Research: Science & Education
Does a Photochemical Reaction Have a Reaction Order?
S. R. Logan
Department of Chemistry, University of Ulster at Coleraine, N. Ireland, BT52 1SA, UK
Among chemical reactions in the gas phase or in so-
lution that require no external agent such as light or
ionizing radiation to bring them about, the concept of
reaction order is well understood as the index of the con-
centration of the reactant that leads to a parameter pro-
portional to the reaction rate. Where the reaction is occa-
sioned by light absorption and is a straightforward con-
version of one species into another, the progress of the
reaction is controlled simply by the rate of light absorp-
tion by the molecules of reactant. However, one can cite
circumstances in which the log of the concentration of
the reacting species will fall linearly with time and there
is then a temptation to describe the photochemical pro-
cess as being a first-order reaction. The propriety of so
doing deserves comment.
If one considers a simple photochemical reaction sys-
tem in which the reactant molecule A absorbs at the
wavelength of the exiting light whereas the product mol-
ecule B does not, assuming that a parallel and uniform
beam of light makes normal incidence on a rectangular
cell, it is possible to produce a simple expression for the
rate of light absorption. If there are Q quanta per sec-
ond entering the cell, of path length l, then the number
of quanta per second absorbed within the cell is given
by Q (1 10-cl), where is the molar decadic absorption
coefficient of A at the wavelength of irradiation and c
denotes the concentration of A. Consequently the num-
ber of moles of A caused to react in unit time will be
Q(1 10-cl) /NA, where is the quantum yield for the
photochemical interconversion of A to B and N A is
Avogadros constant. An equation equivalent to the above
expression is to be found in Levine (1) as eq 21.82. In gen-
eral, the topic of photochemical kinetics is not treated in
physical chemistry texts.
Vol. 74 No. 11 November 1997 Journal of Chemical Education
Two extreme situations are readily identified. One
occurs when cl > 2, so that well in excess of 99% of the
light entering the cell is absorbed within it. Thus the
number of moles of A reacting in unit time is essentially
Q/ NA, which is independent of the concentration of A.
That is, provided that the concentration of A is much
greater than ( l){1, the rate of the photochemical conver-
sion is constant. Consequently, the amount of A in the
cell will now decrease linearly, and if the cell contents
are well stirred, the concentration of A will fall off in
that manner.
The other extreme is when cl << 1, and only a small
fraction of the light entering the cell is absorbed within
it. In this case the factor (1 10 {cl ) is well approximated
by 2.303 cl, so that the number of moles of A reacting
in unit time is given by 2.303 Qcl /NA, which is directly
proportional to the concentration of A. Consequently, the
amount of A in the cell will decrease exponentially.
This shows that, as a consequence of these differ-
ences in experimental conditions, this photochemical con-
version may fit either of two regimes. In the first, the
amount of A in the cell decreases as it would for a reac-
tion of zero order; but in the second, it falls as for a first-
order reaction. Since the manner of the decrease of the
reactant concentration is so totally a function of the re-
action conditions, it makes no sense to speak of a reac-
tion order for such a photochemical reaction. A rate con-
stant quoted in such a connection thus has no sound ba-
sis. The only parameter that may meaningfully be used
to denote how efficiently a photochemical conversion pro-
ceeds is the quantum yield.
Literature Cited
1. Levine, I. N. Physical Chemistry, 4th ed.; McGraw-Hill: New York, 1995.
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