Author's personal copy

Journal of Photochemistry and Photobiology A: Chemistry 255 (2013) 41–49

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Journal of Photochemistry and Photobiology A:

Chemistry
journal homepage: www.elsevier.com/locate/jphotochem

Effects of Fe(III)-concentration, speciation, excitation-wavelength and light

intensity on the quantum yield of iron(III)-oxalato complex photolysis
Christian Weller, Sabrina Horn, Hartmut Herrmann ∗
Leibnitz-Institut für Troposphärenforschung, Permoserstraße 15, 04318 Leipzig, Germany

a r t i c l e i n f o a b s t r a c t

Article history: Iron(III)oxalato complexes do frequently occur in the environment, specifically in surface waters,
Received 24 October 2012 in atmospheric waters (clouds, rain, fog) or in waste waters. Due to their high photo-reactivity
Received in revised form 11 January 2013 and their absorption overlap with the actinic spectrum, Fe(III)oxalato complex photochemistry is
Accepted 19 January 2013
widespread and of broad interest. Fe(III)oxalato complex photolysis in deaerated solutions using
Available online xxx
single excimer laser flash photolysis at 308 and 351 nm and continuous Hg(Xe)-lamp irradiation at
313, 366 and 436 nm was quantified via Fe(II) quantum yield measurements with phenanthroline
Keywords:
complexometry and UV–vis detection. Measured Fe(II) quantum yields showed a dependence on initial
Iron
Oxalate
Fe(III)ferrioxalate concentration and irradiation energy at below millimolar concentrations. Individual
Complex molar extinctions (in l mol−1 cm−1 ) and individual quantum yields (˚) were determined for initial Fe(III)
Photochemistry concentrations of 4.85 × 10−4 M for the 1:2 (FeOx2 − ) and 1:3 (FeOx3 3− ) complexes applying a regression
Quantum yield analysis for solutions containing variable ratios of 1:2 and 1:3 complexes: ε1:2, 308 nm = 2300 ± 90,
ε1:3, 308 nm = 2890 ± 40, ˚1:3, 308 nm = 0.93 ± 0.09; ε1:2, 351 nm = 1040 ± 30, ε1:3, 351 nm = 1120 ± 20,
˚1:3, 351 nm =0.88 ± 0.08; ε1:2, 313 nm = 2055 ± 111, ε1:3, 313 nm = 2663 ± 37, ˚1:3, 313 nm = 0.12 ± 0.05;
ε1:2, 366 nm = 753 ± 357, ε1:3, 366 nm = 709 ± 10, ˚1:2, 366 nm = 1.17 ± 1.46, ˚1:3, 366 nm = 0.91 ± 0.09;
ε1:2, 436 nm = 55 ± 9, ε1:3, 436 nm = 22 ± 2, ˚1:2, 436 nm = 1.40 ± 0.40, ˚1:3, 436 nm = 1.00 ± 0.20. Individual
quantum yields for the 1:2 complex could only be determined for the excitation wavelengths 366
and 436 nm due to non-linearity of the data for 308, 351 and 313 nm. The non-linearity is ascribed
to complicated interactions of secondary reactions involving Fe(III)oxalato educt-complexes, carboxyl
radicals and Fe(II)-radical complexes. The 1:2 complex has generally a higher quantum yield compared
to the 1:3 complex at all considered wavelengths.
© 2013 Elsevier B.V. All rights reserved.

1. Introduction investigations of the subject in relation to waste water treat-

The photochemistry of the Fe(III)oxalato or ferrioxalate-system
is one of the most thoroughly investigated Fe(III) polycarboxy-
late systems with many different backgrounds and applications.
It was proposed as a chemical actinometer to measure light inten-
sities in a very convenient, inexpensive and reliable way at well
defined conditions [1] and is still frequently used in photochem-
istry. Furthermore, the photochemistry of ferrioxalate complexes
as a one representative of the class of Fe(III)polycarboxylate
complexes can play a role in environmental systems such as
atmospheric waters (cloud droplets, aqueous particles, rain) [2,3]
where the direct degradation of oxalate via photolysis and the
secondary production of reactive radicals that will react fast
with any present substance can cause the turnover of organic
compounds. The radical generating potential has also led to
∗ Corresponding author. Tel.: +49 341 2717 7024; fax: +49 341 2717 997024.
E-mail addresses: weller@tropos.de (C. Weller), horns@tropos.de (S. Horn),
herrmann@tropos.de (H. Herrmann).
ment via so called advanced oxidation processes [2,4]. Oxalate
forms three different complexes with Fe(III) in acidic to neutral
solutions: mono(oxalato)iron(III), [Fe(C2 O4 )]+ ; bis(oxalato)ferrate,
[Fe(C2 O4 )2 ]− and tris(oxalato)ferrate, [Fe(C2 O4 )3 ]3− , which occur
simultaneously in different proportions depending on the pH
and the Fe(III):oxalate ratio. Iron(III)oxalate complexes exhibit
strong LMCT absorption bands in the UV range. Fe2+ and reactive
oxalate fragments are ultimately produced upon photolysis of an
Fe(III)oxalato complex. The reactive fragments lead to the produc-
tion of CO2 •− , O2 •− /HO2 • and ultimately H2 O2 and • OH from the
Fenton reaction.
The mechanism of photoreduction and subsequent reactions in
the ferrioxalate system were subject of numerous investigations
[5–16]. There are two different basic ideas of the ferrioxalate reac-
tion mechanism, following the excitation of the complex [17]. One
perception is the intramolecular electron transfer from the oxalate
ligand to the center ion Fe3+ and the formation of a long lived radical
complex (R1) or the formation of a C2 O4 •− radical (R2) [11,13]:
[Fe(III) (C2 O4 )3 ]3− + hv → [Fe(II) (C2 O4 • )(C2 O4 )2 ]3− or (R1)

1010-6030/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jphotochem.2013.01.014
 Author's personal copy
42 C. Weller et al. / Journal of Photochemistry and Photobiology A: Chemistry 255 (2013) 41–49
[Fe(III) (C2 O4 )3 ]3− + hv → [Fe(II) (C2 O4 )2 ]2− + C2 O4 •−
The C2 O4 •− radical will then decarboxylate instantly and form CO2
and CO2 •− [18]:
C2 O4 •− → CO2 •− + CO2 k1st = 2 × 106 s−1
Another possibility is the sequential cleavage of the Fe(III) O bond
between iron and one oxalate ligand and its C C bond which would
yield a biradical complex or two carboxylate radicals [9,14,19]:
[Fe(III) (C2 O4 )3 ]3− + hv → [Fe(III) (CO2 • )2 (C2 O4 )2 ]3− or
[Fe(III) (C2 O4 )3 ]3− + hv → [Fe(III) (C2 O4 )2 ]− + 2CO2 •−
Despite a controversial argument on the two pathways [17,19–21],
the discussion on the primary mechanism of ferrioxalate photolysis
still open because neither point of view was sufficiently confirmed
throughout the discussion. It has to be emphasized that in the end
both mechanisms will lead to the formation of Fe2+ and at least one
CO2 •− radical, which is important for secondary reduction reac-
tions.
Regardless of the exact photochemical mechanism, there are a
large number of references that report quantum yields of Fe2+ for-
mation from ferrioxalate photolysis which were determined for the
UV–vis wavelength range from 205 to 578 nm. The values that were
obtained at the actinometry conditions specified by Hatchard and
Parker [1] do generally agree [22–25] but values obtained at differ-
ent experimental conditions, [26–31] which involve mostly lower
initial Fe3+ concentrations, are quite scattered. These observed
inconsistencies in the reported ferrioxalate quantum yields gave
rise to a reinvestigation of the system quantum yield in the present
work and the results will be discussed. Furthermore, the influence
of Fe(III) oxalate speciation, irradiation wavelength and light inten-
sity on the photochemistry and measured Fe(II) quantum yields
will be addressed on the basis of excimer laser flash photolysis and
continuous irradiation experiments.
2. Experimental
2.1. Preparation of experimental solutions
The species distribution of the different oxalate and possibly
inorganic iron(III) complexes was calculated with the com-
puter program Visual MINTEQ (Department of Land and Water
Resources Engineering, Sweden), an equilibrium speciation model.
For all experimental solutions Milli-Q water (Millipore, USA) with
R = 18 M was used. Fe(III) stock solutions were prepared from
Fe2 (SO4 )2 (Aldrich, 97%) and FeClO4 (Aldrich, low chloride) salts
and kept at pH ∼ 1 with H2 SO4 (Fluka, 98%) or HClO4 (Baker, 70%)
to prevent precipitation of insoluble Fe(III) species.
Solutions for the photochemical experiments were always
freshly prepared. When necessary, the ionic strength was adjusted
by addition of NaClO4 . Adjustments of the pH were done with NaOH
and HClO4 . Argon bubbling was used for deoxygenation through-
out all Fe(III) oxalate experiments in the present work. Preparations
of Fe(III) complex solutions and photolysis experiments have been
carried out in the dark under illumination by red light, to avoid
photochemical Fe2+ production prior to the actual photolysis. The
investigated complexes are not photoreactive in the red region of
the spectrum. Additionally, the flasks containing Fe(III) complex
solutions were covered with aluminum foil. All experiments have
been carried out at room temperature 20 ◦ C. An UV–vis spectrum of
the Fe(III) complex solutions has been recorded for each quantum
yield measurement to determine the extinction coefficient at the
excitation wavelengths (Lambda 900 double beam spectrometer,
Perkin Elmer).
(R2) 2.2. Excimer laser flash photolysis
For the photolysis experiments, a volume of 2.6 ml of
iron(III)oxalato-complex solution was transferred to a standard
1 cm optical path length spectroscopy cuvette made of fused sil-
(R3)
ica. Deoxygenated samples were transferred under an argon flow
and the cuvette was capped with a Teflon seal. Then, the cuvette
was placed in a cuvette-holder in front of an excimer laser (Com-
pex 200 and 205, Lambda Physik). The lasers were operated either
at 308 nm or at 351 nm. The cuvette was exposed to a single laser
(R4) flash of about 20 ns duration. The output energy of the laser was
measured with a pyroelectric sensor (Coherent). A volume of 2 ml
(R5) exposed solution was transferred to a prepared flask containing
the necessary agents (see Section 2.4) to detect the photochemi-
cally formed Fe2+ . In a standard course of the measurement of one
quantum yield, the exposure and transfer to the flask have been
repeated six times to calculate an average quantum yield from the
results, including an error with Student t-factor on a 95% confidence
interval.
2.3. Hg(Xe) lamp continuous irradiation
For the continuous irradiation experiments, the preparation of
the Fe(III) complex solutions was the same as for the laser flash
photolysis experiments. The irradiation cell was a 1 cm fused silica
cuvette with a small inset for a magnetic stirrer out of optically non-
transmittive black glass (Hellma). The cell was placed in a holder
above a magnetic stirrer and in front of the output of a prism-
monochromator (model M4QII, Carl Zeiss). A 200 W Hg(Xe) lamp
(Hamamatsu) was used as irradiation source and the 313, 366 or
436 nm lines were selected with the monochromator. Irradiations
have been performed under magnetic stirring typically for 2, 4, 6
and 8 min and no longer than 10 min to observe the kinetics of
Fe2+ formation. Similar to the flash photolysis procedure, a volume
of 2 ml exposed solution was transferred to a prepared flask for
photochemically generated Fe2+ analysis.
The measurement of the photon flux entering the photolysis cell
from the Hg(Xe) lamp/monochromator system was carried out with
standard ferrioxalate actinometry. A 6 mM ferrioxalate solution has
been used for the wavelengths 313 and 366 nm and for 436 nm a
0.15 M ferrioxalate solution has been used with a quantum yield
value of 1.01 [1]. Typical measured photon fluxes reaching the
cell from the lamp-monochromator system were qn,p = 10−10 to
10−9 mol s−1 .
2.4. Detection of photochemically produced Fe2+
Photochemically generated Fe2+ was analyzed by VIS-
spectroscopy as 1,10-phenanthroline complex (phen; Fluka,
puriss, p.a.) [Fe(phen)3 ]2+ using its local maximum extinction at
 = 510 nm with ε510 nm = 11,100 l mol−1 cm−1 [22] from which the
Fe2+ concentration was calculated. The photolyzed solutions con-
tained both a major fraction of unreduced Fe(III) besides a smaller
amount of Fe2+ which had to be detected. Phenanthroline forms
strong complexes with both Fe3+ and Fe2+ , with the [Fe(phen)3 ]3+
complex having a much lower extinction coefficient than the
[Fe(phen)3 ]2+ complex at 510 nm. Nevertheless, it causes a small
but noticeable interference with the Fe2+ analysis. Therefore, a
suppression of this interference was applied, were the Fe3+ is
masked by nitrilo-triacetate (NTA: Fluka, ≥99%) in presence of a
glycine–HCl buffer adjusted to pH = 2.9 (glycine: Sigma, 99%, HCl:
Fluka, 37%, Riedel de Haen, 1 M) [32].
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C. Weller et al. / Journal of Photochemistry and Photobiology A: Chemistry 255 (2013) 41–49 43

2.5. Calculation of Fe2+ quantum yield

The quantum yields ˚ from the excimer laser flash photolysis

experiments were calculated in the following way. The incident
amount of photons per pulse [Ph]I0 was calculated from the mea-
sured excimer laser energy and the amount of photons absorbed
by the ferrioxalate-complex(es), [Ph]abs , was computed via:

[Ph]abs = [Ph]I0 · (1 − 10−εcd ) (1)

Finally, the quantum yield is calculated by:

[Fe2+ ]
˚= (2)
[Ph]abs

The calculation of quantum yields from continuous Hg(Xe) lamp

irradiation experiments was performed with the absorbed pho-
ton flux Iabs from the incident photon flux, qn,p , the rate of Fe2+
production, d[Fe2+ ]/dt and the reaction volume, Vr :

d[Fe2+ ] Vr
˚= · (3)
dt Iabs

Iabs = qn,p · (1 − 10−εcd ) (4)

2.6. Treatment of speciation effects on quantum yield

To measure individual quantum yields of [Fe(Ox)2 ]− and

[Fe(Ox)3 ]3− complexes, it is necessary to distinguish their con-
tributions to the overall quantum yield. It is impossible to fully
isolate all individual Fe(III) oxalato complexes in an aqueous solu-
tion through variation of pH and Fe(III):oxalate ratio because their
stability constants lie too close together or other complexes such
as [FeIII (OH)n ]3−n will form simultaneously. However, the pH and
Fe(III):oxalate ratio can be adjusted in such way that the sum of
bis- and tris(oxalato)ferrate complexes in a solution contains 100%
of the present Fe3+ .
The measured total molar extinction εtot of the Fe(III) complexes
can be expressed as:

εtot = εi fi
i
with εi being the individual molar extinction coefficient of the ith
Fe(III)-complex representing a fraction fi of the total Fe(III) [33]. In
this work, the complex speciation and thus fi was calculated using
the speciation program Visual MINTEQ. Consequently, the over-
all extinction coefficient εtot which is the sum of the individual
extinction coefficients of bis- and tris(oxalato)ferrate complexes is
proportional to the fraction of one complex species fi . In analogy
to the calculation of the individual molar extinction, the individual
quantum yields of different complex species can be determined in
a similar manner:
 [1] with milli-molar Fe3+ concentration the measured quantum
(˚tot ) · (εtot ) = (˚i · εi · fi )
i
˚tot is the measured overall quantum yield of a solution and ˚i
is that of the individual complex species. The repetition of at least
a number of i photolysis experiments under experimental condi-
tions where fi is varied, gives a set of linear equations which can
be solved for ˚i , if εi has been determined before. The measured
quantity ˚tot × εtot can be regarded as a weighted average, where
the weighting is connected to the speciation of the metal [33].
Fig. 1. Top: concentration dependent effective overall Fe2+ quantum yields from
308 nm excimer laser flash photolysis. Conditions: at pH = 1.2 (actinometry con-
ditions) Fe(III):Ox = 1:3, [H2 SO4 ] = 0.05 M; at pH 3 and 5 Fe(III):Ox = 1:10; bottom:
concentration dependent fractions of 1:1, 1:2, 1:3 Fe(III) oxalate complexes of the
total [Fe3+ ] for each quantum yield measurement data point of the top plot (back-
ground color codes the pH of the respective ˚ measurement series in the plot at the
top).
(5) 3. Results and discussion
3.1. Dependence of Fe2+ -quantum yield on initial
Fe3+ -concentration
3.1.1. Overview
Measurements of Fe2+ quantum yields after excimer laser flash
photolysis at 308 nm using initial Fe3+ concentrations between
10−5 and 10−4 M gave much smaller values than expected from
earlier works [1,23]. Consequently, Fe2+ quantum yield measure-
ments as a function of initial Fe3+ concentration in the range of
10−6 to 10−3 M were made using excimer laser flash photolysis at
308 nm (Fig. 1). At actinometry conditions of Hatchard and Parker
(6) yield of the present work (˚308 nm = 1.27) agrees well with the val-
ues of ˚300 nm = 1.25 and ˚313 nm = 1.24 by Goldstein and Rabani
[23] and Hatchard and Parker [1], respectively. Only one work
reports a similar behavior of quantum yields under decreasing Fe3+
concentrations using Hg(Xe) lamp continuous photolysis [30].
3.1.2. Possible effect of speciation change along with [Fe3+ ]
decrease
A decrease of the Fe3+ concentrations at actinometry conditions
(Fe(III):Ox = 1:3, [H2 SO4 ] = 0.05 M, pH = 1.2) down to 5 × 10−4 M
 Author's personal copy
44 C. Weller et al. / Journal of Photochemistry and Photobiology A: Chemistry 255 (2013) 41–49
Fig. 2. Measured effective overall Fe2+ -quantum yield at 308 nm excimer laser flash
photolysis at pH = 1.2 (actinometry conditions) and at pH = 3 compared to Gepasi
modeled overall Fe2+ -quantum yields with different sets of kinetic constants and
initial conditions (see text and Table 1).
did not change the quantum yield (red data points in Fig. 1). A
further decrease of the Fe3+ concentrations at actinometry con-
ditions (pH = 1.2) would have systematically lowered the part of
Fe3+ bound by oxalate in favor of Fe(III)hexaaqua, Fe(III)sulfato
and Fe(III)hydroxo complexes. These complexes would have con-
tributed to the photochemistry which should be exclusively that
of Fe(III)oxalato complexes. Therefore, a tenfold (molar) excess of
oxalate over Fe(III) was used for the measurement series at pH
3 and 5, to ensure complete complexation by oxalate. The sum
of Fe(III)(H2 O)6 , Fe(III)sulfato and Fe(III)hydroxo complexes never
exceeded one percent of the total [Fe3+ ] in all experiments.
Solutions at pH = 3 are dominated by the bis(oxalato) complex
and solutions at pH = 5 dominated by the tris(oxalato) complex
(Fig. 1). Solutions at both pH = 3 and 5 show a decrease of the quan-
tum yield when the initial Fe3+ concentration is lowered, with the
solution at pH = 5 having always the lower value. This points toward
a lower individual quantum yield of the tris(oxalato) complex com-
pared to the bis(oxalato) complex which is confirmed by this work
and Faust and Zepp [28]. When the concentration of Fe3+ is low-
ered, even at a constant pH (3 or 5) and a constant Fe(III):oxalate
ratio, the speciation gradually changes with an increasing amount
of bis(oxalato) complex accompanied by a decreasing amount of
tris(oxalato) complex. The bis(oxalato) complex has in fact a higher
quantum yield than the tris(oxalato) complex, thus the gradu-
ally changing speciation toward lower Fe3+ concentrations cannot
explain the decrease of the quantum yield. Because if the changing
speciation would be the major cause for a quantum yield change,
then the quantum yield would be expected to increase, which is not
the case. Additionally, the four measurements at actinometry con-
ditions (mM [Fe3+ ], red data points in Fig. 1) show a considerable
change in the speciation, while the quantum yield is stable around
1.25. This leads to the conclusion that the speciation change has no
effect and the observed quantum yield decrease with decreasing
[Fe3+ ] is mainly caused by the concentration decrease.
3.1.3. Kinetic effect on secondary Fe(III) to Fe(II) reduction
The concentration dependence of the quantum yield can be
explained by a change of the reaction regime for the secondary
reactions of the carboxyl radical, CO2 •− . The formation of CO2 •−
from the photolysis of [Fe(III) (C2 O4 )n ]3−2n complexes is described
by (R1)–(R5). Theoretically, there is the possibility of the formation
of two Fe2+ ions per one absorbed photon by any [Fe(III) (C2 O4 )n ]3−2n
complex, if there are enough [Fe(III) (C2 O4 )n ]3−2n complexes which
do not receive light, meaning they remain unphotolyzed and
can thus serve as reactants for secondary reductions by formed
CO2 •− during photolysis. The precondition of having a constant
amount of approximately 70% of the initial [Fe3+ ] unphotolyzed
was kept during the above described experiments. Considering the
formation of CO2 •− and Fe2+ via:
[Fe(III) (C2 O4 )n ]3−2n + hv → Fe2+ + (n − 1)C2 O4 2− + CO2 + CO2 •−
(R6)
and the immediately following secondary reduction of unpho-
tolyzed [Fe(III) Oxn ]m complex:
[Fe(III) (C2 O4 )n ]3−2n + CO2 •− → Fe2+ + nC2 O4 2− + CO2 (R7)
leads to the conclusion that the amount of Fe2+ formed through the
secondary reaction path (R7) is most likely diminished between
initial Fe3+ concentrations from 5 × 10−4 to 1 × 10−5 M and even-
tually shut down at initial Fe3+ concentrations below 5 × 10−6 M.
Reaction path (R7) becomes less favorable when the initial Fe3+ con-
centration is lowered because competing reactions, which divert
or “scavenge” CO2 •− , gain more importance. Such competing reac-
tions are the recombination of 2 CO2 •− (R8) and the reaction with
residual dissolved O2 (R9), which can be still around 5 × 10−7 M
[34], despite thorough Argon-purging [35].
2CO2 •− → C2 O4 2− kR8 = 1.2 × 109 M−1 s−1 (R8)
CO2 •− + O2 → CO2 + O2 •− kR9 = 6.5 × 109 M−1 s−1 (R9)
(R9) is only competing when the formed O2 reacts with other
•−
components in the solution than [Fe(III) (C2 O4 )n ]3−2n because O2 •−
and Fe(III) produce also Fe2+ .
3.1.4. Simulation of kinetic effect through [Fe3+ ] decrease
It has been attempted to quantify the experimentally observed
quantum yield dependence on [Fe3+ ] with available rate constants
for (R8) and (R9) and following HOx /HOx + iron reactions
[36–46] using Gepasi, a (bio)chemical kinetic simulation software
(http://www.gepasi.org, [47]). The concentration dependence of
the quantum yields has been modeled with three different sets of
initial conditions and rate constants (Table 1). From Fig. 1 can be
seen that ˚ = 1.26 is a limiting value for the quantum yield at high
concentrations. The quantum yield of 1.26 cannot be further max-
imized by an increase of Fe(III) concentration. Secondary reactions
must clearly contribute to this value, because it exceeds unity. But
under the applied experimental conditions the effect of the sec-
ondary reactions reached its upper limit, which results into the
value of 1.26. Therefore, the theoretical value of 1.26 has been used
together with the measured overall extinction at 308 nm to calcu-
late the formed Fe2+ and CO2 •− as input for initial concentrations
in the model. Two different scenarios have been used for the ini-
tial photolysis mechanism that affects the definition of the initial
model concentrations of Fe2+ and CO2 •− . Mechanism (R5), which
involves formation of 2 CO2 •− , leads to an initial CO2 •− concentra-
tion obtained with ˚ = 1.26 while the initial [Fe2+ ] = 0. The other
possibility, mechanism (R2), is represented by an initial concentra-
tion of CO2 •− which is equal to the initial [Fe2+ ] and both are half
the value of the final [Fe2+ ]. This should account for the initial for-
mation of Fe2+ through inner sphere electron transfer. Model A is
very simplistic containing only two reactions, the secondary reduc-
tion of Fe(III) by CO2 •− and the recombination of CO2 •− as well as
mechanism (R5).
Model A provides the best fit of the experimental data. The
observed trend of the concentration dependence is at least qualita-
tively reproduced. Through model B, only the invariable quantum
yields at high [Fe3+ ] are reproduced, but not the decrease with
concentration decrease. Model B uses the same mechanism (R5)
as A, but a published rate constant for (R7) which is four times
higher than in model A, the rate constant for (R8) is similar to
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C. Weller et al. / Journal of Photochemistry and Photobiology A: Chemistry 255 (2013) 41–49
Table 1
Parameters used in the Gepasi model sets to simulate measured Fe2+ quantum yields with secondary radical reactions displayed in Fig. 2.
Model kR7 [M−1 s−1 ] Ref. kR8 [M−1 s−1 ]
9 9
A 1 × 10 Estimated to lie on 1 × 10
the lower end of
the range
109 –1010 M−1 s−1
[50] [51]
B 4 × 109 [52] 1.2 × 109
C 4 × 109 [52] 1.2 × 109
that used in A. The main factor for the disagreement is the higher
kR7 , which reveals the high sensitivity of the final [Fe2+ ] toward
changes in (R7). Furthermore, model B includes HOx –iron reac-
tions, but their contribution to total Fe2+ formation is below 1%
and therefore negligible. Model C uses the same rate constants as
B, but simulates mechanism (R2) which leads to the poorest agree-
ment with the observed data among all three models. Concluding
for the concentration dependence it can be stated that the reac-
tion system modeling strongly highlights the great influence of the
secondary reactions of the radical species CO2 •− as the main cause
for the observed concentration dependence. This is a major finding
of the present paper and it has to be emphasized that the investi-
gated concentration dependence has to be taken into account when
ferrioxalate photochemistry at below millimolar initial concentra-
tions is dealt with.
3.2. Dependence of Fe2+ -quantum yield on amount of initially
absorbed photons
The amount of absorbed exciting radiation at 308 nm was
changed via increase or decrease of the excimer laser energy
output while keeping all other experimental parameters con-
stant. The ratio [Phabs ]/[Fe3+ ]initial was calculated with the
measured laser energy and the overall extinction coefficient
of [Fe(III) (oxalate)n ]3−2n complex mixtures in the experimental
solution. From Fig. 3 can be seen that the effective overall Fe2+
quantum yields decrease with an increase of the number of
absorbed photons. In a photochemical reaction with only one
primary step, the quantum yield should not change upon variation
of the amount of excitation radiation over a certain range, because
the more molecules are excited, a proportional larger amount
of reaction product should be formed. As mentioned before, in
the Fe(III)oxalato complex photolysis, the amount of one formed
Fig. 3. Dependence of effective overall Fe2+ quantum yield on the amount of
absorbed photons per initial Fe3+ concentration, pH = 3, [Fe3+ ] = 4.85 × 10−4 M,
Fe(III):oxalate = 1:10, excimer laser flash, photolysis = 308 nm.
45
Ref. HOx /HOx + Fe(II)/(III) reactions Photolysis mechanism
Estimated Excluded (R5)
[35] Included (R5)
[35] Included (R2)
reaction product Fe2+ depends also on secondary reactions of the
second reaction product, the carboxyl radical (CO2 •− ). In this case,
the decrease of the effective overall Fe2+ quantum yield with an
increasing amount of absorbed photons can be attributed to a
decrease of the amount of non-photoreduced [Fe(III) (oxalate)n ]3−2n
complexes available for secondary reactions with CO2 •− . At con-
ditions with high ferrioxalate concentrations as used in chemical
actinometry ([[Fe(III) (oxalate)n ]3−2n ] ≥ 6 × 10−3 M), the ferrioxalate
system was reported to have Fe2+ quantum yields independent
of the excitation energy [1], which is of course a prerequisite of a
chemical actinometer. According to the author’s knowledge, this
is the first report of an energy or photon flux dependence of Fe2+
quantum yields at lower (≤6 × 10−3 M) ferrioxalate concentrations.
Hatchard and Parker [1] stated, that under their specified actinom-
etry conditions with [ferrioxalate] ≥ 6 × 10−3 M no quantum yield
dependence on incident photon flux was observed, which would
be a basic requirement for an actinometer. It is important that the
identified energy dependence of ferrioxalate Fe2+ quantum yields
is considered for the interpretation of photolysis experiments with
dilute (<millimolar) initial Fe(III) concentrations.
3.3. Speciation dependence of Fe2+ -quantum yield
3.3.1. Laser flash photolysis of bis- and trisoxalatoferrate at 308
and 351 nm
Individual extinction coefficients of the bis- and
tris(oxalato)ferrate complexes have been determined for the
wavelengths of interest. Fig. 4 shows a set of measured overall
molar extinction coefficients at 308 and 351 nm as a function of the
fraction of [Fe(Ox)2 ]− in the solution including a linear regression.
Note that the higher degree of scatter at 351 nm is due to a
much smaller scale of the y-axis and because the isosbestic point
at 362 nm (where [Fe(Ox)2 ]− and [Fe(Ox)2 ]3− have the same molar
extinction) is closer to 351 nm than to 308 nm. Therefore the change
of εi at 351 nm with f[Fe(Ox)2 ]− is minor, because [Fe(Ox)2 ]−
and [Fe(Ox)3 ]3− have very similar values at close distance to the
Fig. 4. Overall extinction coefficients (εtot ) of [Fe(Ox)2 ]− and [Fe(Ox)3 ]3− mixtures
at 308 (top) and 351 nm (bottom) as a function of calculated [Fe(Ox)2 ]− fraction.
 Author's personal copy
46 C. Weller et al. / Journal of Photochemistry and Photobiology A: Chemistry 255 (2013) 41–49
Table 2
Individual extinction coefficients of bis- and tris(oxalato)ferrate complexes at 308
and 351 nm.
Species ε308 nm [l mol−1 cm−1 ] ε351 nm [l mol−1 cm−1 ]
[Fe(Ox)2 ]−
2300 ± 90 1040 ± 30
[Fe(Ox)3 ]3− 2890 ± 40 1120 ± 20
isosbestic point, so that computational and experimental errors
produce a more pronounced scatter a the given scale of the y-axis.
The regression parameters are as follows:
 = 308 nm; εtot = (−595 ± 78) · f[Fe(OX) − + (2891 ± 39);
2]
R = 0.95, n = 27
 = 351 nm; εtot = (−87 ± 29) · f[Fe(OX) − + (1122 ± 15);
2]
R = 0.75, n = 30
At the intercept of the regression line, where f[Fe(Ox)2 = 0, it fol-
lows that f[Fe(Ox)3 ]3− = 1 and therefore the individual extinction
coefficient of the tris(oxalato)ferrate complex equals the value of
the intercept. The individual extinction coefficients calculated with
the help of Eqs. (7) and (8) are displayed in Table 2, no literature
values are available for these wavelengths.
A similar regression analysis has been done for additional wave-
lengths between 290 and 436 nm to obtain the individual spectra
of the bis- and tris(oxalato)ferrate complexes, shown in Fig. 7.
After the individual extinction coefficients of the ferrioxalate com-
plexes were determined, the individual quantum yields of the
bis- and tris(oxalato)ferrate complexes were measured in two
series at both a higher and a lower initial concentration of Fe3+ .
Because of the observed concentration dependence reported ear-
lier, the concentration range of changing quantum yields between
5 × 10−6 and 4 × 10−4 M [Fe3+ ] was avoided. One measurement
series was performed at constant low initial iron concentration
[Fe3+ ] = 4 × 10−6 M, but levels of photochemically produced Fe2+
were too close to the quantification limit of the phenanthroline
spectroscopic detection method. Therefore, the effects on the quan-
tum yields through a speciation change were most likely within
the magnitude of error introduced by the measurement procedure
(data not shown).
The other series was performed at higher constant initial iron
concentration of [Fe3+ ] = 4.85 × 10−4 M. The fractions of bis- and
tris(oxalato)ferrate complexes in each series were only varied by
changing the pH and the amount of excess oxalate. Taking into
account the observed quantum yield dependence on the amount
of absorbed photons, the amount of photons absorbed by the mix-
ture of ferrioxalate complexes was kept always between 3 and 5%
of the initial [Fe3+ ] through adjustment of the excimer laser output
energy.
The performance of εtot and ˚tot measurements under
variable [Fe(Ox)2 ]− /[Fe(Ox)3 ]3− conditions at a constant
[Fe3+ ]initial = 4.85 × 10−4 M led to the results displayed in Fig. 5.
At both wavelengths the measured εtot correlate well with
f[Fe(Ox)2 ]− , which is an indication for a correct speciation calcu-
lation. However, the product εtot × ˚tot displays a curved behavior
instead of a linear dependence on f[Fe(Ox)2 ]− at both 308 and
351 nm. Speciation dependent measurements of (εtot × ˚tot ) in fer-
rioxalate solutions at 436 nm using continuous lamp photolysis
instead of laser flash photolysis showed a clearly increasing trend
of (εtot × ˚tot ) vs. f[Fe(Ox)2 ]− in a study by Faust and Zepp [28] and
a good linear correlation in this work at 436 nm (see next section).
On the contrary, results from continuous lamp photolysis at 313 nm
(next section) show also such unexpected non-linear behavior.
This unexpected result is not caused by experimental errors,
(7)
Fig. 5. Product of overall quantum yields (˚) and overall extinction coefficients
(εtot ) of [Fe(Ox)2 ]− and [Fe(Ox)3 ]3− mixtures as a function of calculated [Fe(Ox)2 ]−
fraction, laser flash photolysis at 308 and 351 nm, Ar purged (O2 depleted), I = 0.01 M
(8) (NaClO4 ), [Fe3+ ]initial = 4.85 × 10−4 M.
]−
because the detection of photoproduced Fe2+ was in this case per-
formed well above the quantification limit. The product of overall
quantum yield and (εtot ) does not seem to be much affected over
a wide range of changing amounts of bis- and tris(oxalato)ferrate
complexes. Only at the left side of the plots in Fig. 5, (εtot × ˚tot )
shows a marked decrease, when the content of f[Fe(Ox)2 ]− is
smaller than 10%. Thus it can be concluded, that solutions clearly
dominated by [Fe(Ox)3 ]3− have a lower quantum yield than
solutions dominated by [Fe(Ox)2 ]− , which is in agreement with
the photochemical behavior of bis- and tris(oxalato)ferrate com-
plexes at 436 nm in continuous lamp irradiation studies ([28]
and next section). Because the solutions on the leftmost side of
the plot are clearly dominated by [Fe(Ox)3 ]3− with 99% bound
iron, these individual quantum yields are assigned to [Fe(Ox)3 ]3− :
˚308 nm = 0.93 ± 0.09 and ˚351 nm = 0.88 ± 0.08. The values have
been determined for the first time for these wavelengths.
3.3.2. Continuous photolysis of bis- and trisoxalatoferrate with
Hg(Xe) lamp at 313, 366 and 436 nm
The speciation dependent photochemistry of bis- and
tris(oxalato)ferrate complexes at 313, 366 and 436 nm was
measured at constant high [Fe3+ ]initial = 4.85 × 10−4 M. Quantum
yields were obtained from the slope of the regression line of a
plot of Fe2+ production vs. time as described in the experimental
section. The product (εtot × ˚tot ) was plotted against f[Fe(Ox)2 ]−
together with the measured values of εtot (Fig. 6).
From the regression lines in Fig. 6, the individual molar extinc-
tions were determined for bis- and tris(oxalato)ferrate complexes
at 313, 366 and 436 nm, which are compared with literature val-
ues in the case of 436 nm (Table 3). The individual quantum yields
could not be retrieved by regression analysis for 313 nm, which
will be further discussed. Unexpectedly, the individual quantum
yields determination at three different wavelengths led to three
distinct results. The plots for 313, 366 and 436 nm have in common
that the measured total extinction coefficient correlates well with
f[Fe(Ox)2 ]− . A straight correlation of (εtot × ˚tot ) with f[Fe(Ox)2 ]−
on the basis of Eq. 6 did however only appear at 436 nm. At 366 nm,
(εtot × ˚tot ) shows considerable scatter compared to 436 nm, but
an increasing trend toward higher f[Fe(Ox)2 ]− is clearly visible.
It has to be noted that for both 366 and 436 nm (εtot × ˚tot ) and
εtot are increasing with increasing f[Fe(Ox)2 ]− . The higher scatter
at 366 nm is most likely introduced by the close proximity of the
isosbestic point. Thus, the individual quantum yield and extinction
coefficient for [Fe(Ox)2 ]− at 366 nm contains a large error (Table 3).
For 313 nm, a change of f[Fe(Ox)2 ]− between 0.09 and 0.75 shows
only slight variations in (εtot × ˚tot ) but at f[Fe(Ox)2 ]− smaller than
 Author's personal copy

C. Weller et al. / Journal of Photochemistry and Photobiology A: Chemistry 255 (2013) 41–49 47

Table 3
Individual extinction coefficients and quantum yields from Hg(Xe)-lamp photolysis of bis- and tris(oxalato)ferrate complexes at 313, 366 and 436 nm, this work and literature.

photolysis 313 nm 366 nm 436 nm

[Fe(Ox)2 ] −
a
εi [l mol−1 cm−1 ] 2055 ± 111 753 ± 357 55 ± 9 62 ± 6
b
˚i (≥1.23) 1.17 ± 1.46 1.4 ± 0.40 a 1.0 ± 0.25

[Fe(Ox)3 ]3−
a
εi [l mol−1 cm−1 ] 2663 ± 37 709 ± 10 22 ± 2 24 ± 4
c
˚i 0.12 ± 0.05 0.91 ± 0.09 1.0 ± 0.20a 0.60 ± 0.46
Regression, ε m = −609, b = 2663, R = 0.95 m = 45, b = 709, R = 0.86 m = 33, b = 21, R = 0.99
Regression, ˚ – m = 161, b = 648, R = 0.68 m = 56, b = 21, R = 0.98
a
Ref. [28].
b
Highest ˚ measured in FeOx2 /FeOx3 mixture, therefore lower limit for FeOx2 .
c
Measured at 99% FeOx3 .
m = slope, b = intercept, R = correlation coefficient.

0.09 an abrupt decrease is seen, similar to the observations made

using laser flash photolysis at 308 and 351 nm (previous section).
Because of the unusual low quantum yields at low f[Fe(Ox)2 ]− , sev-
eral measurements from the 313 nm plot have been repeated to
exclude random experimental errors. The repeated experiments
involved complete renewal of all stock solutions and use of another
lamp-monochromator photolysis set-up, identical in construction
to the previous one. The quantum yield of ˚i = 0.12 that was mea-
sured in solutions dominated to 99% by [Fe(Ox)3 ]3− was assigned
to the 1:3 complex. Due to the non-linearity of the data, the indi-
vidual quantum yield could not be determined for the 1:2 complex
by linear regression. Since the highest measured overall quantum
yield in the [Fe(Ox)2 ]− /[Fe(Ox)3 ]3− mixtures was ˚ = 1.23, this val-
ues can be regarded as an lower limit for the [Fe(Ox)2 ]− complex
at 313 nm.
The individual extinction coefficients obtained at 436 nm in this
work agree well with the values published [28]. However, higher
values of individual quantum yields have been obtained in this
work, compared with Faust and Zepp [28]. This difference in indi-
vidual quantum yields is attributed to a difference in the [Fe3+ ]initial
in both studies, because it has been shown in the present work that
the quantum yield can depend on initial [Fe3+ ] (see Fig. 1). Taking
into account that Faust and Zepp’s [28] measurements were made
using lower [Fe3+ ]initial of 1 × 10−4 and 5 × 10−5 M which lie in the
region of decreasing and low overall quantum yields shown in Fig. 1,
the lower individual quantum yields could be readily explained by
the observed concentration dependence in the present work.

3.3.3. Concluding remarks to individual quantum yield analysis

Fig. 6. Product of overall quantum yields ˚ and overall extinction coefficients εtot
(regression: dashed line) of [Fe(Ox)2 ]− and [Fe(Ox)3 ]3− mixtures and εtot (regres-
sion: solid line) as a function of calculated [Fe(Ox)2 ]− fraction, continuous photolysis
with Hg(Xe) lamp at 313 (top), 366 (middle) and 436 nm (bottom), Ar purged (O2
depleted), I = 0.01 M (NaClO4 ), [Fe3+ ]initial = 4.85 × 10−4 M.
Wavelength dependent individual molar extinctions and quan-
tum yields are summarized in Fig. 7. A major outcome of this work is
to provide new data not only for one wavelength but also to present
and compare measurements from several wavelengths both using
continuous and laser flash irradiation techniques. The individual
quantum yields of 1:2 oxalato complexes are higher than those of
the 1:3 complexes which can be clearly seen from the experimental
data. Furthermore, the individual quantum yields of the 1:3 com-
plexes are almost constant in the considered range between 308
and 436 nm, except for the value at 313 nm.
Because it has been already shown, that the observed overall
quantum yield of ferrioxalate photolysis depends on reactions of
the carboxyl radical and thus strongly on changes in experimental
parameters, tentative interpretations of the unexpected nonlinear
behavior of (εtot × ˚tot ) vs. f[Fe(Ox)2 ]− for 308 nm (laser), 313 nm
(lamp) and 351 nm (laser) photolysis and the very low quantum
yield of [Fe(Ox)3 ]3− at 313 nm in the present study can be made
accordingly.
The conditions for the secondary reaction of the carboxyl radi-
cal are different comparing flash photolysis with continuous lamp
 Author's personal copy
48 C. Weller et al. / Journal of Photochemistry and Photobiology A: Chemistry 255 (2013) 41–49
Fig. 7. Individual quantum yields ˚i and individual extinction coefficients εi for the
[Fe(Ox)3 ]3− and [Fe(Ox)2 ]− complexes as a function of wavelength.
photolysis. In flash photolysis the generation of carboxyl radicals
happens in 20 ns which then react instantly with non-photolyzed
Fe(III) producing approximately micro-molar concentrations of
CO2 •− , which is in the moles per second range. On the contrary,
the production of CO2 •− in continuous lamp photolysis is in the
nano-mol per second range, so the ratio of the reactants CO2 •−
and non-photolyzed Fe(III) differs by many orders of magnitude
between the experiments, which could possibly cause a differ-
ent overall production of Fe2+ relative to the absorbed photons
given the sensitivity of ferrioxalate photolysis to the experimen-
tal conditions. However, because similar curved behavior is seen
also at 313 nm lamp photolysis, the considerations made above
might account for differences regarding flash versus continuous
photolysis but cannot explain the non-linearity in general.
It is likely that both [Fe(Ox)2 ]− and [Fe(Ox)3 ]3− have a different
initial photoreactivity. [Fe(Ox)2 ]− and [Fe(Ox)3 ]3− have different
redox potentials which would affect the reaction rate of the reduc-
ing radical CO2 •− with them and contribute differently to the
overall quantum yield. The standard reduction potential E◦ of CO2 •−
equals −1.85 V [48]. The E◦ of solutions containing a lower excess
of oxalate is higher (0.035 V), than in solutions dominated by
[Fe(Ox)3 ]3− where E◦ = 0.005 V [49]. Hence, it follows that the reac-
tion of CO2 •− with [Fe(Ox)2 ]− should be favored and proceed faster.
This could be one reason for the higher quantum yield of the 1:2
complex. Increased steric hindrance of the carboxyl radical attack
on the metal center caused by one more oxalate ligand in case of
the 1:3 complex could be another reason for a lower quantum yield
compared to the 1:2 complex. The above mentioned effects of dif-
ferent initial photoreactivity and secondary reaction of the carboxyl
radical could possibly lead to the curved dependence of (εtot × ˚tot )
vs. f[Fe(Ox)2 ]− observed in flash photolysis at 308 and 351 nm in
the present work (Fig. 5) and at 313 nm (Fig. 6).
Possible effects of free excess oxalate on secondary reactions
were considered for solutions with a high fraction of 1:3 com-
plex. Theoretically, it is improbable that formed carboxyl radicals
could be scavenged by excess oxalate. CO2 •− is a reducing rad-
ical which should be unreactive toward oxalate. A key to fully
understand the ferrioxalate system might lie in the reactions of
the excited state and the formed radical complexes, about which
not much information is published. Excited states of [Fe(Ox)3 ]3−*
were reported to undergo quenching by reaction with ground
state [Fe(Ox)3 ]3− (k = (4.5 ± 1.2) × 107 M−1 s−1 ) [11] which could
also affect the quantum yield of ferrioxalate photolysis. Nothing
was reported about quenching with excess oxalate. The importance
of radical complex reactions was shown by an experiment with
ferrioxalate photolysis and added CuSO4 , which remarkably
increased the quantum yield from 1.21 to 1.8 at 365 nm [16]. It was
postulated that Cu2+ ions enhanced the decomposition of the Fe(II)
radical complex and decreased the back electron transfer while
forming Cu+ , which could act as a further reductant of Fe(III) species.
The relevance for the present work is to show that radical complex
reactions can have a large impact, but they are not characterized
well enough to draw conclusions about their influence in solutions
with a changing speciation.
4. Summary and conclusions
The present contribution highlights that the chemistry of the
ferrioxalate system is by far not well understood although numer-
ously investigated by several researchers. It was shown that the
measured overall effective Fe2+ quantum yield of ferrioxalate pho-
tolysis can be a function of initial ferrioxalate concentration in the
range 10−4 M to 10−5 M. The concentration dependence is caused
by a decrease of the efficiency of the secondary Fe(III) reduction
via the CO2 •− radical and the simultaneous increase of CO2 •− rad-
ical recombination to reform oxalate. It has to be emphasized that
this concentration dependence should be taken into account when
published quantum yields for ferrioxalate photolysis are used for
the interpretation of systems with dilute concentrations, such as
environmental compartments like cloud or surface waters. For the
first time it has been shown that in dilute ferrioxalate solutions,
the measured quantum yields after flash photolysis decreased with
increasing photolysis light intensity suggesting a changing kinetic
regime for secondary reactions of the photofragments. Moreover,
the Fe2+ quantum yield depends on the contributions from the indi-
vidual coordination compounds [Fe(Ox)3 ]3− and [Fe(Ox)2 ]− , where
1:2 complexes have a higher quantum yield compared to the 1:3
complexes. Ultimately, it can be concluded that a differentiation
between the two different proposed mechanisms (R2) (concerted
electron transfer) and (R5) (oxalate C-C bond cleavage) is not pos-
sible on the basis of the Fe2+ quantum yield measurements in the
present work. The reason can be found in the design of the exper-
iments that measures only the net formed Fe2+ produced by a
number of processes, some of which remain poorly characterized.
The benefit of the present work is to highlight that the depend-
ence of the Fe2+ quantum yield on secondary reactions is very
pronounced, which are sensitive to initial concentration and irra-
diation intensity. The ferrioxalate photolysis experiments appear
similar to radical scavenging experiments, where the obtained yield
can depend on reactive species, mainly CO2 •− but possibly also
Fe(II) radical complexes or excited states of ferrioxalate complexes,
and the concentration of the scavenger, which would be ground
state ferrioxalate complexes. Hopefully, the present paper could
raise some awareness about the complicated interactions of the
ferrioxalate system and maybe trigger future investigations which
further aim at the investigation of secondary processes, possibly
under consideration of speciation effects.
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