose standard rate laws.166,167 Experiments are commonly
performed systematically as a function of temperature to
extract activation energies via an Arrhenius type analysis,
and as a function of the pressures of each of the reactants to
extract reaction orders.86 Further post-mortem surface char-
acterization is also often performed by returning the sample to
the UHV environment in order to correlate structural and
chemical information about the surface with activity and
selectivity data obtained under reaction conditions.162,168,169
One common additional type of work performed in these
studies is the titration of the sites remaining on the surface
by using an appropriate molecular probe such as carbon
monoxide.170 In hydrocarbon catalysis, high pressure cells
have been used to acquire useful knowledge on the kinetics
and mechanisms of alkane reforming and hydrogenoly-
sis,171179 methane combustion,180 alkene hydrogenations
and dehydrogenations,158,181184 olefin metathesis,185 alkyne
trimerizations,186,187 ethylene epoxidation,163,188 hydrode-
sulfurizations,189,190 and dechlorinations,191 among others.
We have also carried out experiments of this type on metal
foils to study HD exchange reactions in alkanes,192 alkane
combustions,193 and alcohol partial oxidations.194,195 An ex-
ample of the results obtained from studies on the first system is
presented in Fig. 5.192 There, the main frame displays typical
product accumulation curves (collectively for all possible
deuterated ethanes, as detected by mass spectrometry) as a
function of time for a series of reaction temperatures, from
which initial rates were extracted and plotted in Arrhenius
form to extract activation energies. This, a typical procedure in
high-pressure cell experiments, highlights one of the main
limitations of the high-pressure cell methodology, which is
that although the quality of the raw data appears to be
excellent, the reaction rates, which are calculated by
Fig. 5 Main frame: Total product accumulation curves as a function
of time obtained from studies on the catalytic isotope exchange of
normal ethane with deuterium over a platinum foil at 545, 588, 605,
and 625 K.192 The symbols represent the experimental data, obtained
by following the disappearance of the light alkane, while the solid lines
are the result of fits to a first-order rate law. Analysis of this type of
data was used to obtain activation energies, pre-exponential factors,
and reaction orders. Inset: Isotopomer composition of the product
spectrometry197 and NMR196 characterization of the trapped pro-
ducts. The relative importance of the formation of ethylene vs.
ethylidene in the overall reaction mechanism could be assessed from
these studies.
Phys. Chem. Chem. Phys., 2007, 9, 38303852 | 3837

dierentiation, are not nearly as good. Additional interference
may arise from conversion of the reaction mixture on other
surfaces within the reactor, in particular on those of the
materials used to support and heat the catalytic sample. On
the positive side, batch reactors can be easily modified to trap
the accumulated products for further analysis. This turned out
to be particularly useful in our studies on the isotope exchange
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in ethane, where NMR196 and high-resolution and tandem
mass spectrometry197 techniques were used to determine the
regiospecificity of the deuterium substitutions (Fig. 5, inset),
and with that the relative importance of ethylidene versus
ethylene adsorbed intermediates in the reaction mechanism.192
It should be noted that these types of study using single
crystals and other pure metal model samples has not always
been capable of explaining observations from measurements
using supported catalysts. For instance, in the case of hydro-
carbon reforming, data for the conversion of n-hexane on
dierent crystallographic faces of platinum single crystals
could not account for the large fraction of benzene produced
by typical reforming catalysts.154,174,198 This is most likely due
to the fact that small metal particles dispersed on high surface-
area oxides do not simply exhibit a performance sum of the
activities of the dierent crystallographic facets exposed; both
the size of the metal particles and their interactions with the
underlying oxide are also important in defining the overall
catalytic performance.10,199201 This so-called materials gap mass spectrometer located in a dierentially-pumped chamber
has been recently dealt with by the development of new model
catalysts consisting of small metal particles deposited on thin
oxide films.86,202,203 Kinetic measurements on such surfaces
using high-pressure cells are still sparse, but promise to get us
one step closer to the understanding of more realistic catalytic
systems.
3.3 Nanoliter-sized reactors
As mentioned above, one diculty with high-pressure cells is
that they immerse not only the surface of interest but the
whole crystal and supporting materials inside the catalytic
reactor. The conversion of the reaction mixture on those
additional surfaces interferes with the accurate determination
of reaction rates on specific single-crystal surfaces, and typi-
cally blurs subtle dierences in rates among dierent surfaces.
In the case of the hydrocarbon reforming reactions discussed
before, the measured rates for reactions on dierent planes of
platinum single-crystals often dier by small factors, on the
order of 2 to 5,64,86,172,174 of magnitudes similar to the error
involved in the measurements. To study such subtle structure
sensitivities, it is crucial to measure reaction rates exclusively
on the surfaces of interest, isolated from any other interfering
elements of the reactor.
Clearly, much more surface structure control is possible
under ultrahigh vacuum (UHV) conditions, and therefore it
would be ideal to perform such kinetic measurements in those
types of apparatus. On the other hand, as mentioned above,
the catalytic conversion of olefins depends on the total pres-
sure at which the reaction is carried out (Section 3.1), and it is
not easily sustainable under those conditions.123,139,146,160 To
resolve this issue, we in our laboratory have recently developed
a UHV-compatible nanoliter-sized reactor capable of generat-
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ing high local gas fluxes reminiscent of atmospheric pressure
conditions on a small surface while maintaining a good back-
ground vacuum.149 A schematic representation of this instru-
ment, together with a picture of its end probe inside the UHV
chamber, is shown in the left panel of Fig. 6. A high-flux beam
of reactants is introduced and directed towards the front face
of the crystal via a small (diameter B1 mm) capillary, and the
gases trapped in a small volume defined by an outer concentric
tube also used to collect the products for mass spectrometry
detection into a separate dierentially-pumped volume. By
bringing the whole assembly within a few microns of the
surface, the load of gases into the UHV environment is
minimized. This design was partially inspired on related,
although significantly dierent, instruments developed
for screening of potential catalysts by combinatorial
methods.204,205
The right panel of Fig. 6 displays some recent results
obtained with this arrangement for the deuteration of ethylene
on a Pt(110) single-crystal surface. In this example a deuter-
ium-rich (D2 : C2H4 = 200 : 1) beam of F B 1 "
1020 molecules cm#2 total flux, the equivalent to a local
pressure of about 0.04 Torr, was directed at the platinum
surface while ramping its temperature in steps from about 370
to 430 K (top trace and left scale), and the production of
dideuteroethane (C2H4D2) was followed with the help of a
directly connected to the outer product-collecting cone of the
nanoliter-sized probe. The data obtained from this experiment
are reported in raw form in the lower trace of the main frame
of Fig. 6 (right scale), and in Arrhenius form in the inset of the
same figure. It does appear that steady-state reactions may be
sustainable with this arrangement, at least for olefin hydro-
genation and HD exchange catalytic processes, but further,
long lasting kinetic runs are required to corroborate this
tentative conclusion. We are at present adding a flow control
mechanism to the gas inlet to be able to perform such
experiments.
4. Kinetics of reactions involving adsorbed species
One key limitation common to all the techniques mentioned so
far is that they rely on the detection of the products that
desorb from the surface. TPD, molecular beam, and nanoliter-
size reactor measurements rely on the use of mass spectro-
metry, whereas analysis of the gases in high-pressure cell
reactors is typically performed by gas chromatography. None
of these methodologies is capable of directly looking into the
conversion of one surface species into another; for that, the use
of a surface-sensitive spectroscopic technique is required. In
fact, by detecting desorbing products, the kinetics measured in
TPD, beam, and reactor experiments often reflect the cumu-
lative eect of complex mechanisms involving several surface
reactions. As in many other fields, the overall kinetics of
surface reactions are nevertheless often used to speculate on
the formation of certain surface intermediates and on the
occurrence of specific surface steps.206208 Much information
can be extracted from cleverly designed experiments using
particular compounds, including isotope labeling, or parti-
cular conditions. However, no amount of indirect kinetic
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Fig. 6 Left: schematic depiction and picture of the nanoliter-sized reactor designed in our laboratory for isothermal kinetic measurements of low-
probability catalytic reactions on small surface-area samples. The gas mixture is fed through a small capillary tube onto the sample, and the
scattered gases and products collected by a concentric outer cone for mass spectrometry detection in a separate dierentially-pumped
compartment. By keeping the feeding tube small and close to the sample (a few mm away), a high local partial pressure can be reached above
the catalytic surface while keeping vacuum conditions in the main chamber. Right: kinetic data obtained using this setup for the conversion of
ethylene with D2 on a Pt(111) single-crystal surface. The temperature of the crystal was ramped in a stepwise manner while monitoring the
production of dideuteroethane (main frame), and the resulting data plotted in Arrhenius form to extract the value of the activation energy of this
reaction (inset). Steady-state reaction rates could be measured after temperature stabilization following the temperature jumps, indicating
significant catalytic conversion.

evidence can completely substitute direct evidence on surface
reactions obtained by spectroscopic determinations. This is
one of the strengths of the modern surface science approach to
the study of surface kinetics.
In principle, any spectroscopy capable of discriminating
between the surface species of interest and all others (as well
as of yielding signals proportional to surface concentrations)
can be used for the measurement of the kinetics of reactions on
surfaces. The idea is to tune the chosen spectroscopy to the
signal ascribed to the reactant or product for which the
kinetics is sought, and to follow that over time while holding
the temperature of the sample at a fixed predetermined
temperature (in isothermal studies). The main problem here
is that most surface-sensitive spectroscopies are slow, have
fairly restricted dynamic ranges, and yield noisy signals.
Nevertheless, there have already been many reports on the
measurement of kinetics of surface reactions by using a variety
of surface-sensitive analytical techniques, too many to prop-
erly review here. Instead, a few key examples will be provided
below from studies in our laboratory both in vacuum and
in situ under atmospheric pressure conditions.
4.1 UHV experiments
Although many surface-sensitive spectroscopies are in princi-
ple available to modern surface scientists to follow reaction
kinetics, the sensitivity limitations cited above narrow the field
of viable techniques for these studies considerably. Examples
are available in the literature for the measurement of surface
reaction rates using Auger (AES) and photoelectron spectro-
scopies (PES),100,209212 infrared spectroscopy,213,214 sum-fre-
quency generation (SFG),215 ion scattering,216 near-edge
X-ray absorption fine structure (NEXAFS),211,217 and work
function measurements,218 among others.
In Fig. 7 we provide two examples from our laboratory on
the application of surface-sensitive spectroscopies to the mea-
surement of surface reaction kinetics. In both cases synchro-
tron radiation was used as the excitation source to take
advantage of its high intensity and tunability.217,219223 The
left panel displays results from isothermal kinetic measure-
ments on the conversion of ethylene to ethylidyne on a Pt(111)
single-crystal surface by using NEXAFS.224,225 In this case,
the unique X-ray absorption feature at 285.8 eV seen for
ethylidyne at normal light incidence was chosen to follow its
buildup on the surface over time; data from isothermal runs
for three temperatures are shown in Fig. 7 (left) in the form of
the corresponding decrease in surface ethylene coverage. Ap-
propriate kinetic parameters were extracted from those data,
including the (first) order dependence of the reaction rate on
ethylene coverage and its activation energy, and a normal
isotope kinetic eect was measured by comparison of the
conversion with normal versus perdeutero ethylene.
In cases where the signals are strong, kinetic data can be
acquired in a temperature programmed fashion. This is illu-
strated by the data in the right panel of Fig. 7, which
correspond to a study of the trimerization of acetylene to
benzene on a Pd(111) single-crystal surface as followed by the
intensity of the C 1s X-ray photoelectron spectroscopy (XPS)
signal for acetylene at 283.0 eV.226 The design of this

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Fig. 7 Examples of kinetic measurements of surface reactions using surface-sensitive spectroscopies. Left: time dependence of the conversion of
ethylene to ethylidyne on a Pt(111) single-crystal surface at three dierent temperatures, as followed by the signal for ethylidyne seen at 285.8 eV in
near-edge X-ray absorption fine structure (NEXAFS) spectra.224,225 Right: evolution of the C 1s XPS signal versus temperature in temperature
programmed experiments for the conversion of acetylene to benzene on Pd(111).226 Both examples show how spectroscopic techniques can be used
to follow the kinetics of surface reactions as long as a spectroscopic feature unique to the species of interest can be identified, and provided that its
intensity can be calibrated to convert it to surface coverages. The left panel shows an example of isothermal kinetics, while the right displays results
from an experiment carried out in a temperature programmed mode.

experiment was helped by the fact that the product, benzene,
desorbs from the surface upon its formation (although some
surface benzene could still be identified in full XPS spectra by
the appearance of a new peak at 283.9 eV). In fact, the decay
of the C 1s XPS signal versus temperature could be roughly
correlated with the detection of benzene in TPD experiments.
It should be noted that, because of the speed at which the data
needs to be collected in this thermal programmed mode, the
signals are particularly noisy. This problem has been some-
what mitigated in recent times by the use of more intense
synchrotron sources,227 but the risk here is that such intense
radiation may promote the decomposition of the adsorbed
reactants, and hence aect the kinetics of the systems being
studied.
A related technique is static secondary ion mass spectro-
scopy (SSIMS), where the surface is radiated with a low-
current ion beam to induce the ejection of ionic fragments
from the adsorbed species.234,235 The experiment is run in a so-
called static (low ion current) mode to minimize damage of the
surface during the kinetic experiments.27 We have used this
technique to look into the uptake and thermal conversion of
ethylene on a Ni(100) single-crystal surface,236 and work has
also been reported by other groups on the use of SSIMS for
the characterization of hydrocarbons on metal surfaces. Here
it is worthwhile citing the temperature-programmed SIMS
studies by White et al. on the conversion of adsorbed ethylene
on Pt(111),237,238 Ru(0001),239 Ni(100),240,241 and
241,242
Ni(111), of acetylene on Ni(100) and Ni(111),241 and
240

To overcome the limitations imposed by the low sensitivity
of most surface-sensitive spectroscopies, several intermediate
techniques have been conceived where adsorbed species are
removed from the surface into the gas phase for mass spectro-
metry detection. One of these such methods is laser-induced
thermal desorption (LITD), where a laser beam is used to
locally heat a small spot on the surface to induce the molecular
desorption of the adsorbates. Molecular desorption is favored
in this procedure over lower activation-energy competing
pathways such as surface dehydrogenation by the fast heating
rate induced by the laser.228230 LITD kinetic experiments are
performed by sampling and analyzing small aliquots of the
surface species (by flashing the laser beam on dierent spots on
the surface) as a function of time during the course of the
surface reaction.231 The kinetics of ethylene conversion on
nickel232,233 and platinum213 single-crystal surfaces have been
investigated this way. An example of the data obtained in the
latter study is reported in Fig. 8.213
of ketene on Pt(111).243 Also worth mentioning is the research
by the group of Niemantsverdriet on the conversion of ethy-
lene244 and on the formation of CN bonds245 on rhodium
surfaces.
A third approach to these mixed surface reaction character-
ization by gas phase detection techniques is that pioneered by
Muetterties et al. based on the chemical displacement of one
adsorbate from the surface by another.246 Unfortunately this
method, although promising and potentially quite flexible, has
hardly been employed to date. The Muetterties group origin-
ally reported a few characterization studies on the thermal
chemistry of unsaturated247 and aromatic248 hydrocarbons on
Ni(111) single-crystal surfaces, and also on nitrogen-contain-
ing compounds such as acetonitrile and methyl isocyanide249
and on cyclic compounds250,251 on Pt(111). Campbell et al.
later advanced the use of bismuth as a potential displacement
agent for many organic adsorbates,252 but studies with this
methodology have so far been limited to a handful of

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Fig. 8 Time evolution of the production of C2D3H (31 amu signal) by
conversion of perdeuteroethylene (C2D4) with coadsorbed hydrogen
on a Pt(111) single-crystal surface at 215 K, as measured by laser-
induced thermal desorption (LITD) experiments.213 Three traces are
reported here, for ethylene initial coverages of 0.08, 0.13, and 0.20 ML.
The data in this figure show that the degree of HD exchange on the
adsorbed olefin decreases with increasing C2D4 coverage, perhaps
because of the restrictions in hydrogen mobility induced by the
coadsorbed hydrocarbon as the surface becomes more crowded. This
is a nice example of how LITD can be used to molecularly desorb and
detect stable surface intermediates in kinetic studies; more standard
and slower heating procedure lead to olefin decomposition instead.
systems.253256 A variation of the same idea was proposed by
White et al. where a small amount of oxygen is predosed on
the surface to scavenge any hydrogen released by dehydro-
genation reactions with adsorbed hydrocarbons to form water.
That water desorbs promptly, and can be easily detected by
mass spectrometry.257 However, questions remain about the
potential distortions introduced on the chemistry being probed
by the surface oxygen. Regardless, the use of this approach has
been quite limited. Also, none of the chemical displacement
methods discussed here have been yet used in kinetic experi-
ments.
4.2 In situ spectroscopic measurements in catalytic
environments
Spectroscopic detection can also be used for kinetic measure-
ments under conditions more closely resembling those asso-
ciated with catalysis and other surface processes of industrial
interest. This is most commonly performed to study reactions
in situ under atmospheric pressures in combination with high-
pressure cells (Section 3.2). Optical spectroscopies are parti-
cularly amenable for this use, and have indeed been incorpo-
rated into many high-pressure studies.258,259 Interesting
mechanistic conclusions on hydrocarbon surface reactions
have already derived from such work using infrared spectro-
scopy260263 and sum-frequency generation.258,264 Other tech-
niques such as NMR265 and Raman266,267 spectroscopies are
not sensitive enough for use with single crystals, but have been
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incorporated in studies with other model surfaces. Finally, the
use of synchrotron radiation has allowed for the incorporation
of X-ray absorption60,268,269 and photoelectron spectro-
scopy270,271 for this purpose.
A recent trend in this area has been to perform kinetic
measurements and surface characterization experiments simul-
taneously on the same system. This approach, dubbed oper-
ando, has started to produce some interesting observations
on real catalysts, in particular in terms of correlations between
kinetics and active surface intermediates.272277 For instance,
the reducibility of the dierent surface metal oxide species in
supported metal oxide catalysts, the relevance of surface
coverage (surface monomeric vs. polymeric species), and the
specific nature of the oxide support have been investigated
in situ during the selective oxidation of methane, other lower
(C2C4) alkanes, methanol, or hydrogen.276 In another study,
the destruction of chlorinated hydrocarbons with steam over
lanthanide oxide-based catalysts has been addressed.274 In
some instances, operando studies have shown that catalysts
may undergo dynamic structural transformations upon small
changes in reaction conditions, and that such transformations
have a strong impact on the performance of the catalysts.275
However, they have yet to be fully implemented for single-
crystal studies.
Fig. 9 shows results from an example from our laboratory
regarding the use of reflection-absorption infrared spectro-
scopy (RAIRS) in conjunction with a high-pressure cell to
look into the kinetics of surface reactions.278 In this case, the
stability of propylidyne surface moieties formed by room-
temperature adsorption of propylene on a Pt(111) single-
crystal surface was probed in the presence of a hydrogen
atmosphere at three dierent temperatures. Previous studies
have suggested that alkylidynes can be removed by such
treatment,182,279,280 and the data in this figure corroborates
that fact. Moreover, it is also seen here that the process is
activated, with almost no propylidyne removal from the sur-
face after more than an hour of H2 exposure at 310 K but
complete removal in less than 20 min at 375 K. Some addi-
tional changes are seen on the adsorbed species, as indicated
by the shift of the CH stretching frequency at 2960 cm#1
characteristic of propylidyne under vacuum to a slightly higher
value (2966 cm#1) immediately after exposure to the high H2
pressure environment. Finally, at 375 K, a new infrared
feature develops at about 2975 cm#1 after about 50 min, most
likely due to the partial hydrogenation of propylidyne to
propylidene or propyl moieties. Clearly, the surface chemistry
of alkylidyne under catalytic conditions is complex, and in
need of further studies.
The use of optical spectroscopies promises to extend the
study of in situ kinetics in catalysis to cases where the reactions
occur at solidliquid interfaces. This application is still recent,
but may be one of the new frontiers of modern surface
science.86,123,267,281 Fig. 10 shows results from studies in our
group on the displacement of cinchona adsorbed on the sur-
face of a platinum foil as a function of the amount of solvent
used in flushing experiments with dierent liquids.282,283 We
have also recently reported similar experiments on the dis-
placement of one cinchona by another.284 However, more
direct kinetic experiments using this approach have so far
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Fig. 9 In situ reflectionabsorption infrared spectroscopy (RAIRS) data obtained during the hydrogenation of propylidyne species adsorbed on a
Pt(111) single-crystal surface under 200 Torr of H2. Traces are shown as a function of reaction time for three temperatures (310, 335, and 375 K). A
few observations are relevant to the kinetics of this conversion: (1) the CH stretching frequency at 2960 cm#1 characteristic of propylidyne under
vacuum shifts to slightly higher frequencies (2966 cm#1) immediately after exposure to the high H2 pressure environment; (2) only very slow
changes are seen in the spectra at 310 K, but almost all the initial species are removed after 50 min at 335 K; (c) at 375 K, all the propylidyne is gone
after 20 min of reaction, but a new infrared feature (2975 cm#1) also develops after about 50 min, most likely because of the partial hydrogenation
of the propylidyne to new propylidene or propyl species.

been impaired by mass transport limitations.285,286 There are

no intrinsic reasons why this diculty cannot be surpassed,
but more work is needed to resolve the problem.

5. Isotope labeling and other chemical substitutions

Fig. 10 Kinetics of the extent of desorption of adsorbed cinchonidine
induced by dierent solvents as a function of the rinsing volumes
used.282 In these experiments the cinchonidine was first adsorbed from
a saturated carbon tetrachloride solution onto a polished polycrystal-
line platinum disk, and then flushed with sequential 20 mL aliquots of
the stated solvents. The evolution of the coverage of the adsorbate was
followed in situ by using the intensity of the infrared absorption signal
at 1512 cm#1, which corresponds to an in-plane deformation of the
quinoline ring,267 using a cell specifically designed to characterize these
solidliquid interfaces.281 It is clearly seen here that the reversibility of
the desorption is severely aected by the nature of the solvent, going
from fast desorption with water and dichloromethane to virtually
irreversible adsorption with cyclohexane and other alkanes. This is a
rare example of a kinetic measurement of a process involving hydro-
carbons on a model liquidsolid interface.
Additional mechanistic and kinetic information may be ob-
tained using selective isotope labeling in both TPD and
isothermal experiments. Isotope labeling is quite useful in
studies on hydrocarbon surface chemistry, and oers many
options, the limit being the imagination of the research-
er.287290 In fact, isotope labeling has already been used
extensively in conventional catalytic research.18,291,292 By far
the most used and useful isotope labeling approach, especially
in studies on hydrocarbon surface chemistry, is the substitu-
tion of hydrogen for deuterium atoms.293 Below, we initially
discuss the dierent ways in which deuterium substitution can
be employed in kinetic studies, and then a brief discussion is
put forward on the use of other isotopes and of chemical
substitutions.
5.1 Deuterium labeling: determination of reaction
regiospecificity
In its simplest and more straightforward application, selective
deuterium labeling can be used to identify the regioselectivity
of a given hydrocarbon conversion reaction. This approach
has been used extensively in the past. For instance, a series
of deuterium substitutions were employed by us to esta-
blish the preferential dehydrogenation of adsorbed al-
kyl80,99,101,102,104,110,294,295 and alkoxide88,109 species from
the b (second from the surface) carbon. Similar selective

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deuterium labeling has also been quite useful in determining
the relative rates of dehydrogenation at the a vs. g posi-
tions.110,296,297 Deuterium labeling is certainly used frequently
by many groups in mechanistic studies of surface reac-
tions.69,78,298,299
Fig. 11 provides a subtler example. In this case, the reaction
mechanism for the conversion of di-s adsorbed ethylene
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(PtCX2CX2Pt, X = H or D) to ethylidyne (PtRCCX3)
on a Pt(111) single-crystal surface was probed by exploring the
thermal chemistry of CD2 Q CDH in TPD experiments as a
function of initial coverage.300 Early studies had yielded
contradictory results as to the mechanism of this reaction,
with both ethylidene (PtQCXCX3)301303 and vinyl
(PtCXQCX2)304306 as possible intermediates. The data in
Fig. 11 resolved the previous conflicting results by suggesting a
change in mechanism with initial coverage, since the relative
probability of removal of one of the three deuterium versus the
normal hydrogen in CD2QCDH is quite high at low coverages
but falls to values significantly below the statistical expectation
at saturation. A two-step mechanism involving an ethylidene
intermediate was used to explain the results, with the rate-
limiting step being the initial 1,2-hydrogen shift to produce
ethylidene from ethylene at low coverages and the ethylene
ethylidene interconversion being fast and reversible and the
slow step being the subsequent dehydrogenation of ethylidene
to ethylidyne at high coverages. This example illustrates both
the potential and the limitations of the isotope labeling
experiments, because although they may help in the unraveling
Fig. 11 TPD results from studies on the thermal decomposition of
CD2QCDH on a Pt(111) single-crystal surface. The left panel shows
typical TPD traces for H2, HD, and D2 production in the case of a
saturated surface. Stepwise dehydrogenation is observed,75 with the
first feature peaking around 300 K due to the conversion of ethylene to
ethylidyne. A key result here is the observation of dierent relative
yields for the production of hydrogen at 300 K versus higher tempera-
tures for the three dierent isotopomers (compare the relative heights
of the 300 vs. 500 K peaks in the H2, HD, and D2 traces). The right
panel summarizes the D-to-H yield ratios obtained for the 300 K peak
of TPDs such as those in the left panel as a function of initial ethylene
coverage. A dramatic reduction of that ratio is seen with increasing
coverage, attesting to a change in the mechanism for the overall
ethylene to ethylidyne conversion.
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of multi-step mechanisms, they provide only indirect informa-
tion about them, and usually rely on certain assumptions (in
this case that CH bond scissions take precedent over CD
bond-breaking steps in the rate-limiting step because of a
normal kinetic isotope eect).
5.2 Deuterium labeling: kinetic isotope eects
As stated above, regioselective labeling has been quite useful in
kinetic studies as a way of identifying reactive moieties.
However, interpretation of the results from those experiments
must be done carefully, since they can be aected by unfore-
seen and unintended collateral eects. For one, the substitu-
tion of hydrogens for deuteriums introduces significant kinetic
isotope eects, since CH bonds dissociate (and form) at
rates typically two to six times faster than CD bonds (as
mentioned in connection with the analysis of the data in
Fig. 11).224,225,232,304 This eect can certainly aect selectiv-
ities, and in extreme cases even induce a switching between
competing reactions.
One elegant example of such a selectivity change by isotope
labeling is provided by the results from our studies on the
decomposition of neopentyl moieties on a Pt(111) single-
crystal surface.110,297,307 In this work, the dehydrogenation
of the neopentyl species was followed via the detection of the
neopentane produced in TPD experiments by subsequent
rapid elimination of other neopentyl surface groups with the
resulting hydrogen (or deuterium) atoms. Data were collected
for the conversion of neopentyl groups selectively deuterated
at either the a (left panel) or g (right panel) positions, and
plotted in Arrhenius form in Fig. 12 for easier visualization of
Fig. 12 Arrhenius plot of the leading edge of neopentane TPD data
from selectively isotope-labeled neopentyl iodides adsorbed on a
Pt(111) single-crystal surface.297,353 Results are presented for experi-
ments with neopentyl groups selectively deuterium-labeled at the a
(left panel) and g (right) carbons. Given that hydride elimination from
those moieties leads to the rapid subsequent hydrogenation of addi-
tional neopentyl groups to neopentane, the isotope composition of the
products can be used to identify the regioselectivity of the rate-limiting
dehydrogenation step. In both cases it was found that H elimination
steps dominate over any possible D eliminations, even if that means
that the relative rates for a-hydride vs. g-hydride eliminations is
reversed. This is a dramatic example of a control of reaction selectivity
based on kinetic isotope eects.
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the dierences in reaction rates between the competing a- and
g-H elimination reactions. A particular interesting observation
deriving from this data is the fact that the resulting kinetic
isotope eects not only aect the relative rates of the dierent
hydride elimination steps, but actually control the selectivity
of the reaction: selective dehydrogenation always occurs at the
position with normal hydrogen atoms. The example in Fig. 12
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also illustrates the fact that although activation energies
estimated from TPD experiments may be no more accurate
than B10%, much more subtle kinetic dierences can be
identified by a direct comparison of reaction rates at a given
temperature in the raw TPD data, in particular in the case of
competing reactions within the same chemical system. Indeed,
in this example significant rate dierences, of the order of a
factor of B5, are clearly seen in the raw TPD data in spite of
the fact that the activation energies of the a- and g-hydride
elimination competing steps dier by less than 5% of their
absolute values.
5.3 Deuterium as a reactant
Another way to use isotopes in TPD experiments for kinetic
studies is as a reactant. In hydrocarbon conversions in parti-
cular, hydrogenation (deuteration) reactions can be studied
comparatively by performing contrasting experiments with
surfaces predosed with H2 vs. D2. The use of deuterium instead
of hydrogen leads to the formation of heavier molecules, and
therefore allows for easier separation and identification from a
complex pool of potential products.81,308,309 In addition, by
looking at the specific cracking pattern of a given product,
these experiments oer the potential of helping in the identi-
fication of the position in which the hydrogenation takes place.
An example of the latter is provided by our study on
carboncarbon double bond migrations in cyclic olefins.89
Fig. 13 shows TPD traces for the key masses followed in
experiments with coadsorbed methylene cyclopentane (MeCp)
and deuterium on a Pt(111) single-crystal surface. Previous
TPD experiments with MeCp on clean and hydrogen-predosed
surfaces were sucient to identify the three main reaction
channels leading to C6 hydrocarbon desorbing products,
namely, molecular desorption at around 220 K, isomerization
to 1-methyl-cyclopentene (1MCp=) at about 260 K, and
hydrogenation to methyl cyclopentane (MCp) at about
205 K. By analyzing the distribution of intensities among the
mass spectrometry signals for the dierent masses correspond-
ing to the ions of both the cyclopentyl (left panel) and
molecular (right panel) fragments, the data in Fig. 13 add to
that conclusion the fact that the first hydrogen (deuterium)
incorporation step occurs at the exo methylene group. This
type of information is virtually impossible to obtain without
the aid of isotope labeling.
Fig. 13 also highlights another advantage of using deuter-
ium instead of hydrogen as a reactant in hydrocarbon thermal
conversion experiments: the potential opening of HD ex-
change reactions.310312 HD exchange is often quite useful in
determining mechanistic details in surface reactions. For
instance, a careful analysis of the data in Fig. 13 provides a
clearer picture of how the bond migration and hydrogenation
reactions take place in cyclic olefins. The TPD results are
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Fig. 13 TPD data from studies on the thermal conversion of methy-
lene cyclopentane (MeCp) with coadsorbed deuterium on a Pt(111)
single-crystal surface.89 Shown are the traces for key fragments
representing the molecular ions (right panel) as well as those originat-
ing from the cyclopentyl ring (formed during cracking in the mass
spectrometer ionizer, left panel). These data were used to determine
not only the products of this reaction (non-, mono-, and di-deuterated
methylene cyclopentane at lowB220 Ktemperatures, 1-methyl-
cyclopentene at higher, B 260 K, temperatures, and dideutero methyl
cyclopentane around 205 K), but also the regioselectivity of the
deuteration steps. The first deuterium incorporation occurs at the
exo methylene position.
consistent with the initial incorporation of a deuterium atom
in the methylene moiety of MeCp to form an intermediate
1-methyl-cyclopentyl intermediate.89 That alkyl surface spe-
cies can then either accept a second deuterium atom to form
MCp-d2 (as seen in the 71 and 86 amu traces), or undergo
b-hydride elimination to return a new olefin. A complication
arises from the fact that, depending on the regioselectivity of
the dehydrogenation step, dierent products are possible.
Here, an early elimination at the methyl group returns mono-
deuterated MeCp-d1 (the 220 K peak in the 68 and 83 amu
traces), and a subsequent elimination at one of the C2 position
of the ring produces monodeuterated 1MCp=-d1 (the 260 K
peak in the 68 and 83 amu traces). A new round of deuterium
incorporation and b-hydride elimination steps yields the di-
deuterated products detected in the 69 and 84 amu traces. All
these observations have shed some light on the driving force
for double bond migration reactions in olefins.89
HD exchange reactions can also be used to separate
dierent elementary steps with similar kinetics. One interesting
application of this idea is provided by the recent example from
our group on the use of HD exchanges as a proxy for
cistrans carboncarbon double-bond isomerizations.66,313
The idea there is that, by following the so-called Horiuti
Polanyi mechanism illustrated in the previous paragraph (half
hydrogenation of an adsorbed olefin followed by either re-
ductive elimination with a second hydrogen to the alkane or
b-hydride elimination back to another olefin), each cistrans
isomerization conversion in olefins is accompanied by a
replacement of one hydrogen by another in the molecule. If
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deuterium is used as a reactant instead, this can be easily
followed by identifying the number of deuterium substitutions
in the product. In our initial studies using this powerful
approach, we determined that on Pt(111) single-crystal sur-
faces it is easier to isomerize trans-2-butene to its cis isomer
than the other way around. This is somewhat counterintuitive,
since trans configurations are generally more thermodynami-
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cally stable than their cis counterparts, and points to a possible
control of selectivity away from trans fat production in
oil hydrogenation processes by tuning the structure of the
catalyst.313
As in the other cases discussed previously, kinetic isotope
eects can also alter selectivities in hydrogenation and HD
exchange reactions. These eects can be seen when substitut-
ing molecular hydrogen for deuterium, but also in going from
normal to perdeutero hydrocarbons. The laser-induced ther-
mal desorption experiments on the conversion of adsorbed
ethylene to vinyl moieties on Ni(100) single-crystal surfaces
reported earlier (Section 4.1) provide a nice example of the
latter.232,233,314 There is also the case of ethylene conversion on
Pt(111) surfaces, where the molecular TPD shows two peaks
populating sequentially with increasing coverage.75,300,308 In-
terestingly, the first peak occurs at similar temperatures with
C2H4 and C2D4, but the second shifts, peaking at significantly
higher temperatures in the case of the perdeutero molecule.
This strongly suggests that the second TPD peak is not due to
simple molecular desorption of the original adsorbate, but
may be the result of reversible hydrogenationdehydrogena-
tion (deuterationdedeuteration) steps on the surface instead.
Similar behavior has been observed in other systems.
5.4 Isotope switching
An elegant use of isotope labeling is isotope switching during
isothermal kinetic experiments. In these, steady-state kinetics
is first reached using a reaction mixture with regular isotopes,
and then the original mixture is replaced with a second of
equal composition but an appropriate isotope labeling. This
procedure is reasonably well established in catalysis,315317 but
less common in surface science. One nice illustration of the use
of this approach comes from our molecular beam research on
the reduction of nitrogen oxide on rhodium surfaces using
eusive molecular beams.136,318 Another informative example
relates to our investigations of olefin hydrogenation reac-
tions,11,13,139,140 where some relevant information could be
extracted on the dynamics of the adsorption of olefins on
metal surfaces even though no steady-state reactivity could be
reached.
It is known that the adsorption of ethylene (and other
olefins) on Pt(111) single-crystal surfaces involves two distinct
and separate states, a di-s species irreversibly bonded on the
clean surface and a p reversible state which develops at high
coverages.75,261,319322 Our isotope switching experiments in-
dicated that those two states can slowly interchange on the
surface.139,140 This is illustrated by the data in Fig. 14, which
shows how some of the normal ethylene adsorbed during
exposure of the Pt(111) surface to a beam of C2H4 (as
manifested by the dip in its trace between 10 and 15 s) is
displaced by C2D4 upon switching to a beam of perdeuter-
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Fig. 14 Data from isotope switching molecular beam experiments on
the adsorption of ethylene on a Pt(111) single-crystal surface.139,140 In
this case the Pt surface was first predosed with 0.5 ML of atomic
hydrogen, after which it was exposed to a 0.04 ML s#1 beam of normal
ethylene. The beam was let to impinge on the surface at t = 10 s (flag
up), at which point the dip in the mass spectrometry signal indicates
adsorption, until saturation was reached once the signal returns to its
original value. After about 20 s that beam was turned o, and at t =
30 s a new, identical beam of C2D4 was turned on. At that point some
C2H4 desorbs, displaced by the incoming C2D4, and both C2D4 uptake
and C2H4 evolution are seen in the data. However, the amount of
C2D4 taken up by the surface does not fully account for the extent to
which normal ethylene is displaced. This is due to a complex adsorp-
tion process involving the slow interconversion of di-s and p bonded
ethylene molecules on the surface.
oethylene (hence the detection of some signal for C2H4 starting
at the 30 s mark and the corresponding dip in the C2D4 trace
due to its adsorption). A more careful analysis of these data
suggests an adsorption mechanism at high coverages via an
initial interaction with the few metal atoms left exposed by an
imperfect monolayer followed by a collective rearrangement of
the neighboring molecules into a new compressed layer.140
5.5 Other isotopes
Although the use of other isotopes is not as common in surface
kinetic studies as that of deuterium, it is nevertheless done on
occasion. In hydrocarbon research, useful substitutions in-
clude 13C for 12C, 15N for 14N, and 18O for 16O. Since the mass
dierences between these pairs of isotopes are not nearly as
significant as in the case of the substitution of hydrogen for
deuterium, their kinetic eects are fairly subtle. Instead, the
heavy isotopes are employed mostly to dierentiate between
two or more reactants with similar or overlapping mass
spectra.323,324 For instance, both 13C and 18O are often used
to separate reaction-produced from background carbon mon-
oxide (and also from molecular nitrogen),325 and 15N to do the
same in studies with NO.134,326
18
O labeling in particular is quite useful in studies of
oxidation reactions.327329 Typically, that isotope is used to
dierentiate among the various possible sources of oxygen in
the production of oxygen-containing compounds, as in the
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case of water decomposition and recombination on clean and
oxygen-treated metal substrates.330,331 Similar issues can also
be resolved in this way in connection with the conversion of
alcohols, aldehydes, and other oxygenated hydrocarbons.332
Fig. 15 reports results from a subtler study aimed at identify-
ing particular reaction sites in the case of the oxidation of
methylene on oxygen-treated Ni(110) single-crystal sur-
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crystal surface by following the appropriate changes in radio-
activity.280 Finally, isotope labeling also helps in the assign-
ment of peaks in vibrational spectroscopy experiments.342,343
This latter application is the most common with deuter-
ium,83,88,295,344 but it is also applied to heavier isotopes.

5.6 Chemical substitutions

faces.333 It has been well established that in the initial stages
of the oxygen uptake Ni(110) reconstructs to form rows of
alternating nickel and oxygen atoms on the topmost
layer,334336 and it has also been suggested that the terminal
oxygens in those NiO rows are the most reactive for the
conversion of hydrocarbons.11,330,337,338 With that in mind, an
experiment was designed to attempt to prepare such NiO
rows with the inner atoms selectively 18O-labeled by sequen-
tially dosing a small amount of 18O2 and then a larger quantity
of 16O2 to 16O-cap the row ends in order to test the source of
the oxygen that incorporates into coadsorbed methylene moi-
eties to form formaldehyde.333 The key result, illustrated by
the TPD traces in the middle panel of Fig. 15, was that, still,
significant amounts of 18O-labeled formaldehyde are made on
those surfaces. The implication is that the rows are suciently
dynamic to rearrange and expose all the oxygen atoms for
reaction.
Another interesting, albeit rare, use of isotopes is in con-
junction with a new analytical technique only applicable to
that isotope. A typical example of this in catalysis is the
employment of 57Fe, 193Ir, or 197Au for Mossbauer Absorp-
tion Spectroscopy.339341 A more relevant illustration of this
idea for this review is our past use of 14C-labeled ethylene to
study the kinetics of its thermal conversion on a Pt(111) single-
Specific positions within the structure of the reactants can also
be labeled by using chemically analogous moieties. In hydro-
carbons, hydrogen atoms may be replaced by alkyls of dier-
ent sizes, or even by halogen atoms. In this case the interest
often is to identify reactivity trends, by, for instance, blocking
particular reactive points within a molecule (by substituting
hydrogens for methyl groups),110,296 or by changing the in-
ductive or steric properties of a moiety. A nice example of the
latter is the use of fluorine as a strong electronegative group to
replace hydrogens in hydrocarbons.345 We have used this
approach in the past to study the oxidation of alcohols to
aldehydes and ketones, in that case to inhibit b-hydride
elimination from alkoxide surface groups and to enhance the
competing g-hydride elimination step.346
In Fig. 16 we show data from another study, in this case
involving the use of fluorine labeling for the characterization
of carboncarbon double bond isomerizations.347 Cis- and
trans-2-butenes were fluorine-labeled at the end methyl posi-
tions in an attempt to dierentiate the two by mass spectro-
metry, since normal 2-butenes are indistinguishable by that
technique. Unfortunately, the dierences in cracking patterns
between the cis and trans difluorobutenes (Fig. 16, inset) were
still not significant enough for us to unequivocally deconvolute

Fig. 15 Deconvoluted TPD traces obtained for the thermal conversion of methylene groups (prepared by decomposition of CH2I2) on oxygen-
treated Ni(110) single-crystal surfaces (at 400 K to assure molecular dissociation). Three panels are shown for three dierent experiments with
dierent oxygen isotope labelings in an attempt to identify the nature of the species that react with the hydrocarbon. The main product in all cases
is ethylene (from the coupling of two methylene groups), but ethane is also produced (by hydrogenation of that product), and, more to the point of
this research, formaldehyde (via oxygen insertion into the metalmethylene bond). The key result is shown in the middle panel, for a surface
prepared by sequential dosing of 1.0 L of 18O2 and 6.0 L of 16O2. Oxygen adsorption on Ni(110) is known to create NiO rows on the
surface,334336 so such a sequential dosing was designed to deposit Ni18O rows capped by 16O ends. Since it is the terminal oxygens which are
believed to be the most reactive,11,330,337,338 this experiment was expected to lead to the preferential formation of H2C16O. The detection of
significant amounts of H2C18O contradicts this hypothesis, and indicates high mobility of the oxygen atoms on the surface leading to their
scrambling within the NiO rows.

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Fig. 16 Main: key TPD traces from studies with saturation coverages
of cis (left panel) and trans (right panel) 1,4-difluoro-2-butenes ad-
sorbed on a Pt(111) single-crystal surface. The signals for 72, 77, and
92 (and many more) amu were recorded in an (unsuccessful) attempt
to identify any possible cistrans isomerization. What is clear is that
the cis isomer displays an additional desorption state at around 265 K,
and that with both molecules a new HF formation channel with no
parallel in the chemistry of regular 2-butenes opens up.
their contributions in these TPD experiments. On the other
hand, new interesting chemistry was identified, as highlighted
by the production of HF seen in the TPD experiments (Fig. 16,
main frame). Based on what is known from the gas-phase
chemistry of these compounds it would be tempting to propose
a 1,4 elimination reaction for this HF production, but the fact
that similar results were obtained with the cis and trans
isomers argues against such a hypothesis. Further deuterium
labeling experiments are underway to identify the mechanism
of this surface reaction.
6. Concluding remarks
In this review a critical discussion is provided on the main
techniques available in modern surface-science laboratories
for the study of the kinetics and mechanisms of hydrocarbon
reactions on metal surfaces. It was argued that, although a
simple and reasonably old and well-established technique,
temperature programmed desorption (TPD) is still the work-
horse in this field. Indeed TPD continues to be a very useful
method for the study of the kinetics of surface reactions
because of the richness of the resulting data, which provides
estimates for activation barriers and relative yields and much
information on reaction mechanisms. On the other hand, TPD
suers from several significant limitations, and is prone to
over-interpretation. In this vein, it must be remembered that
activation barriers extracted from TPD data are often not
reliable to better than B10%, and that the yields measured by
TPD are usually not representative of what may be obtained in
steady-state processes. Finally, mechanistic information de-
rived from TPD studies must be extrapolated with caution to
catalytic or other problems where reactions occur under
significantly dierent conditions.
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Better kinetic data can in principle be obtained isothermally,
but advances in this direction have so far been limited. One
possibility here is the use of molecular beams, but this has not
been widely utilised to date, perhaps because of the perceived
sophistication of the instrumentation needed. It is also true
that steady-state kinetics can only be emulated under vacuum
for very high probability (41%) reactions, a severe limitation
that precludes the study of most hydrocarbon conversions. So-
called high-pressure cells have been used to obtain kinetic
catalytic data ex situ on surfaces prepared and characterized in
controlled vacuum environments, but that approach is limited
as well, in this case because of possible contamination of the
sample under the atmospheric pressures used, and also be-
cause of possible interference from other parts of the reactor in
the kinetic measurements. A hybrid nanoliter-sized reactor has
been developed in our laboratory to address these problems,
but its implementation is still incomplete, and its usefulness
has not yet been fully tested.
Most kinetic techniques in surface science rely on the
detection of desorbing species by mass spectrometry, but
complementary work can also be carried out on the temporal
evolution of adsorbed species by using any of the many
surface-sensitive techniques available nowadays. These experi-
ments are often performed under vacuum, but can be designed
for in situ use during catalytic runs too, in particular when
optical spectroscopies are employed. This is critical, because
no amount of kinetic experimentation, no matter how cleverly
those are designed and interpreted, can replace the direct
detection of surface intermediates and surface elementary
steps. On the other hand, it should also be kept in mind that
surface intermediates in catalytic reactions are often unstable
and short-lived. This means that many of the surface species
seen in surface science studies are too stable to be involved in
the actual catalytic conversion, and may act as spectators
instead. The problem of isolating and characterizing relevant
intermediates may be overcome by reducing the surface tem-
perature, performing spectroscopic studies in situ at high
pressures, or using appropriate precursors.
Finally, the determination of reaction rates and kinetic
parameters is often accompanied by additional mechanistic
studies of surface conversions aided by the use of isotope
labeling. In this review a number of approaches were discussed
for this, including simple regiospecific substitutions, measure-
ments of kinetic isotope eects, isotope switching in steady-
state kinetics, and the use of isotopes as reactants. Collectively,
all these techniques provide an extensive and powerful toolbox
for the study of hydrocarbon reactions on solid surfaces.
An additional tool not discussed in this review but of
increasing importance in surface science studies is computa-
tional calculations.321,348351 Many theoretical groups have
made significant strides in understanding adsorbates on sur-
faces. The work of Neurock deserves particular mention here,
because his group has combined quantum mechanics with
kinetic calculations to identify transition states and to high-
light the importance of weakly bound intermediates and sur-
face coverage eects in surface chemistry. However, modern
cluster and density functional quantum mechanics calculations
are not yet accurate enough to estimate activation barriers for
competing reactions with sucient accuracy to predict
Phys. Chem. Chem. Phys., 2007, 9, 38303852 | 3847

selectivities in most cases. This is nevertheless a very promising
area of research with potential predictive power unmatched by
experiments.
Although not the central objective of this review, the
examples cited above have also provided a reasonable over-
view of the central lessons learned from kinetic studies on the
surface chemistry of hydrocarbons on metal surfaces.3,33,76
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For one, a few illustrations were provided of studies on the
regioselectivity of the first dehydrogenation step from ad-
sorbed alkyl species, key intermediates in many hydrogena-
tion, dehydrogenation, isomerization, and other reforming
catalytic processes. The data in Fig. 2 and 3 indicated the
high preference for elimination at the b position, that is, from
the carbon adjacent to that bonded to the surface, and the
results in Fig. 12 showed that when that position is not
available (and also at the higher temperatures employed in
oil reforming)8 a close competition between a- and g-hydride
elimination ensue instead.
Other work has focused on the complexity of the adsorption
and reactivity of chemisorbed olefins. Two types of adsorption
states are known for those, a strong di-s bonding and a more
weakly and reactive p mode.75 It is commonly accepted that
the second type of adsorption is the one relevant to most
catalytic reactions,139 but that picture is further complicated
by the possible interchange between the two states (Fig. 14).
The surface interconversion between alkyl and alkene ad-
sorbed moieties has also been explored, to a great extent by
studies involving HD isotope exchange (Fig. 5 and 8),192,213
and in connection with key olefin hydrogenation (Fig. 6)66,352
and carboncarbon double-bond isomerization (Fig. 13 and
16)89,313 reactions. Olefin dehydrogenation also competes with
those processes,80,300 though, and leads to the formation of the
strongly-bonded carbonaceous deposits encountered in many
hydrocarbon conversion catalysts (Fig. 7, 9 and 11).8,71
Finally, some mention was made of hydrocarbon oxidation
reactions. In one example, reference was made to the possible
reforming of alkanes with oxygen to produce hydrogen
(Fig. 4). The selective formation of oxygenated products via
oxygen insertions is also possible, although that competes with
other steps such as alkyl and carbene couplings and carbene
insertions (Fig. 15).65,88,194,329 Overall, the examples discussed
above highlight one of the key issues still unresolved in
hydrocarbon catalysis, that of controlling selectivity among
the wide range of competing reactions available to those
systems.12,13 This remains a challenge for surface scientists
and catalysis researchers alike, one that kinetic studies should
help advance.
This review has tried to provide a personal and critical
review of the techniques available to surface scientists for the
study of the kinetics of surface reactions, in particular those
relevant to catalysis. It is clear that we now have at our
disposal a nice battery of techniques for this purpose, although
they may still have serious limitations and require further
development. It is also important to stress the need for further
studies of surface kinetics. This has acquired renewed rele-
vance in recent times with the increased need for highly
selective catalytic processes in industry. Problems of selectivity
are definitely more dicult to address and understand than
those related to absolute activity, but this can be viewed as a
3848 | Phys. Chem. Chem. Phys., 2007, 9, 38303852
View Article Online
challenge for the next generation. It would be good to see the
new surface scientists embracing kinetic problems in addition
to the more popular material characterization themes in vogue
today.
Acknowledgements
Major funding for this research was provided by the US
National Science Foundation. We also acknowledge the help
of Prof. Thomas Morton in the synthesis of the difluoro-
butenes used in the experiments reported in Fig. 16.
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