Journal of Fluorescence, Vol. 15, No. 2, March 2005 (©2005)
DOI: 10.1007/s10895-005-2518-2
Fluorimetry Studies of Oscillating Chemilumnescence
in the Luminol H
2
O
2
KSCN CuSO
4
TMAOH System
Abdolraouf Samadi-Maybodi,
1,2
Niloofar Naseri,
1
and M. J. Chaichi
1
Received March 14, 2004; accepted December 2, 2004
Oscillating chemical reactions are complex systems, involving a large number of chemical species.
In oscillating chemical reaction, some species, usually a reaction intermediate, exhibit fluctuation
in its concentration. In this report, visible oscillating chemiluminescence produced by the addition
of luminol (3-aminophthalhydrazide) to the oscillating system of H
2
O
2
KSCN CuSO
4
TMAOH
was investigated using spectrofluorimetry method. The effects of ingredient concentration of the
oscillating system and complexing agents like citric acid and cysteine on the behavior of the oscillating
system were investigated. Moreover, the influence of nonaqueous solvents such as ethanol and
ethylene glycol has been studied.
KEY WORDS: Oscillating chemiluminescence; luminol; fluorimetry; complexing agent; non-aqueous solvents.
INTRODUCTION
Oscillating chemical reactions are always complex
systems involving a large number of chemical species,
which can be categorized as reactants, products and inter-
mediates that show unusual mechanisms [1,2]. Basically,
an oscillating chemical reaction is the one where some
species (usually a reaction intermediate) exhibit fluctua-
tions in their concentration; such fluctuations are period-
icity or non-periodicity under specific reaction conditions.
For such oscillating reaction, at least three requirements
must be met [3]. (a) The system should be far from thermo-
dynamic equilibrium, under such conditions, spontaneous
oscillations can be generated [4]; (b) there should be at
least one autocatalytic step or, alternatively, cross cataly-
sis between the two steps of the reaction mechanism; and
(c) the system should possess at least two steady states
under the initial conditions.
1
Department of Chemistry, Faculty of Basic Science, Mazandaran
University, Babolsar, Iran.
2
To whom correspondence should be addressed. E-mail: samadi@umz.
ac.ir
The fluctuations are reflected in color changes (if the
oscillating species exhibit different colors), pH changes
(variations in the H
+
or OH
−
concentration in the
medium), redox potential changes, etc. Several meth-
ods, such as pH metery, potentiometry [5–8] and chemi-
luminescence [9–11], have been applied in the inves-
tigation of oscillating reactions. One of the oscillating
reactions reported recently has an initial composition
of H
2
O
2
KSCN CuSO
4
TMAOH, determined using
conductometry method [12].
The sharp pulses of blue light (λ
max
= 424 nm)
produced by the addition of luminol to the oscillating
system H
2
O
2
KSCN CuSO
4
TMAOH are unlike the
oscillation characteristic to this system. In basic aqueous
solution, chemiluminescence results from the oxidation of
luminol by hydrogen peroxide catalyzed by a transition-
metal ion such as copper or cerium. The light-generating
reaction of luminol has been the subject of many
researches.
Typical oscillation attributes such as the oscillation
period and amplitude were recently used to evaluate their
use in chemical analysis [7,8]. In regular oscillations, the
oscillating period and amplitude depend strongly on the
concentrations of the reaction ingredient [11].
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1053-0509/05/0300-0117/0 C 2005 Springer Science+Business Media, Inc.