Topics in Catalysis 1 (1994) 233-252 233

Ammonia synthesis kinetics: surface chemistry,

rate expressions, and kinetic analysis
Luis M. Aparicio and James A. Dumesic
Department of Chemical Engineering, Universityof Wisconsin,
Madison, WI53706, USA

The results of surface science studies of nitrogen adsorption and desorption on iron single
crystals are summarized with respect to ammonia synthesis reaction kinetics. Analytical rate
expressions for ammonia synthesis on high surface iron catalysts at industrial reaction condi-
tions are presented and compared to the behavior of microkinetic models based on the surface
science results. Microkinetic models based on uniform surfaces are successfulin extrapolating
"results from surface science studies at low surface coverages to describe the performance of
iron catalysts at industrial ammonia synthesisreaction conditions. We suggestthat the value of
rate constant for recombination of nitrogen atoms on the surface is a weak function of surface
coverage. Furthermore, modest variations in the heat of N2 adsorption are sufficient to
achieve fractional ammonia orders that are relativelyinsensitiveto the ammonia pressure.
Keywords: ammonia synthesis; microkinetic modeling; reaction kinetics; surface science
studies; adsorption isotherms

1. I n t r o d u c t i o n

The synthesis of a m m o n i a over iron catalysts has been studied for over 70
years. During the past 20 years, experiments involving surface science techniques
such as Auger electron spectroscopy, X-ray photoelectron spectroscopy, work
function measurements and temperature-programmed desorption have been con-
ducted to probe the adsorbed species and the kinetics o f nitrogen adsorption a n d
desorption. M o s t o f these experiments have been conducted at sub-atmospheric
pressures on iron single crystals. Furthermore, several investigators have
a t t e m p t e d to incorporate these surface science data into microkinetic models a n d
to use these models to describe reaction kinetics data collected at industrial reac-
tion conditions (e.g., temperatures near 430°C and pressures near 100 atm). The
results o f the modeling efforts, through their successes and shortcomings, have con-
tributed further to our understanding of the reaction mechanism, as described
later in this review.
In the following sections, we review the surface science work of the last
20 years relevant to elucidation of the reaction mechanism of a m m o n i a synthesis

© J.C. Baltzer AG, SciencePublishers

234 L.M. Aparicio, J.A. Dumesic / Ammonia synthesis kinetics

over iron catalysts and the kinetics of the elementary steps in the mechanism. We
also review efforts to extrapolate these data to reaction conditions using microki-
netic modeling. Finally, we review proposed analytical rate expressions and their
relationships to the microkinetic models. For more complete reviews, readers are
referred to articles byNielsen [1] and Ertl [2].

2. K n o w l e d g e prior to surface science studies

Before the extensive surface science studies were undertaken, much was already
known about the mechanism of ammonia synthesis over iron. It was generally
believed that ammonia synthesis proceeded through elementary steps in which
both nitrogen and hydrogen adsorb and dissociate on the surface, atomic hydrogen
adds stepwise to atomic nitrogen, and ammonia desorbs from the surface, as
shown below:
1 N2 + * ~ *N2
2 *N2 ~ 2 , N
3 ,N + ,H ~ ,NH + •
4 , N H + , H ~ ,NH2 + •
5 *NH2 + , H ~ ,NH3 + •
6 *NH3 ~ NH3 + •
7 H2 + 2, ~ 2 , H
where • signifies a vacant site on the surface.
Early studies established that under typical reaction conditions the rate deter-
mining step involves nitrogen adsorption and/or dissociation. This conclusion was
reached after observing that nitrogen adsorption on iron catalysts proceeded at a
rate approximately equal to that of ammonia synthesis [3,4]. Further confirmation
was obtained in studies showing that hydrogenation proceeded much faster than
nitrogen adsorption [5].
Evidence for the stepwise hydrogenation of surface nitrogen atomic species was
also found. Infrared spectroscopy experiments identified N H and NH2 species on
the surface [6]. In addition, N H + species were detected by secondary ion-ion emis-
sion studies during ammonia synthesis, suggesting the presence of N H species on
the surface [7].
It was known that nitrogen adsorbed molecularly at low temperatures but could
dissociate at higher temperatures. Various experiments showed that different spe-
cies result from nitrogen adsorption at different temperatures. For example, it was
found that nitrogen adsorbed at temperatures from 130 to 300°C inhibits the
adsorption of carbon monoxide, whereas nitrogen adsorbed at 450°C does not
[8,9]. In another study, nitrogen adsorbed at 210°C had different reactivity toward