If the macroscopic (observed, empirical or phenomenological)
rate of reaction
(v) for any reaction can be expressed by an empirical differential rate equation (or
rate law) which contains a factor of the form
...
(expressing in full the dependence of the
rate of reaction on the concentrations
,
...)
where
,
are constant exponents (independent of concentration and time) and
is independent of
and
etc. (rate constant,
rate coefficient), then the reaction is said to be of order
with respect to A,
of order
with respect to B, ... , and of (total or overall) order
The exponents
,
, ... can be positive or negative integral or rational nonintegral numbers. They are
the reaction orders with respect to A, B, ... and are sometimes called '
partial orders of reaction'. Orders of reaction deduced from the dependence of initial rates of reaction on
concentration are called '
orders of reaction with respect to concentration'; orders of reaction deduced from the dependence of the
rate of reaction on time of reaction are called '
orders of reaction with respect to time'. The concept of order of reaction is also applicable to chemical rate processes
occurring in systems for which concentration changes (and hence the
rate of reaction) are not themselves measurable, provided it is possible to measure a
chemical flux.
For example, if there is a dynamic equilibrium according to the equation:
and if a
chemical flux is experimentally found,
(e.g. by NMR
line-shape analysis)
to be related to concentrations by the equation:
then the corresponding reaction is of order
with respect to A ... and of total (or overall) order
.
The proportionality factor
above is called the
(
th order) '
rate coefficient'. Rate coefficients referring to (or believed to refer to)
elementary reactions are called '
rate constants' or, more appropriately '
microscopic' (hypothetical, mechanistic) rate constants. The (overall) order of a reaction cannot
be deduced from measurements of a '
rate of appearance' or '
rate of disappearance' at a single value of the concentration of a species whose concentration is constant
(or effectively constant) during the course of the reaction. If the overall
rate of reaction is, for example, given by:
but [B] stays constant, then the order of the reaction (with respect to time), as
observed from the concentration change of A with time, will be
, and the
rate of disappearance of A can be expressed in the form:
The proportionality factor
deduced from such an experiment is called the '
observed rate coefficient' and it is related to the
th
order
rate coefficient by the equation:
For the common case when
,
is often referred to as a '
pseudo-first order rate coefficient'
(
).
For a simple
(elementary) reactions
a partial order of reaction is the same as the
stoichiometric number of the reactant concerned and must therefore be a positive integer
(see
rate of reaction ).
The overall order is then the same as the
molecularity .
For
stepwise reactions there is no general connection between
stoichiometric numbers and partial orders. Such reactions may have more complex rate laws, so that
an apparent order of reaction may vary with the concentrations of the
chemical species involved and with the progress of the reaction: in such cases it is not useful to
speak of orders of reaction, although apparent orders of reaction may be deducible
from initial rates. In a
stepwise reaction, orders of reaction may in principle always be assigned to the elementary steps.
Source:
PAC, 1994, 66, 1077
(Glossary of terms used in physical organic chemistry (IUPAC Recommendations 1994))
on page 1147
PAC, 1993, 65, 2291
(Nomenclature of kinetic methods of analysis (IUPAC Recommendations 1993))
on page 2296
PAC, 1996, 68, 149
(A glossary of terms used in chemical kinetics, including reaction dynamics (IUPAC
Recommendations 1996))
on page 176