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Mechanism of the Fenton reaction. Evidence for a new intermediate

Mordechai L. Kremer

Department of Physical Chemistry, Hebrew University, Jerusalem, Israel

Received 17 May 1999, Accepted 7th June 1999

For the Ðrst time, the time dependence of the amount of O evolved in the reaction of Fe2` with H O (the
2 2 2
Fenton reaction) was measured by following the decrease of the total [Fe3`] formed upon quenching the
reaction mixture with an excess of a strongly acidic solution of Fe2`. The disappearance of Fe2` in the
reaction was followed by quenching it with o-phenanthroline and measuring the absorbance of the
Fe2`-phenanthroline complex formed at j \ 510 nm. At [H O ] \ 10~4 mol dm~3, and quenching the
2 2
Published on 01 January 1999 on http://pubs.rsc.org | doi:10.1039/A903915E

reaction with Fe2` ions, the formation of a new intermediate was observed. It was identiÐed as the mixed
valence binuclear species MFeOFeN5`. A new mechanism for the reaction has been proposed in which FeO2`
acts as the key intermediate. Several rate constants and ratios of rate constants have been determined. The
existence of free radicals in the system does not seem to be compatible with the data.

Introduction concentrations of the reactants (about 1 ] 10~3 mol dm~3

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[Fe2`] and [H O ] [ 1 mol dm~3). There was, thus, no iden-

The investigation of the mechanism of the reaction of Fe2`
ions with H O (the Fenton reaction) has by now a history of
2 2
over a hundred years.1,2 Still, the question of its mechanism
has not yet been settled satisfactorily. Present day theories are
based on a landmark suggestion of Haber and Weiss accord-
ing to which OH and HO free radicals are the key interme-
2
diates in the reaction.3,4 The original mechanism of Haber
and Weiss has been subsequently modiÐed by Barb et al.5 In
its modiÐed form, it accounted successfully for several basic
features of the reaction :
(a) In an excess of Fe2` ions over H O , the reaction is
2 2
restricted to the quantitative oxidation of Fe2` ions by H O .
2 2
2 Fe2` ] H O ] 2 Fe3` ] OH~ (a)
2 2
(b) In an excess of H O over Fe2` ions, catalytic decomposi-
2 2
tion of H O
2 2
2 H O ]2 H O]O (b)
2 2 2 2
accompanies the oxidation of Fe2` ions.
(c) The mechanism also accounted for the observation that
the rate of the reaction is of the Ðrst order in both [Fe2`] and
[H O ] at the beginning, but subsequently the apparent order
2 2
of the reaction increases in regard to [Fe2`]. (A detailed dis-
cussion of the mechanism of Barb et al. is given in the Appen-
dix.)
A complete kinetic investigation of the overall reaction
requires the measurement of two concentration variables as a
function of time, either of the pair [Fe2`]È[O ] or of the pair
2
[Fe3`]È[H O ] or of some other equivalent combination.
2 2
Haber and Weiss measured, using relatively concentrated solu-
tions, the overall changes of [H O ] and [Fe2`] but did not
2 2
follow their separate courses in time. By using more dilute
solutions, Barb et al. measured [Fe2`] as the function of time
([Fe2`] about 1.5 ] 10~5 mol dm~3 and [H O ] in the range
2 2
1 ] 10~4 [ 1 ] 10~3 mol dm~3). They determined also the
total amount of O evolved in the reaction prior to the onset
2
of the relatively slow evolution of O through pure Fe3` ion
2
catalysis. They have obtained, thus, a single point of the total
[O ] vs. time curve. Because of the necessity of producing
2 2
measurable quantities of gas, they increased considerably the
2 2
tity of experimental conditions in the two sets of measure-
ments. To obtain analytically closed solutions of the rate
equations, Barb et al. used always a large excess of H O over
2 2
Fe2`. This fact also restricted the scope of their experimental
work.
The present work was undertaken with the aim of extending
the experimental basis of the investigation of the reaction by
measuring the amount of O evolved as a function of time.
2
Also, the excess of H O over Fe2` was greatly reduced in the
2 2
experiments (down to [H O ] /[Fe2`] \ 0.4) in order to
2 2 0 0
investigate e†ects which are unobservable when a large excess
of H O over Fe2` ions is applied.
2 2
The measurement of [O ] was based on the following con-
2
sideration : if to a reacting mixture of Fe2` and H O , after
2 2
the lapse of a certain time interval, excess Fe2` ions in a
strongly acidic solution are added, then in the absence of for-
mation of O , the amount of Fe3` ions formed will always be
2
equal to twice the initial amount of H O , no matter at what
2 2
stage of the reaction the addition of Fe2` ions occurred. If, on
the other hand, part of the H O was decomposed to O and
2 2 2
H O prior to the addition of Fe2`, then for every mole of O
2 2
formed four moles of Fe3` ions will be missing. The absorb-
ance (A) of the quenched reaction mixture will then be given
by
A \ A [ 4 e 3`[O ]l (1)
0 Fe 2
A is the absorbance at t \ 0, e 3` is the molar absorptivity
0 Fe
of Fe3` ions and l is the length of the light path in the solu-
tion. As the reaction progresses and O is formed, the absorb-
2
ance of the quenched reaction mixture will decrease (see Fig. 7
later). Using this method, [O ] in the concentration range of
2
10~6È10~5 mol dm~3 could be determined. As a comparison,
measuring [O ] with a Clark type O electrode, the concen-
2 2
tration of dissolved O could not be reduced below 6 ] 10~5
2
mol dm~3 by purging the solution with N for 30 min setting,
2
thus, a lower limit of the applicability of the method.6 It may
be remarked that it would have been possible, by using eqn.
(1), to determine [O ] also beyond its solubility limit in case
2
of a stronger evolution of O than actually observed. In reac-
tions in which the initial ratio [H O ] /[Fe2`] was less than
2 2 0 0
Phys. Chem. Chem. Phys., 1999, 1, 3595È3605 3595

one, eqn. (1) was insufficient to account for the absorbance. In
that range of concentrations, a modiÐed form of eqn. (1) was
used.
Experimental
Iron powder puriss. of Fluka and H O 30%, unstabilized,
2 2
Selectipur grade of Merck were used. Deionized water was
further puriÐed in a Milli Q Reagent Water System apparatus.
The speciÐc resistance measured was [10 M) cm. Other
materials used were of analytical grade.
Preparation of Fe(ClO )
42
Fe(ClO ) was prepared from iron powder and HClO in a
42 4
closed vessel in a N atmosphere. The apparatus is shown in
2
Fig. 1. Initially, the apparatus was dismantled. 50 ml of a fac-
torized D0.5 mol dm~3 solution of HClO and a calculated
4
volume of water were introduced to Flask A. The concentra-
tion of the acid and the volume of the water were adjusted so
Published on 01 January 1999 on http://pubs.rsc.org | doi:10.1039/A903915E
as to give (after the dissolution of Fe and appropriate dilution)
the desired pH in the reaction mixture. 2.5È70 mg of Fe
powder (weighed with a precision of ^0.02 mg) was placed in
a small beaker on the hanging platform B. The apparatus was
assembled and a stream of N , previously saturated with
2
water vapours, was passed through the solution for 30 min.
Excess N was removed through the rubber septum E by
2
using a syringe needle with an attached plastic tube leading to
a water trap (similar to trap I in Fig. 2). After 30 min by
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slightly tilting the apparatus, the beaker containing the Fe
powder was allowed to fall into the acid. Dissolution was
complete after 12 h in a water bath of 27 ¡C. Small amounts,
usually a few drops, of the liquid could be withdrawn through
the outlet F by slightly increasing the pressure of N in the
2
vessel and by opening the TeÑon valve D. No trace of Fe3`
ions could be detected in the solution. At no stage of the prep-
aration were reactant solutions in touch with grease. All
burets used to dispense solutions had TeÑon taps. The calcu-
lated values of [Fe2`] , (1) based on the weight of Fe dis-
0
solved and (2) determined with o-phenanthroline agreed
within 1%. The latter value was taken uniformly as [Fe2`] .
0
The subscript 0 denotes t \ 0. Kept in the closed vessel, the
reagent remained stable for over one week.
Determination of Fe2‘ ions
The method of Hardwick7 was used with one modiÐcation :
instead of 95% C H OH, o-phenanthroline was dissolved in
2 5
an aqueous solution on a water bath. 0.37 g NH F and 1.93 g
4
CH COONH (corresponding to 0.2 mol dm~3 NH F and
3 4 4
0.5 mol dm~3 CH COONH ) were dissolved in 50 cm3 of
3 4
cold water in an Erlenmeyer Ñask. Subsequently, 0.15 g of
crystalline o-phenanthroline was poured into the solution and
Fig. 1 Closed vessel for the preparation of Fe(ClO ) under N .
42 2 2
3596 Phys. Chem. Chem. Phys., 1999, 1, 3595È3605
View Online
heated on a water bath under constant swirling until all the
crystals were dissolved. The cooled solution, kept in a dark
Ñask, remained stable. Blanks showed no signiÐcant absorp-
tion at j \ 510 nm even after several days. In contrast, o-
phenanthroline solutions kept in ordinary daylight darkened
after several hours. 1 cm3 of the reagent was used for every 10
cm3 of Ðnal volume. Absorbance was measured at j \ 510
nm. Calibration, using two independent standards prepared
from solid (NH ) Fe(SO ) É 6H O, gave a molar absorptivity
42 42 2
of e \ 1.141 ] 104 mol~1 dm3 cm~1 (compared with
1.125 ] 104 mol~1 dm3 cm~1 given by Hardwick). The initial
concentration of H O was determined by titration with
2 2
KMnO .
4
Measurement of the absorbance after quenching the reaction
mixture with excess Fe2‘ ions
The absorbance is due to several contributions : (a) absorb-
ance of Fe3` ions formed in the reaction until the addition of
the quenching solution, (b) absorbance of Fe3` ions formed
after quenching as a result of the reaction of excess Fe2` ions
with H O present in the reaction mixture at the time of
2 2
quenching and (c) the absorbance of any other species formed
in the reaction.
In order to obtain reproducible results, several conditions
must be met : (a) the reagent must be free from Fe3` ions, (b)
the oxidation of Fe2` ions by air during the determination
must be negligible, (c) after quenching, the reaction of Fe2`
ions with H O must be quantitative and (d) Fe3` ions must
2 2
be converted to a stable well deÐned complex. To meet these
conditions, solid (NH ) Fe(SO ) É 6 H O was dissolved in 1
42 42 2
mol dm~3 H SO . With the rubber septum J removed, the
2 4
solution was introduced to the upper reservoir F of the appar-
atus shown in Fig. 2. The apparatus was closed again and the
solution was allowed to pass a Cd column of 20 cm length.
The solution was collected in the Ñask G. N was passed
2
through the solution, the gas being removed through the trap
I. By a slight increase of the pressure of the gas and by suit-
able settings of the three-way taps B and C, the solution was
forced into the upper reservoir F. The reduction cycle was
repeated, until a sample removed through the outlet H gave a
Fig. 2 Reduction column under N .

Fig. 3 Absorbance of sulfate and phosphate complexes of Fe3`.
[Fe3`] \ 5.05 ] 10~5 mol dm~3, l \ 1 cm. (a) Absorbance in
2.5 ] 10~2 mol dm~3 H SO ] 5.0 ] 10~2 mol dm~3 H PO . (b)
2 4 3 4
Absorbance in 2.5 ] 10~2 mol dm~3 H SO .
2 4
Published on 01 January 1999 on http://pubs.rsc.org | doi:10.1039/A903915E
blank absorbance of not more than 0.010È0.015. In the
strongly acidic solutions used, air oxidation of Fe2` was neg-
ligible during the duration of the measuring procedure. To
ensure the quantitative reaction between Fe2` ions and
H O , high [Fe2`] in the reagent would be required. It is
2 2
difficult however to reduce the residual [Fe3`] in such solu-
tions to an acceptable level. Thus, a compromise had to be
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found between the two conÑicting requirements. Further
adjustable parameters were the time and temperature for the
reaction between Fe2` and H O after quenching. They were
2 2
adapted to the range of concentration of H O to be deter-
2 2
mined and are given in Table 1. To obtain accurate data, the
conversion of Fe3` ions into a stable, well deÐned form is
necessary. The method used by Rigg et al. for converting Fe3`
ions into their sulfate complex(es) at a constant temperature
was found not to give sufficiently accurate results.8 Accuracy
was greatly improved by adding H PO to the mixture. Fig. 3
3 4
shows the absorbance of solutions of Fe3` ions in the pres-
ence of (a) H PO and H SO and (b) H SO alone.
3 4 2 4 2 4
Fig. 4 shows the e†ect of increasing [H PO ] on the
3 4
absorbance of Fe3` ions at two wavelengths. The curve at
j \ 210 nm shows the gradual conversion of the sulfate into
the phosphate complex. At the isosbestic point at j \ 222 nm,
the addition of H PO does not a†ect the absorbance.
3 4
The following procedure was adopted. The reaction mixture
(3.09 or 3.14 cm3) was quenched with 2 cm3 of a solution of
Fe2` ions in 1 mol dm~3 H SO . The quenched solution was
2 4
immersed in a thermostat at a given temperature. After a
certain time, 0.2 cm3 of 1 mol dm~3 H PO for every cm3 of
3 4
the Ðnal volume was then added and the solution was trans-
ferred to a volumetric Ñask. It was Ðlled up to the mark and
the absorbance of the solution was measured. Absorbance
readings were constant for incubation times ranging from 15
min to 1 h. As a matter of routine, an incubation time of 30
min was chosen (in procedure no. 4, also 15 min was found to
be sufficient). The constancy of the absorbance and its pro-
portionality with known concentrations of H O proved that
2 2
the reaction of H O with the reagent was complete. The
2 2
Table 1 Determination of Fe3` formed in di†erent ranges of concentration of H O
[Fe2`] in
Procedure Range of [H O ]/mol dm~3 quenching solution/mol dm~3
2 2
1 1.1 ] 10~3È2 ] 10~4 1 ] 10~2
2 5 ] 10~4È1 ] 10~4 5 ] 10~3
3 2 ] 10~4È4 ] 10~5 1.25 ] 10~3
4 8 ] 10~5È2.5 ] 10~5 5 ] 10~3
View Online
Fig. 4 E†ect of H PO on the absorbance. [Fe3`] \ 5.05 ] 10~5
3 4
mol dm~3, l \ 1 cm, [H SO ] \ 2.5 ] 10~2 mol dm~3. (a) j \ 210
2 4
nm, (b) j \ 222 nm.
wavelength, j, the width of the optical cell and the Ðnal
volume were adjusted so that the absorbance measured
remained in the range 0.2È0.6. Table 1 summarizes the details
of the experimental procedures followed in di†erent ranges of
[H O ]. [H O ] in the second column is calculated for the
2 2 2 2
volume of the reaction mixture. In fact, the absorbance of
Fe3` in a Ðnal constant volume was measured. Knowing the
two volumes and the stoichiometry of the reaction, the respec-
tive concentrations of Fe3` and H O could readily be inter-
2 2
converted. On the basis of the calibration curves in the four
ranges listed in the table, the apparent molar absorptivity of
Fe3` (e 3`) was calculated. j \ 222 nm was used for absorb-
Fe
ance measurements, except in the lowest range of [H O ],
2 2
where j \ 270 nm was chosen (in order to lower the absorb-
ance of blank solutions). In ranges 1È3, a single blank was run
for a series of measurements and absorbance was measured
against a water Ðlled cell. In range 4, a separate blank was run
with each determination. Absorbance measurements in this
range were made against identically treated blank solutions.
Kinetic measurements
Reaction vessels were small 6 cm3 test tubes whose upper
parts have been widened into small bulbs with a wide neck at
the top. 0.0990 or 0.0494 cm3 of H O was introduced in a
2 2
series of reaction vessels with micropipettes (nominal volumes
0.1 and 0.05 cm3, respectively). [H O ] was determined with
2 2 0
permanganate both at the beginning and at the end of the
measurements (6È8 h). The two values agreed within 1%. 2.99
cm3 (3.00 cm3) of a 4.81 ] 10~2 mol dm~3 NaClO solution,
4
kept in the thermostat, was added to H O , prior to initiating
2 2
a run. To start a run, a few drops of Fe(ClO ) were with-
42
drawn from the closed storage vessel and collected in a small
beaker. 0.0496 cm3 (0.05 cm3) of this solution was transferred
to the Ñattened end of a glass rod. A stop watch was started
and at a pre-set time, the rod was plunged into the H O
2 2
solution with vigorous stirring. After the lapse of a given time
interval, the quenching solution was injected using a syringe
the needle of which was replaced by a short plastic tube. It
was either 1 cm3 of phenanthroline or 2 cm3 of an acidic
ferrous ion reagent (appropriate for the range of the concen-
tration of H O ). The reaction could be quenched 4 s after its
2 2
initiation. The quenched solutions were treated as described.
2 2
Temperature/¡C Final volume/cm3 l/cm j/nm
25 50 1 222
25 25 1 222
35 25 2 222
27 25 5 270
Phys. Chem. Chem. Phys., 1999, 1, 3595È3605 3597
 View Online
In the case of the determination of [Fe2`], it consisted of
diluting the solution to 10 ml (or 25 ml) and measuring the
absorbance. In a typical experiment 10È12 measurements of
the absorbance were made. The decrease of [Fe2`] was fol-
lowed until about 90% of the Fe2` ions were oxidized.
Absorbance, after the quenching of the reaction with Fe2`
ions, was measured until the major change of it was over. In
all cases investigated, the disappearance of Fe2` ions was
quicker than the evolution of O , although the two time
2
scales approached each other at very low [H O ]. The pH of
2 2
the solution was calculated from the knowledge of the concen-
tration of HClO used to dissolve Fe, by taking into account
4
(a) the amount of acid used up in dissolving Fe and (b) the
extent of diluting the reagent in forming the reaction mixture.
The pH in all experiments was uniformly 2.43. There was an
increase of the pH during the reaction due to the oxidation of
Fe2` ions :
2 Fe2` ] H O ] 2 Fe3` ] 2 OH~ (c)
2 2
Published on 01 January 1999 on http://pubs.rsc.org | doi:10.1039/A903915E

This e†ect was partly compensated by hydrolysis of the Fe3`

ions formed
Fe3` ] H O \ FeOH2` ] H` K (d)
2 d
The setting of the initial pH at 2.43 and in the range of [Fe2`]
used, it was calculated that the increase of the pH during the
reaction did not exceed 0.01 units. Milburn and VosburghÏs
value of 3.40 ] 10~3 mol dm~3 was taken for K .9 The ionic
d
strength (I) of the reaction medium was adjusted to 0.05 mol
dm~3 using NaClO .
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4
Absorbance measurements were performed on a Beckman
DU spectrophotometer. It was equipped with a digital output
device to increase the accuracy of the readings and to increase
their range. Calculations were performed on the VAX com-
puter of the Computer Center of the Hebrew University using
numerical integration programs of the IMSL library.
Results
All experiments were run at pH 2.43, I \ 5.00 ] 10~2 mol
dm~3 and t \ 25.0 ¡C. [H O ] was varied between 4 ] 10~5
2 2 0
and 1 ] 10~3 mol dm~3. The limits of the range of [Fe2`]
0 0
were 6 ] 10~6 and 2 ] 10~4 mol dm~3. Tables 2A and 2B
show in detail two experiments in which the reaction was
quenched at various times (A) with o-phenanthroline and (B)
with Fe2` ions.
The decrease of the absorbance in time in Table 2B shows
the formation of O . Comparing the data of Table 2A and 2B
2
it is seen that the disappearance of Fe2` ions is much more
rapid than the formation of O . Also, the disappearance of
2
Fe2` ions can be monitored much more accurately than the
formation of O : the extent of change of the absorbance in
2 2 2 0
Table 2B is much smaller than that in Table 2A. The results of
several series of measurements are shown in Figs. 5È8.
Fig. 5 shows the absorbance, after quenching the reaction
with o-phenanthroline, as a function of time. In the series,
[Fe2`] was kept virtually constant at 1 ] 10~4 mol dm~3
0
while [H O ] was decreased from 1 ] 10~3 to 5 ] 10~5 mol
2 2 0
dm~3. (Curve a is a graphic presentation of the data of Table
2A.) The curves in Fig. 6 show another series in which the
reaction was quenched with o-phenanthroline. Here [H O ]
2 2 0
was approximately constant at 3.2È3.3 ] 10~4 mol dm~3
while [Fe2`] was varied between 6 ] 10~6 and 2 ] 10~4
mol dm~3. Fig. 7 shows the change of absorbance in time
when the reaction was quenched with Fe2` ions. Curves aÈc
represent a series in which [H O ] was varied between
2 2 0
1 ] 10~3 and 1 ] 10~4 mol dm~3 at virtually constant
[Fe2`] (1 ] 10~4 mol dm~3). In curves dÈf, [Fe2`] was
0 0
varied between 5 ] 10~5 and 2 ] 10~4 mol dm~3 at approx-
imately constant [H O ] , (3.2È3.3 ] 10~4 mol dm~3). The
2 2 0
data of Table 2B appear as curve a in the Ðgure. Fig. 8 shows
the absorbance vs. time curves, after quenching the reaction
with Fe2` ions, in experiments in which [H O ] was in the
10~5 molar range, while [Fe2`] was kept at D1 ] 10~4 mol
0
dm~3. There was a change in the course of the absorbance vs.

Table 2A Absorbance after the addition of o-phenanthroline

Time/s 0 4 5 6 8 10 15 20 30 45 60
Absorbance 0.360 0.228 0.214 0.200 0.170 0.150 0.109 0.085 0.057 0.039 0.031
[Fe2`] \ 1.005 ] 10~4 mol dm~3, [H O ] \ 1.057 ] 10~3 mol dm~3, I \ 5.00 ] 10~2 mol dm~3, pH 2.43, t \ 25.0 ¡C, l \ 1 cm, j \ 510 nm.
0 mixture (3.14 cm3) diluted to 10
2 cm3.
2 0 Absorbance of o-phenanthroline blank : 0.000.
Reaction

Table 2B Absorbance after the addition of excess Fe2` ions

Time/s 0 15 30 60 90 120(2 ] ) 180 300 420 600 720 900

Absorbance 0.626 0.608 0.598 0.588 0.579 0.572 0.569 0.560 0.552 0.550 0.545 0.545
[Fe2`] \ 9.82 ] 10~5 mol dm~3, [H O ] \ 1.075 ] 10~3 mol dm~3, I \ 5.00 ] 10~2 mol dm~3, pH 2.43, t \ 25.0 ¡C, l \ 1 cm, j \ 222 nm.
0 mixture (3.14 cm3) diluted to2 502 cm3 (measurements according to Procedure 1 in Table 1). Blank absorbance of quenching solution :
Reaction
0.010.

3598 Phys. Chem. Chem. Phys., 1999, 1, 3595È3605

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time curves : an initial increase was observed followed by a
decrease to a varying extent. At [H O ] \ 7.23 ] 10~5 mol
2 2 0
dm~3, the absorbance decreased below A . At lower [H O ]
0 2 2 0
(4.03 ] 10~5 mol dm~3), a decrease only to about A
0
occurred. The extent of evolution of O in this region was
2
very slight and the shape of the absorbance vs. time curves
indicated the formation of an intermediate which was neither
Fe2` nor Fe3` ion.

Phys. Chem. Chem. Phys., 1999, 1, 3595È3605 3599

 View Online
Quantitative kinetic analysis
A simulation of the experimental curves on the basis of the
above scheme was performed. In the following, details of the
analysis will be given and some alternatives to the proposed
mechanism will be discussed.
Preliminary calculations showed that some assumptions are
necessary for a quantitative simulation of the system by using
a minimal set of independent parameters (1) a steady state
exists both in regard of [Fe2` É H O ] and [FeO2`], (2)
2 2
MFeOFeN5` is able to react with o-phenanthroline.¤ Because
of the steady state of [Fe2` É H O ], only the combination of
2 2
the rate constants k@ \ k k /(k ] k ) could be determined. It
1 1 3 2 3
implies that there is no direct kinetic evidence for the existence
of MFe2` É H O N and the formation of FeO2` from Fe2` and
2 2
H O may occur in a single step. Still, it has been included in
2 2
the mechanism since it is more probable that the complex
chemical changes involved in the formation of FeO2` occur in
more than one step. Note that for k > k , k@ \ k . As the
2 3 1 1
consequence of the steady state in regard of [FeO2`], the rate
Published on 01 January 1999 on http://pubs.rsc.org | doi:10.1039/A903915E

constants k , k and k are not all independent. Only the

4 5 6
ratios k /k and k /k (or some other equivalent combination)
4 5 6 5
form an independent set.
There are three independent concentration variables which
were chosen as [FeOFe5`], [O ] and [Fe2`]. By inserting
2
the steady state concentrations of MFe2` É H O N and FeO2`
2 2
[Fe2` É H O ] \ k@ [Fe2`][H O ]
2 2 1 2 2
The mechanism and
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Any scheme for the Fenton reaction must account both for [FeO2`] \ (k@ [Fe2`][H O ] ] k [FeOFe5`])/(k [H O ]
the oxidation of Fe2` ions and the concominant development 1 2 2 8 4 2 2
of O . The following scheme is consistent with the obser- ] k [Fe2`] ] k [Fe3`])
2 5 6
vations given in the previous section : we obtain the following rate equations :
(d[FeOFe5`]/dt) \ (k /k )[Fe3`]
6 5
] (v ] k [FeOFe5`])/DENOM
1 8
[ (k [H O ] ] k )[FeOFe5`] (2)
7 2 2 8
(d[O ]/dt) \ (k /k )[H O ](v ] k [FeOFe5`])/DENOM
2 4 5 2 2 1 8
] k [H O ][FeOFe5`] (3)
7 2 2
The reaction starts with the reversible formation of a (d[Fe2`]) \ [M2[Fe2`] ] (k /k )[Fe3`]N
primary intermediate MFe2` É H O N from Fe2` and H O 6 5
2 2 2 2
(exchange of a H O molecule in the hydration shell of Fe2` ] (v ] k [FeOFe5`])/DENOM
2 1 8
ions by H O ). From the primary complex a secondary inter-
2 2 ] (k [H O ] ] k )[FeOFe5`] (4)
mediate FeO2` is formed by the loss of H O. This species is 7 2 2 8
2
the key intermediate in the reaction. It can react either with v \ k@ [Fe2`][H O ]
Fe2` ions to produce Fe3` (k ), or with H O to produce O 1 1 2 2
5 2 2 2 DENOM \ (k /k )[H O ) ] [Fe2`] ] (k /k )[Fe3`]
(k ). FeO2` can further react with Fe3` and form a binuclear 4 5 2 2 6 5
4
species MFeOFeN5` (k ). This species can react with H O to In addition, two material balance equations have to be satis-
6 2 2
produce O (k ) or to decompose back to FeO2` and Fe3` Ðed
2 7
(k ).
8 [Fe2`] \ [Fe2`] ] [Fe3`] ] 2[FeOFe5`] (5)
The basic features of the kinetics can be explained qualit- 0
atively in the following way. At the beginning of the reaction
[H O ] \ [H O ] ] 2[O ] ] 0.5[Fe3`] ] 1.5[FeOFe5`]
at high [H O ]/[Fe2`], there is competition between H O 2 2 0 2 2 2
2 2 2 2
and Fe2` for FeO2` : both evolution of O (step 4) and oxida- (6)
2
tion of Fe2` (step 5) occur. As Fe2` is oxidized to Fe3`, Fe3`
ions also start competing for FeO2` and form MFeOFeN5`, The simultaneous di†erential equations were integrated
opening a second path for the evolution of O (step 7). At low numerically and the instantaneous values of [FeOFe5`], [O ]
2 2
[H O ]/[Fe2`], the rate of step 4 becomes negligible in com- and [Fe2`] were evaluated at di†erent times. Theoretical
2 2 absorbance values were calculated by using either
parison to the rates of steps 5 and 6. The competition is then
between steps 5 and 6. As Fe2` ions become oxidized and the A \ e 2`M[Fe2`] ] [FeOFe5`]Nl f (7)
ratio [Fe3`]/[Fe2`] increases, MFeOFeN5` starts to accumu- Fe
late its decomposition occurring mainly through step 8. As
little O is evolved under these circumstances, the change of
2 ¤ The reaction may be an oxidation of o-phenanthroline by
absorbance of the ferrous ion quenched reaction mixtures MFeOFe5`N producing Fe2`-phenanthroline and Fe3` ions or a dis-
reÑects the formation and decay of MFeOFeN5`. The quanti- sociative breakup of MFeOFe5`N by phenanthroline producing Fe2`-
tative aspects of the mechanism will be examined in the fol- phenanthroline and FeO3`. The contribution of MFeOFe5`N to the
lowing section. total absorbance was minor.

3600 Phys. Chem. Chem. Phys., 1999, 1, 3595È3605


Table 3 Rate parameters from simulation of the reaction in di†erent ranges of concentration of H O . (Mechanism A)a
Setb k@ /mol~1 dm3 s~1 k /k k /k
1 4 5 6 5
1 55.4 ^ 0.3 (7.5 ^ 0.3) ] 10~3 (2.55 ^ 0.07) ] 10~1
2 54.8 ^ 0.4 (7.5 ^ 0.4) ] 10~3 (2.25 ^ 0.04) ] 10~1
3 55.2 ^ 0.3 (7.4 ^ 0.4) ] 10~3 (2.40 ^ 0.06) ] 10~1
4 56.3 ^ 0.4 (7.4 ^ 0.4) ] 10~3 (3.6 ^ 0.1) ] 10~1
a The residual sum of squares of deviations are listed in column 6 of Table 4. b Numbers in the Ðrst column refer to the respective ranges of [H O ] listed in Table 1.
when the reaction mixture was quenched
phenanthroline, or
A \ A [ M4e 3`[O ] ] (e [ 3e 3`)[FeOFe5`]Nl f (8)
0 Fe 2 FeOFe Fe
when excess Fe2` ions were the quenching agent. f is the
factor of dilution of the reaction mixture in the measuring
procedure. The third term on the right hand side of eqn. (8)
presents the contribution of MFeOFeN5` to the total absorb-
Published on 01 January 1999 on http://pubs.rsc.org | doi:10.1039/A903915E
ance. It is signiÐcant only in experiments in which
[H O ] \ 1 ] 10~4 mol dm~3. The simulation required the
2 2 0
adjustment of 6 parameters : 5 rate constants and com-
binations of rate constants and the absorptivity of
MFeOFeN5`. (The absorptivity of Fe3` has been determined in
the various calibration procedures.) The determination of the
parameters required the use of a large number of accurate
experimental data in a wide range of experimental conditions.
On the other hand, in a wide range of conditions, di†erent
Downloaded on 13 September 2012
parameters inÑuence the values of the calculated quantity
(here absorbance) to a varying degree. As a consequence, the
parameters themselves are determined to various degrees of
accuracy using di†erent sets of data. Therefore, the data were
divided in groups and the parameters in each group were
evaluated. The weighted average of the parameters obtained
in the di†erent groups was then calculated. Because of their
greater accuracy, the data of 18 [Fe2`] vs. t runs formed the
basis for the simulations (11 data points in each run). These
data were combined with ““ O evolution data ÏÏ in each of the
2
four concentration ranges of H O , listed in Table 1. The
2 2
results of the simulations are shown in Figs. 5È8. The fully
drawn lines are curves obtained in the simulations. The
parameters of the curves are summarized in Table 3. The stan-
dard deviations listed are conditional standard deviations, i.e.
standard deviations of the parameters, when other parameters
were kept constant. The rate constants of the dominant
““ ferrous path ÏÏ (k@ , k /k , k /k ) were obtained with reason-
1 4 5 6 5
able accuracy. Rate constants relating to the ““ ferric path ÏÏ
were less accurate. k obtained at very low [H O ] (group 4
7 2 2
with very little evolution of O ), deviated greatly from the
2
values obtained at higher [H O ]. e could not be deter-
2 2 FeOFe
mined at all in the group of experiments 1È3, where the evolu-
tion of O dominated the change of the absorbance.
2 2 2
The average rate constants obtained from groups 1È4 are :
k@ \ 55.4 ^ 0.4 mol~1 dm3 s~1
1 3
k /k \ (7.45 ^ 0.04) ] 10~3
4 5
k /k \ (2.4 ^ 0.4) ] 10~1
6 5
k \ (9 ^ 6) ] 10~3 s~1
8 2
e (270 nm) \ (1.28 ^ 0.04) ] 105 mol dm3 cm~1
FeOFe
k is estimated to be 1 ] 102 mol~1 dm3 s~1.
7
The most striking feature of the results is the transient
increase of the absorbance at low [H O ] in Fe2` ion
2 2
quenched solutions. Various possible reasons for this transient
increase were investigated. In one of the mechanisms con-
sidered, it was attributed to FeO2`. In that case (k put to
6 2
zero and MFeOFeN5` excluded from the mechanism), the
analysis showed that at low [H O ] step 5 still provided an
2 2
View Online
2 2
e (222 nm)/ e (270 nm)/
k /mol~1 dm3 s~1 k /s~1 FeOFe dm3 cm~1
mol~1 FeOFe dm3 cm~1
mol~1
7 8
(1.3 ^ 0.2) ] 102 (1.1 ^ 0.1) ] 10~2 È È
(4.9 ^ 0.3) ] 101 (8.8 ^ 0.4) ] 10~3 È È
(8.7 ^ 0.7) ] 101 (8.6 ^ 0.5) ] 10~3 È È
(2.7 ^ 0.1) ] 102 (3.1 ^ 0.2) ] 10~2 È (1.28 ^ 0.04) ] 105
2 2
with o- efficient way of removing FeO2` from the system preventing,
thus, the accumulation of that intermediate. To explain accu-
mulation of an intermediate, it was necessary to include a
reaction of Fe3` with FeO2` (step 6). In one of the versions
examined, the reaction was formulated as an oxygen atom
transfer
FeO2` ] Fe3` ] FeO3` ] Fe2` (e)
This mechanism resulted in a worse Ðt of the calculated curves
to the experimental data. Also, the rate constants of the sub-
sequent reactions of FeO3` (which is the active intermediate
in the ““ complex mechanism ÏÏ of the catalytic decomposition of
H O by Fe3` ions) deviated from the previously determined
2 2
values of the respective rate constants.10 Considering the
decomposition reactions of MFeOFeN5`, simulations showed
that step 7 alone was insufficient to account for its disap-
pearance. With [H O ] \ 4.03 ] 10~5 mol dm~3 and with
2 2 0
only step 7 operating, [FeOFe5`] had an increasing phase
only, tending to a maximum constant value as t ] O (This
behaviour has been encountered in the reactions of Fe3` ions
and catalase with H O in which the intermediates are both
2 2
formed and decomposed by H O .11 The inclusion of step 8
2 2
in the mechanism provided an explanation for the decreasing
part of the [FeOFe]5` vs. t curves. H` ions probably have an
inÑuence on the rate of this step since MFeOFeN5` becomes
stable upon the addition of a strongly acidic solution of Fe2`
ions as a quencher to the reaction mixture (otherwise it could
not have been detected). A study of the pH dependence of the
rate of the reaction may provide more information on this
point. Concerning the determination of Fe2` ions, it was not
known a priori, whether or not MFeOFeN5` will react with
o-phenanthroline. Both possibilities were investigated. Better
agreement with the experimental data was obtained when a
reaction between MFeOFeN5` and o-phenanthroline was
assumed. It was a minor e†ect, MFeOFeN5` contributing not
more than a few percent to the absorbance of the Fe2`-
phenanthroline complex at 510 nm.
Finally, the possibility of an oxidation of Fe2` ions by the
primary complex MFe2` É H O N was considered
2 2
MFe2` É H O N ] Fe2` ] 2 Fe3` ] 2 OH~ (5@)
Simulations showed that the parameters converged in a region
where k ? k@ [Fe2`] indicating that this mode of oxidation of
5
Fe2` ions is kinetically insigniÐcant.
Fig. 9A shows the calculated curves of [O ] as a function of
2
time at a constant [Fe2`] and at varying [H O ] . The
0 2 2 0
separate contributions of the two pathways for the evolution
of O is shown in Fig. 9B. Curve a shows the amount of O
2
evolved in step 4 as a function of time. Curve b shows the
contribution of step 7 to the total amount of O evolved
2
(curve c). Curves c in Figs. 9A and 9B are identical. In the
early phase of the reaction, O evolution through FeO2` is
2
dominant, but later MFeOFeN5` provides the main path for
the evolution of O . This feature of the mechanism is in agree-
2
ment with the observation of Barb et al. concerning the
importance of Fe3` ions for the evolution of O .5 Curve b
has an inÑection point, since [FeOFe]5` has Ðrst to build up
before O evolution via step 7 can commerce. The resultant
2
Phys. Chem. Chem. Phys., 1999, 1, 3595È3605 3601
 View Online

Fig. 10 [FeOFe5`] as a function of time. Concentration parameters

to curves a, b and c are identical with those of the corresponding
curves in Fig. 8. Parameter set : 4.
Published on 01 January 1999 on http://pubs.rsc.org | doi:10.1039/A903915E

By increasing [H O ], the [H O ] containing terms in the

2 2 2 2
denominator become dominant and eqn. (9) becomes
[FeOFe5`] \ M(k@ k )/(k k )N[Fe2`][Fe3`]/[H O ] (10)
max 1 6 4 7 2 2
For Ðxed [Fe2`] , [FeOFe5`] will, therefore, decrease in
0 max
this region with increasing [H O ] . Using parameter set 4
2 2 0
Downloaded on 13 September 2012

and for [Fe2`] \ 1 ] 10~4 mol dm~3, [FeOFe5`] has

0 MAX
been calculated as 2.2 ] 10~6 mol dm~3, i.e. about 2% of
[Fe2`] . (It occurred at [H O ] \ 9 ] 10~4 mol dm~3.)
0 2 2 0

Reaction of FentonÏs reagent with substrates

The active intermediate FeO2` may oxidize suitable sub-
strates when present in the system. It may react both with
one-equivalent reducing agents of the type HA
FeO2` ] HA ] A ] Fe3` ] OH~ (f )
and two-equivalent reducing agents of the type H A
2
FeO2` ] H A ] A ] Fe2` ] H O (g)
2 2
In case (f ), one of the two equivalents of H O is transferred
2 2
to Fe2` and one to HA. In case (g), both oxidation equiva-
lents are transferred to H A. In both cases, the two oxidation
2
equivalents of H O are transferred simultaneously. Baxen-
2 2
dale et al. observed that a mixture of Fe2` and H O can
2 2
imitate the polymerization of unsaturated compounds.12 This
curve c also shows (as well as curves obtained at lower
phenomenon can be explained, if it is assumed that monomers
[H O ]) an inÑection. It was not detected experimentally,
2 2 (M \ HA) can react with FeO2` in an (f ) type reaction.
partly due to the limited accuracy of the measurements and
Under acidic conditions with Fe2` in excess of H O , there
partly due the accumulation of MFeOFe5`N in this region 2 2
will be competition for FeO2` between Fe2` ions and M. By
a†ecting the absorbance of the system. Fig. 10 shows the
increasing [M], step (f ) will become dominant, leading to the
kinetics of MFeOFeN5`. The curves show a rapid increase fol-
stoichiometry [*[H O ]/[*[Fe2`] \ 1. Under conditions
lowed by a relatively slow decrease. In the range investigated, 2 2
of O evolution and in a large excess of H O over Fe2` ions,
the maximum of [FeOFe5`] ([FeOFe5`] ) increased with 2 2 2
max steps 5 and 6 of the mechanism will be eliminated. There will
[H O ] . In a wider range of [H O ] , however, the behav-
2 2 0 2 2 0 be competition for FeO2` between M and H O . In a large
iour is more complex. At a certain value of [H O ] , 2 2
2 2 0 excess of M, step (f ) will become dominant eliminating step 4,
[FeOFe5`] reaches a maximum ([FeOFe5`] ) and a
max MAX thus suppressing O evolution. Both e†ects have been
further increase of [H O ] causes a decrease of 2
2 2 observed by Baxendale et al.
[FeOFe5`] . The e†ect is due to competition between steps
max Merz and Waters studied the oxidation of several organic
4 and 6 : by increasing [H O ], FeO2` will react predomi-
2 2 compounds by FentonÏs reagent.13 The experiments were per-
nantly with H O , preventing the formation of FeOFe5`.
2 2 formed in acidic media in an excess of Fe2` ions over H O .
Treating the e†ect quantitatively, we equate d[FeOFe5`]/dt 2 2
Assuming that the substrate H A reacts with FeO2` accord-
in eqn. (2) to zero and obtain 2
ing to step (g) and that the dominant reactions in the system
[FeOFe5`] \ k@ (k /k )[Fe2`][Fe3`][H O ]/DENOM@ are steps 5 and (g), we have
max 1 6 5 2 2
DENOM@ \ Mk /k )[H O ] ] [Fe2`] ] (k /k )[Fe3`]N (d[Fe3`]/dt) \ 2 k (FeO2`][Fe2`]
4 5 2 2 6 5 5
] (k [H O ] ] k ) [ k (k /k )[Fe3`] (9) [(dH A]/dt) \ k [FeO2`][H A]
7 2 2 8 8 6 5 2 g 2
3602 Phys. Chem. Chem. Phys., 1999, 1, 3595È3605

The relative rate becomes
[(d[Fe3`]/d[H A]) \ (2 k /k )([Fe2`]/[H A]) (11)
2 5 g 2 product or intermediate in the free radical scheme, at least as
If, on the other hand H A reacts with FeO2` in two consecu-
2 scheme (A2) becomes insigniÐcant at low [H O ] as a mode
tive one-equivalent oxidation steps
FeO2` ] H A ] Fe3` ] HA~ ] OH~ (h)
2 Fe2` ] OH ] Fe3` ] OH~
FeO2` ] HA~ ] Fe3` ] A ] OH~ (i)
Then, by assuming a steady state for [HA~], we have the rate
equations
(d[Fe3`]/dt) \ 2 k [FeO2`][Fe2`] ] 2 k [FeO2`][H A]
5 h 2 If this reaction occurred, then it would be even more plausible
[(d[H A]/dt) \ k [FeO2`][H A]
2 h 2
The relative rate becomes
[(d[Fe3`]/d[H A]) \ 2 ] (2 k /k )([Fe2`]/[H A] (12)
2 5 h 2
Eqns. (11) and (12) are equivalent to eqns. (A) and (E) of Merz
and Waters.13 These equations were considered to indicate
Published on 01 January 1999 on http://pubs.rsc.org | doi:10.1039/A903915E
chain or non-chain oxidations, respectively, of the substrates
by OH radicals. Having the form of competition kinetics, they
are not speciÐc in regard to the underlying mechanism and
are subject to alternative interpretations.”
Active intermediates in the Fenton reaction
The question of identity of the active intermediate(s) in the
Fenton reaction responsible for the evolution of O and the
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2
oxidation of Fe2` has been the subject of numerous investiga-
tions.2,15h21 Ideally, experimental conditions in probing the
identity and structure of the intermediates should be as close
as possible to the conditions under which the kinetics of the
reaction has been investigated i.e. aqueous Fe2` ions, no
extreme ratios of [H O ]/[Fe2`] and a pH in the range 1È2.5.
2 2
The more the two sets of conditions di†er from each other, the
less the relevance of the species so identiÐed to the true inter-
mediates in the reaction. For example, evolution of O is
2
totally suppressed in strongly acidic solutions. Thus, measure-
ments made in strongly acidic solutions can provide no infor-
mation regarding the intermediate responsible for the
evolution of O . Similar limitations apply to measurements in
2
which a large excess of a substrate suppresses all reactions
except the one involving the substrate. No investigations
involving iron chelates will be considered here as there are
considerable di†erences between the kinetics of chelated and
unchelated Fe2` with H O : (a) the rates of various chelates
2 2
of Fe2` with H O are by orders of magnitude higher than
2 2
that of non-chelated Fe2`, (b) no O is evolved in the reaction
2
with chelates and (c) the kinetics of the reaction with chelated
Fe2` has been investigated at pH 7, while that of unchelated
iron at pH 2.65 and lower. There is no certainty that the same
intermediates are formed in the two systems.
Haber and Weiss postulated the formation of the radicals
OH and HO as active intermediates in the following reac-
2
tions :
Fe2` ] H O ] Fe3` ] OH ] OH~ (A0)
2 2
OH ] H O ] HO ] H O (A2)
2 2 2 2
The radical OH was assumed to be involved in the oxidation
of Fe2`, while HO was seen as the key intermediate in the
2 2 2
evolution of O .3,5 It is difficult to reconcile the existence of
2 OH ] H O ] H O ] HO
free radicals with the results of the present study. The free
radical mechanism, either in the formulation of Haber and
Weiss or in that of Barb et al., recognizes only Fe2` and Fe3`
” Walling and Kato have shown that in the free radical scheme,
Fe3` can be subsitituted for H O as oxidant in the reaction with the
2 2
organic radical AH~, without changing the kinetics (ref. 14).
View Online
as the forms of iron in the system. It cannot accommodate a
species which is neither Fe2`, nor Fe3`, nor any other reactant,
formulated by the two groups of authors. In the free radical
2 2
of reaction of OH. OH could then react with Fe2`
(A1)
and produce Fe3`. As an alternative, OH could react with
Fe3`
Fe3` ] OH ] FeOH3` (A5)
to assume that the pair Fe3` ] OH as products of reaction
(A0) would not become separated at all and the species
FeOH3` would appear instead. Then, reaction (A0) would
become equivalent to the set of reactions (1)È(3) of the present
scheme as the species FeOH3` is merely the protonated form
of FeO2` (FeO2` ] H` ] FeOH3`).
Bains et al. and Takakura and Ranby failed to detect any
free radicals in the system by using EPR.15,16 Czapski et al.,
using 4 mol dm~3 H O , report the observation of an EPR
2 2
signal which they attribute to the uncomplexed radical
HO .17 The signiÐcance of this Ðnding is, however, doubtful
2
with regard to the mechanism of the reaction occurring at 104
times lower [H O ]. Rush and Koppenol measured the rela-
2 2
tive extent of C H OH oxidation and Fe3` ion formation in
2 5
the Fenton reaction.18 They found that the ratio of rate con-
stants was 6.3 and concluded that the OH radical was
involved in the oxidation on the basis of the agreement of this
value with the published rate constants of the OH radical with
C H OH and Fe2`. A recent reexamination of the data of
2 5
Rush and Koppenol shows, however, that the value is, in fact,
3.2 indicating that some other intermediate may be involved
in the process.19
The existence of FeO2` has Ðrst been postulated by Bray
and Gorin.20 Their mechanism failed, however, to account for
the full complexity of the reaction. Cahill and Taube sug-
gested, on the basis of 18O fractionation studies, the partici-
pation of Fe(IV) (which is another way to denote FeO2`) in
the reaction.21 Sutin and coworkers argued against the forma-
tion of FeO2`, basing their conclusion on the lack of obser-
vation of the dimeric species Fe (OH) 4` when Fe2` ions
2 2
were oxidized in 0.1È3 mol dm~3 HClO by H O .22 In their
4 2 2
view, the dimer should have been formed, if Fe3` ions were
produced in the reaction of FeO2` with Fe2`. There is,
however, no reason for the formation of this intermediate. The
hypothetical binuclear species FeOFe4` could yield directly,
after double electron transfer and in a strongly acidic medium,
two Fe3` ions without forming Ðrst the dihydroxo-bridged
ferric dimer which is unstable under the conditions of the
experiment. More recently, it was suggested that iron(II)-per-
oxide complexes are involved in the oxidation of biologically
important substrates by FentonÏs reagent.28
Appendix
The free radical mechanism of Barb et al. consists of the fol-
lowing steps
Mechanism B
Fe2` ] H O ] Fe3` ] OH ] OH~ (0)
(2)
2 2 2 2
Fe3` ] HO ] Fe2` ] H` ] O (4)
2 2
Fe2` ] HO ] Fe3` ] HO ~ (3)
2 2
Fe2` ] OH ] Fe3` ] OH~ (1)
It is a chain reaction, step (0) serving as chain initiation, steps
Phys. Chem. Chem. Phys., 1999, 1, 3595È3605 3603
 View Online
Table 4 Simulation of the reaction on the basis of Barb et al.Ïs free radical scheme (Mechanism B)

RSSa RSSa
Set k /mol~1 dm3 s~1 k /k k /k Mechanism B Mechanism A
0 1 2 3 4
1 50.3 ^ 0.4 5.7 ^ 0.4 1.77 ^ 0.06 1.03 ] 10~2 7.36 ] 10~3
2 49.1 ^ 0.4 4.1 ^ 0.2 2.48 ^ 0.06 1.64 ] 10~2 1.11 ] 10~2
3 52.4 ^ 0.4 5.5 ^ 0.2 1.32 ^ 0.04 8.67 ] 10~3 6.86 ] 10~3
4 È È È È 8.67 ] 10~3
a RSS \ Residual sum of squares of deviations.

(1) and (3) as termination. The cycle (0)È(2)È(4) forms the hand sides of eqns. (AVIII) and (AIX) become inÐnite while
chain, which is the site of O evolution. Assuming steady the left hand sides remain Ðnite. To see this, we write the
2
states for the concentration of the radical intermediates OH steady state expression for [Fe2`]. In the steady state,
and HO , the following equations are obtained for the rates d[Fe2`]/dt \ 0. We obtain from eqn. (AI)
2
of the disappearance of Fe2` ions and of the formation of O .
2 1 \ k k [Fe3`][H O ]/M(k [Fe2]
2 4 2 2 1 e
[(d[Fe2`]/dt) \ 2 k [Fe2`][H O ](1 [ R) (AI)
0 2 2 ] k [H O ]) (k [Fe2`] ] k [Fe3`])N (AX)
2 2 2 3 e 4
Published on 01 January 1999 on http://pubs.rsc.org | doi:10.1039/A903915E

d[O ]/dt \ k [Fe2`][H O ]R (AII)

2 0 2 2 From here
R \ k k [Fe3`][H O ]/M(k [Fe2`] ] k [H O ])
2 4 2 2 1 2 2 2 [Fe2`] (k k [Fe2`] ] k k [Fe3`] ] k k [H O ) \ 0
e 1 3 e 1 4 2 3 2 2
] (k [Fe2`] ] k [Fe3`])N (AIII)
3 4 (AXI)
Eqn. (AI) can be integrated in closed form for the conditions
The only physically meaningful solution for [Fe2`] is zero.
(a) k [H O ] ? k [Fe2`], or (b) k [Fe3`] ? k [Fe2`]. e
2 2 2 1 4 3 Thus, no steady state is established in regard of [Fe2`] within
In case (a) we obtain
the given set of reactions of Barb et al.
2k [H O ]tÈln([Fe2`] /[Fe2`]) It seemed to be of interest to try to apply eqns. (AI) and
0 2 2 0
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(AII) to the present set of data. The results of simulations are

\ (k /k )M([Fe2`] /[Fe2`])[1[ln([Fe2`] /[Fe2`])N
4 3 0 0 summarized in Table 4. The data listed in columns 5 and 6 of
(AIV) Table 4 show that when a comparison is possible, Mechanism
A always gives better agreement with the experiment than the
where [H O ] is constant. In case (b) : free radical scheme of Barb et al. does. The value of k in the
2 2 0
2k [H O ]t[ln([Fe2`] /[Fe2`]) Table Ðts well that of Barb et al. (53.0 mol~1 dm3 s~1) and
0 2 2 0 also k@ of the present scheme. k /k D 0.2 and k /k D 0.5, cal-
\ (k /k )[H O ]M(1/[Fe2`]) [ (1/[Fe2`] )N (AV) 1 2 1 4 3
2 1 2 2 0 culable from the data of Table 4, should be compared with the
where again [H O ] should be constant. Eqns. (AIV) and corresponding values of Barb et al. : k /k \ 3 ] 10~2 and
2 2 2 1
(AV) correspond to Barb et al.Ïs eqns. (Iii) and (IViii), respec- k /k \ 0.8 (interpolated to pH 2.43 using their data in Table
4 3
tively. Finally, at [H O ] > [Fe2`], R > 1 III). The agreement between the respective values of these
2 2 parameters is, thus, only partial. It is not possible to simulate
[(d[Fe2`]/dt) \ 2 k [Fe2`][H O ] (AVI) meaningfully the data in group 4 on the basis of the free
0 2 2
radical scheme.
By following the disappearance of Fe2` ions under conditions
in which eqns. (AIV), (AV) and (AVI) are valid, Barb et al.
determined the rate parameters k , k /k and k /k .
0 2 1 4 3
Acknowledgement
The amount of O evolved can be calculated by dividing
2 I am indebted to Mr Marian Dodu from the Computer
eqns. (AII) and (AI) :
Center of the Hebrew University for invaluable help given in
d[O ]/([d[Fe2`]) \ 0.5 R/(1 [ R) (AVII) writing the computer programs. Step 8 of Mechanism A has
2
been modiÐed as a result of dealing with a point raised by the
For condition (a) one obtains
referee. My thanks are due for the remark.
[O ] \ (k /k )([Fe2`] /2) lnM([Fe2`] /[Fe2`] )[1N
2 4 3 0 0 e
(AVIII) References
where [Fe2`] is the (Ðnite) steady state concentration of 1 H. J. H. Fenton, J. Chem. Soc., 1894, 65, 899.
e 2 C. Walling, Acc. Chem. Res., 1975, 8, 125.
Fe2` reached in an excess of H O at the end of the ““ ferrous
2 2 3 F. Haber and J. Weiss, Proc. R. Soc. L ondon, Ser. A, 1934, 147,
phase ÏÏ of the reaction, i.e. at a point where pure catalytic 332.
decomposition of H O by Fe3` ions begins. [O ] is the 4 N. Uri, Chem. Rev., 1952, 50, 375.
2 2 2
amount of O evolved per 1 dm3 of solution until this point. 5 W. G. Barb, J. H. Baxendale, P. George and K. R. Hargrave,
2 T rans. Faraday Soc., 1951, 47, 462.
For condition (b), the expression becomes
6 Y. Kuo, K. Kustin and I. R. Epstein, Inorg. Chem., 1988, 27, 2849.
[O ] \ (k /k )([H O ]/2)lnM([Fe2`] /[Fe2`] )N (AIX) 7 T. J. Hardwick, Can. J. Chem., 1957, 35, 428.
2 2 1 2 2 0 e 8 T. Rigg, W. Taylor and J. Weiss, J. Chem. Phys., 1954, 22, 575.
Eqns. (AVIII) and (AIX) correspond to the appropriate eqns. 9 R. M. Milburn and W. C. Voshburg, J. Am. Chem. Soc., 1955, 77,
on pages 480 and 494 of the cited work of Barb et al. (a \ 1352 ; R. M. Milbourn, J. Am. Chem. Soc., 1957, 79, 537.
[Fe2`] appearing in the denominator of the pre-logarithmic 10 M. L. Kremer and G. Stein, T rans. Faraday Soc., 1959, 55, 959 ;
0 M. L. Kremer, T rans. Faraday Soc., 1962, 58, 702 ; M. L. Kremer,
factor in the eqn. on p. 494 is apparently a printerÏs error.)
Int. J. Chem. Kinet., 1985, 17, 12.
There is serious difficulty in applying eqns. (AVIII) and 11 M. L. Kremer, Arch. Biochem. Biophys., 1974, 161, 658 ; M. L.
(AIX) to the amount of total O evolved during the ““ ferrous Kremer and G. Stein, Int. J. Chem. Kinet., 1977, 9, 179.
2
phase ÏÏ of the reaction. It is assumed in the treatment that 12 J. H. Baxendale, M. G. Evans and G. S. Park, T rans. Faraday
[Fe2`] is a Ðnite quantity. In fact, it is zero. Thus, the right Soc., 1946, 42, 155.
e
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13 J. H. Merz and W. A. Waters, Discuss. Faraday Soc., 1947, 2, 179 ; 23 T. Shiga, J. Phys. Chem., 1965, 69, 3806.
J. Chem. Soc., 1949, S.15. 24 H. Sutton and C. C. Winterbourn, Free Radical Biol. Med., 1989,
14 C. Walling and S. Kato, J. Am. Chem. Soc., 1971, 93, 4275. 6, 53.
15 M. S. Bains, J. C. Arthur and O. Hinojosa, J. Phys. Chem., 1968, 25 S. Croft, B. C. Gilbert, J. R. L. Smith and A. C. Whitwood, Free
72, 2250. Radical Res. Commun., 1992, 17, 21.
16 K. Takakura and B. Ranby, J. Phys. Chem., 1968, 72, 164. 26 W. H. Koppenol and J. F. Liebmann, J. Phys. Chem., 1984, 88,
17 G. Czapski, H. Levanon and A. Samuni, Isr. J. Chem., 1969, 7, 99.
375. 27 S. Goldstein, D. Meyersein and G. Czapski, Free Radical Biol.
18 J. D. Rush and W. H. Koppenol, J. Inorg. Biochem., 1987, 29, Med., 1993, 15, 435.
199. 28 D. A. Wink, R. W. Nims, J. E. Saaverda, W. E. Utermahlen, Jr.
19 M. L. Kremer, unpublished work. and P. C. Ford, Proc. Acad. Sci. USA, 1994, 91, 6604.
20 W. C. Bray and M. H. Gorin, J. Am. Chem. Soc., 1932, 54, 2124.
21 A. E. Cahill and H. Taube, J. Am. Chem. Soc., 1952, 74, 2313.
22 T. J. Conochiolli, E. J. Hamilton, Jr. and N. Sutin, J. Am. Chem.
Soc., 1965, 87, 926. Paper 9/03915E
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