Top Catal (2017) 60:631–633

DOI 10.1007/s11244-017-0735-y

ORIGINAL PAPER

What is the Order of a Reaction?

Jordi Burés1

Published online: 9 May 2017

© The Author(s) 2017. This article is an open access publication

Abstract The order of a reaction in some species seems
an obvious, trivial concept that all chemists master. How-
ever, in complex situations such as catalytic systems, the
order of a reaction is not always that simple: it can be par-
tial, negative and function of other parameters. In order to
analyze rate laws and experimental orders of complex reac-
tion networks, it is necessary to have a proper mathematical
description of what the order of a reaction is. In general,
chemists working in catalysis are unaware that such a math-
ematical description exists and therefore they are restricted
to analyzing only extreme limit cases of rate laws. This
manuscript offers a description and a simple demonstration
of this concept, known as elasticity coefficient or normal-
ized sensitivity. It also presents several examples of appli-
cations on classic and usual catalytic scenarios.
Keywords Order · Elasticity coefficient · Rate laws ·
Kinetics
1 Introduction
each time. This information is useful from a practical point
of view, and it also allows discerning between different
mechanistic proposals. Each mechanistic proposal has a
different rate law, which is the equation that indicates the
expected effect of each parameter on the rate of a reaction.
However, this information is not always easy to extract and
interpret for catalytic reactions due to the inherent com-
plexity of their rate laws.
Chemists usually quantify the effect that a parameter has
in the rate of a reaction with the order. The IUPAC defines
that a reaction is of order α with respect to a substrate A
only when the macroscopic rate can be expressed by a
power law: r = k[A]α[B]β… [1]. For reactions with more
complex rate laws, as catalytic reactions usually have, it is
necessary to identify a surrogate power law that best repro-
duces the real equation at each point ­(s0.3 in Fig. 1). These
surrogate power laws must have the same value (Eq. 1) and
the same slope (Eq. 2) as the rate law at that specific point
­([A]i). By using these two conditions, it is possible to find a
general mathematical description for the order of a reaction
in A.

(1)
( ) ( )
r [A]i = si [A]i = ki [A]i 𝛼i
Kinetic studies of catalytic reactions are an essential part of
experimental mechanistic studies, performed to understand dr ds (𝛼 −1)
these reactions at a molecular level. Kinetic studies reveal ([A]i ) = ([A]i ) = ki 𝛼i [A]i i (2)
d[A] d[A]
how much each parameter affects the rate of a reaction at
From (1):

Electronic supplementary material The online version of this

( )
r [A]i
article (doi:10.1007/s11244-017-0735-y) contains supplementary ki = 𝛼 (3)
material, which is available to authorized users. [A]i i

* Jordi Burés From (2) and (3):

jordi.bures@manchester.ac.uk
dr [A]i d ln r([A]i )
1
School of Chemistry, University of Manchester, Oxford αi = 𝜀r([A]) = ([A]i ) ⋅ = (4)
d[A] r([A]i ) d ln [A]i
Road, Manchester M13 9PL, UK

13
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632
Fig. 1  The surrogate power-law function, ­s0.3, which best fits the real
curve, r, at [A] = 0.3 M is the one with an order of 0.4
The alternative mathematical formulas shown in Eq. 4 are
known as elasticity coefficient or normalized sensitivity
(𝜀r([A]) ) and are used in mathematics, physics, economics [2],
and enzymology [3–6]. However, this concept has been
underused in mechanistic studies of organic and inorganic
catalytic reactions. Instead, the analysis of the orders for rate
laws has usually been restricted to unrealistic limit cases and
therefore really valuable information has been discarded.
Currently, there are available free tools to take the derivative
of the rate law in order to quickly find the elasticity of any
complex rate law equation of a catalytic reaction without
requiring advanced knowledge of calculus [7]. Therefore, the
normalized sensitivity analysis should get routinely included
in the studies of rate laws of catalytic reactions.
2 Examples
There are several scenarios where the use of the normal-
ized sensitivity function can be useful. For the popular
13
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Top Catal (2017) 60:631–633
Fig. 2  The order in catalyst for a reaction catalyzed by a dimeric spe-
cies changes from 2 to 1
unireactant catalytic reaction of Fig. 1 following the
Briggs-Haldane kinetics [8], the order of the reaction in
substrate A is defined by Eq. (5).
KM k + k2
εr[A] = ; where KM = −1 (5)
KM + [A] k1
This equation allows us to plot the curve of order in
[A] against the concentration of [A] (Fig. 1). Also, the
equation makes it evident that the order of the reaction
in [A] is independent of the total concentration of cata-
lyst. Therefore, higher concentrations of catalyst do not
require higher concentrations of substrate to achieve satu-
ration conditions as it might appear at first glance.
Another usual scenario with complex orders in cata-
lytic reactions results from equilibria involving catalytic
species composed by multiple units of catalytic mol-
ecules, such as dimers or trimers. Figure 2 shows the
analysis of the order in catalyst for a reaction catalyzed
by a dimeric species in equilibrium with an inactive
monomeric species. In this case, the order in catalyst is
between 2 and 1 depending on the range of concentra-
tions of catalyst analyzed, as well as the concentration of
substrate and the kinetic constants.
Different reaction mechanisms can lead to the same
dependency of the order in catalyst or any other param-
eter of the reaction. For example, the reaction scheme
shown in Fig. 3, where one of the byproducts of one of
Top Catal (2017) 60:631–633 633

Fig. 4 shows that, in this case, the expected constant first

order in catalyst is disturbed at low concentrations close to
the concentration of the inhibitor. The lack of awareness of
this alternative scenario can mislead some researchers, who
may misinterpret the higher order in catalyst at low concen-
trations of catalyst as the consequence of either having an
active dimeric species in equilibria with an out-cycle mon-
omeric inactive species (Fig. 2), or a reaction where one of
the byproducts is used as a reactant (Fig. 3).
Fig. 3  The order in catalyst for a reaction where a byproduct is used
as a subsequent reactant changes from 2 to 1
3 Conclusions

The elasticity coefficient is the mathematical description

of what chemists call order of a reaction. The awareness of
this quantitative description of the order of a reaction facili-
tates the kinetic analysis of complex reaction mechanisms,
such as catalytic reactions. A better understanding of the
concept “order of reaction” by the catalysis community will
enable a better interpretation of kinetic data thus allowing
the consideration of alternative mechanisms.

Acknowledgements Stimulating discussions with Dr Julia Vila-

doms and David Bures are gratefully acknowledged.

Open Access This article is distributed under the terms of the

Creative Commons Attribution 4.0 International License (http://
creativecommons.org/licenses/by/4.0/), which permits unrestricted
use, distribution, and reproduction in any medium, provided you give
appropriate credit to the original author(s) and the source, provide a
link to the Creative Commons license, and indicate if changes were
made.

References
Fig. 4  The order of a reaction in catalyst added in the presence of an
irreversible inhibitor
the steps in the cycle is used as a reactant in a subsequent
catalytic step, has the same dependency of the order in
catalyst as the reaction previously analyzed in Fig. 2
(indeed, for the values shown, the curves would be identi-
cal). This is a good example of how the analysis of the
order of the reaction in catalyst facilitates the comparison
of rate equations for different reaction mechanisms.
The elasticity analysis is especially useful in more com-
plex scenarios. For example, it enables the prediction of
the order in catalyst for a reaction where a constant quan-
tity of the catalyst gets irreversibly deactivated by some
impurity contained in the reaction media. The analysis in
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