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INDUCED AUTOXIDATION OF OXALATE IN RELATION

TO THE PHOTOLYSIS OF POTASSIUM FERRIOXALATE
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BY C. A. PARKER
Admiralty Materials Laboratory, Holton Heath, Poole, Dorset
Received 5th April, 1954 ; in final form, 7th July, 1954
The effect of oxygen upon the quantum yields in the photolysis of ferrioxalate in
neutral solution containing oxalate has been reinvestigated in the light of recent observa-
tions in acid solution.1 The zero yield of ferrous iron and the doubled yield of carbon
dioxide observed by Livingston 2 in the presence of oxygen is explained by thermal
autoxidation of the photochemically produced ferrous iron and the concurrent induced
autoxidation of oxalate ion. There is also some evidence that molecular oxygen can
itself participate directly in the photochemically initiated reaction chain. A mechanism
involving the photochemical formation of Fe2f and C204- and the subsequent com-
petition between these two primary products for the molecular oxygen and its primary
reduction product (02-) formally accounts for the results obtained.
The results of spectrophotometric measurements suggest that in acid solution at
least monoxalato- and bioxalato-ferric complexes are present. In neutral solution the
trioxalato complex appears to be the predominating species.

It has recently been shown 1 that photolysis of potassium ferrioxalate in 0.1 N

sulphuric acid is but little affected by oxygenation of the solution. This result
is in marked contrast to the results obtained by Allmand and Webb 3 using neutral
solutions containing an excess of oxalate. Livingston 2 found a striking difference
in behaviour in acidified solutions containing an excess of oxalate compared with
that observed by the present author. The experiments to be described were de-
signed to clarify this situation and to determine the cause of the doubled quantum
yield for C02 observed by Livingston.
Livingston's solution contained 0.1 M sodium oxalate and 0.02 M sulphuric
acid and was thus buffered to a pH of about 4. Apart from the excess of oxalate

by the author 1 (PH -

therefore, it was considerably less acid than the solutions previously investigated
1). Accordingly the effect of oxygen on the quantum
yield of ferrous iron was investigated both in acid solutions and in neutral solu-
tions, at various oxalate concentrations. The thermal autoxidation of ferrous
iron under similar conditions was also investigated. Finally, using larger quan-
tities of ferrous iron the induced thermal oxidation of oxalate was determined.

EXPERIMENTAL
In all the photochemical experiments 15 ml of solution were exposed to the 365-366 mp
group of mercury lines. Either oxygen or oxygen-free nitrogen was passed through the
liquid. The apparatus was similar to that previously described 1 employing mercury
lamp, copper sulphate and Chance OX1 filters and a phototube monitoring unit. As
before the irradiation vessels were fitted with loosely fitting polythene covers and in this
sense exclusion of air was not absolutely complete. Access of air was also possible
during the short period of manipulation before colorimetric reaction. Immediately
after irradiation, 1 ml aliquots were withdrawn for ferrous iron determination by the
standard method.1 The liquid was then allowed to stand for 2 h without further passage
of gas and a second determination of ferrous iron made. The results are shown in
table 1. The time of irradiation was 5 min for expt. 1-4 and 10 min for expt. 5-8.
Quantities of ferrous iron found are expressed as g equiv. x 10-6/min.
Thermal oxidation experiments were carried out using 15 ml quantities of solutions
of composition corresponding to expt. (3), (4), ( 5 ) and (6) in table 1. The solutions were
1213
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1214 AUTOXIDATION OF OXALATE

saturated with the appropriate gas, 1 ml of ferrous iron solution was added, containing
10.0 x 10-6 mole of ferrous iron in 0.01 N sulphuric acid. The ferrous iron remaining
in the solution after 10 min and 2 h was determined by the standard method using 1 : 10-
phenanthroline.1 The results are shown in table 2.

TABLE1.-PHOTOLYSIS
OF POTASSIUM FERRIOXALATE-EFFECT OF OXYGEN
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Quantities of Fe2+ found are expressed as g equiv. x 10+/min

Fez+ found at following times
after completion of irradiation
gas
nil 2h
1 0.006 nil nil 1*48 1-06
2 0.006 nil nil 1 *28 0.45
3 0.006 0-06 nil 0.76 nil
4 0.006 0-06 nil 0.05 nil
5 0.02 0.10 0.02 nil nil
6 0.02 0.10 0-15 1-40 1-17
7 0.006 nil 0.05 1-51 1-51
8 0.006 nil 0.05 1-45 1-44

TABLEAIR OXIDATION OF FERROUS IRON

10.0 x 10-6 mole of ferrous iron were taken in each case

Fez+ found after the
following periods
expt. no. [K3Fe(C204)3] [Kz$041 [Hzso41 (mole x 10-6) gas
M M -
10 min 2h
1 0.006 0.06 nil 5-1 - N2
2 0.006 0.06 nil 0.1 - 0 2
3 0.02 0.10 0.02 nil - 0 2
4 0.02 0.10 0.15 9.6 8.6 0 2
5 0.02 nil 0.05 10.0 10.0 0 2

TABLE
3 .-FERR~US-INDUCED AUTOXIDATION OF OXALATE

1 0.1 M Na2C2O4 0.02 M FeS04 < 0.01 h nil 49.65 5-00 0.35 0.07
0.02 M H2SO4 (25 ml) (02 for 3 h)
(50 ml)
2 ditto ditto 3h nil 48-16 5.00 1.84 0.37
3 0.1 M Na2C204 0.01 M FeS04
0-02 M H2SO4 0005 M H2SO4 < 0.01 h 0.01 49.33 9.99 0.67 0.07
(50 ml) (100 ml) ( 0 2 for 4 h)
pH = 4.0
4 ditto ditto 4h 0.24 46-64 9.76 3.36 0.34
5 50ml water 001 M FeS04 < 0.01 h 9-97 - 0.03 - -
(100 ml) (subse-
quently
oxygen-
ated for
4 h) final
pH=4.4
6 0.12 M NaAc ditto ditto 9-95 - 0.05 - -
0.036M H2S04 (final
(50 ml) pH 4-6)
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C . A. PARKER 1215
Two pairs of experiments were carried out using larger quantities of ferrous iron.
In one of each pair the ferrous iron solution was added all at once while in the other it
was added gradually over a period of several hours to the vigorously stirred oxalate
solution. A current of oxygen was passed through the oxalate solution throughout the
tests. The ferrous iron remaining in the solution was determined colorimetrically by the
standard method.1 The oxalate remaining was titrated with standard permanganate
solution, a correction being applied, where necessary, for the small amount of ferrous
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iron present.
Two similar oxidation experiments were performed in the absence of oxalate to confirm
the comparative insensitivity to autoxidation under these conditions. In this case the
extent of the oxidation was small and it was determined by measuring the increase in
the extinction at 300 mp due to the formation of ferric iron, after adjusting the acidity
to 0.8 N sulphuric acid. The results are shown in table 3.

Wave length my
FIG. 1.-Absorption spectra.
Curve 1, 0.018 M Fe3+ in 0.1 N sulphuric acid ;
curve 2, 0.018 M Fe3+ and 0.018 M oxalic acid in 0.1 N sulphuric acid ;
curve 3, 0.018 M Fe3+ and 0.054 M oxalic acid in 0.1 N sulphuric acid ;
curve 4, 0.018 M Fe3+ and 0-108 M oxalic acid in 0.1 N sulphuric acid ;
curve 5, 0.018 M potassium ferrioxalate in water.

All absorption spectra were measured with a Beckman spectrophotometer using

10-cm cells. The relevant spectra are shown in fig. 1. Optical densities at 480 and 490 mp
of various solutions as a function of oxalate/iron ratio are shown in fig. 2 and 3. All
solutions were prepared in a dark room illuminated by Kodak OB safelights and were
allowed to stand overnight, to come to equilibrium, before measurement.
The solutions used to determine the quantum efficiency of the monoxalato-ferric
complex (see table 5) contained added ferric sulphate, some of which was not combined
with oxalate and therefore acted as an inner filter at 366 mp. The actual concentrations
of " free " ferric iron were determined by electrode potential measurements as follows.
A series of solutions was prepared, all of which contained 0.001 M ferrous sulphate in
0.1 N sulphuric acid. Quantities of ferric sulphate were added to give ferric iron con-
centrations between O.oooO1 and 0.05 M. A bright platinum electrode was immersed in
39
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1216 AUTOXIDATION OF OXALATE

each solution in turn, a current of nitrogen was passed through the solution and the
potential of the platinum electrode measured against a saturated calomel electrode. The
results are shown in table 4 (expt. 1-6), and can be represented by a straight line when
plotted against log [Fe3+]. Some similar solutions were prepared which contained in
addition 0.006 M potassium ferrioxalate and concentrations of added ferric sulphate
I
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I 2 3 4 6
Molar ratio, bxalic acid/Ee’I
FIG. 2.-Optical density as a function of oxalate/iron ratio.
Curve 1,0*018M Fe3+in 0.1 N sulphuric acid with oxalic acid concentrations as indicated
(measured at 490 mp) ;
curve 2, 0,006 M Fe3+ in 0.1 N sulphuric acid with oxalic acid concentrations as indicated
(measured at 480 mp).

%
MoI a r ra t i0, f=e3 xa I at 4
FIG. 3.-Reaction of ferric iron with acid potassium ferrioxalate.
All solutions contained 0.006 M potassium ferrioxalate to which were added [Fe3+] to
give the indicated iron/oxalate ratios.
Slope of dotted line corresponds to extinction per unit (1/3) of ferric iron added assuming
no reaction with oxalate.

corresponding to those in the solutions used for photolysis (table 5). The electrode po-
tentials of the solutions (expt. 7-11 in table 4) were assumed to correspond to the ferric
iron not combined as oxalate (i.e. it was assumed that the activity coefficient of the ferric
sulphate was not affected by the addition of 0.006 M potassium ferrioxalate) and on this
basis they were converted to concentration of “ free ” ferric iron by reference to the plot
of expt. 1-6. Using these concentrations of ferric iron (column 5 of table 4), the
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C . A. PARKER 1217
proportion of light absorbed by uncombined ferric iron and by ferric oxalate complexes
was calculated and the results are shown in table 5. With these values and the observed
gross quantum efficiencies it was then possible to calculate the actual quantum efficiencies
of the ferric oxalate complexes present (column 8 of table 5).
TABLE4.-sUMMARY OF ELECTRODE POTENTIALS
+ 0.001 M FeS04
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All solutions contained 0.1 N H2SO4

[K3Fepo4)31 [Fe3+] mV [Fe3+]
expt. nu. added found
1 - 0~00001 327 -
2 - o*ooo1 379 -
376
3 - 0.00 I 430 -
43 1
4 - 0.006 478 -
476
5 - 0.02 506 -
6 - 0.05 526 -
7 0.006 - 283 1.6 x 10-6
8 0.006 0.006 406 0.0003
9 0.006 0.0 12 458 0.0028
10 0.006 0.018 48 1 0.0074
480
11 0.006 0.024 494 0.0130

TABLE5.-QUANTUM EFFICIENCY OF FERRIOXALATE IN THE PRESENCE OF

ADDED FERRIC ION

All solutions contained 0.006 M K3Fe (C204)3 in 0.1 N sulphuric acid.

Optical densities (0.d.) refer to 366 mp and 1 mm depth.
propor-
[Fe3+]
added M
[Fe3+J
found M
o*t$flto0.d.
(talc.)
total
(obs.)
0.d. due to
ferric-oxa-
la;e~sm-
tion of
light
a&sy:-c! ~~~~~~
grOSS corrected
zgtny
plexes
nil 1.6 x 10-6 < 0.001 0-414 0.414 1-00 1.18 1-18
0.006 0.0003 0.007 0.707 0.700 0.99 1.18 1.19
0.012 0.0028 0.069 0-847 0.778 0.92 1-11 1.21
0.018 0.0074 0.181 0.989 0.808 0.82 0.94 1.15
0-024 0.0130 0.318 1-125 0.807 0.72 0.85 1.18

RESULTS
The following conclusions can be drawn from the results in table 1.
(9 In neutral solution oxygenation reduces the quantum yield of ferrous iron, On
subsequent standing a further consumption of ferrous iron occurs (expt. 1 and 2).
(ii) The presence of excess oxalate in neutral solution causes a marked decrease in
ferrous iron yield and no ferrous iron remains even in the nitrogenated solution
(i.e. low but not zero [OZ]after 2 h (expt. 3 and 4)).
(iii) In weakly acid oxygenated solution containing excess oxalate no ferrous iron
was formed (expt. 5-i.e. in agreement with Livingston) but if an excess of
sulphuric acid is present the " inhibiting effect of oxalate is greatly reduced
"

(expt. 6).
(iv) In strongly acid solution without added oxalate the presence of oxygen causes
only a very slight reduction in the yield of ferrous iron. Subsequent thermal
oxidation in such solutions is negligible (expt. 7 and 8).
It would appear therefore that the " inhibiting effect " of oxygen in the photochemical
reaction is favoured both by low acidity and high oxalate concentration and that the thermal
oxidation of ferrous iron is the most rapid in conditions where the " inhibiting effect " is
the most prevalent. Nevertheless expt. 7 and 8 indicate that a small inhibiting effect
can occur in the photochemical reaction under conditions where thermal oxidation is
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1218 AUTOXIDATION OF OXALATE

negligible and (in this case at least) oxygen must be participating slightly in the photo-
chemically initiated reaction chain. That a purely thermal oxidation of ferrous iron
is sufficient to account for the major inhibiting effects observed in the other experiments
is shown by the results in table 2 where ferrous sulphate (10 x 10-6 mole) was added
to 15 ml quantities of solutions of composition corresponding to expt. 3, 4, 5 and 6 in
table 1, and the rate of oxidation determined.
The first two pairs of experiments in table 3 demonstrate that (i) ferrous iron is readily
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oxidized by oxygen in weakly acid oxalate solutions, and (ii) this autoxidation induces
the oxidation of oxalate, the relative consumption of oxalate being critically dependent
on the concentration of ferrous ions allowed to accumulate in the solution. Clearly,
the consumption of oxalate by this mechanism is likely to be favoured in the photochemical
reaction where, with normal light intensities, the ferrous iron is produced gradually and
uniformly. A consumption ratio of 0.37 was observed in one experiment (table 3) where
ferrous iron addition was slow and a ratio of 0-5 might well apply in the photochemical
reaction. The ferrous-induced autoxidation of oxalate could then account for the doubled
quantum efficiency observed by Livingston.
Naturally this does not rule out the possibility of direct reaction of molecular oxygen
with photochemically produced oxalate radical ion as an additional cause of the increased
oxalate consumption, but it is significant that under conditions where oxygen has little
effect on the ferrous iron yield (e.g. expt. 8 in table 1) it was found to have little effect on
the oxalate consumption also.

ABSORPTION SPECTRA OF SOLUTIONS AND QUANTUM EFFICIENCY OF

THE MONOXALATO FERRIC COMPLEX
In view of the critical effect of acidity upon the rate of oxidation of the photolysis
product it was of interest to determine what oxalato-ferric complexes are present in acid
and neutral ferrioxalate solutions. The data shown in fig. 1 and 2 provide a qualitative
picture although they are not sufficient for quantitative interpretation.
Addition of small quantities of oxalic acid to ferric sulphate in 0.1 N sulphuric acid
cause a marked increase in the optical density in the 480-500 mp region (compare curves
1 and 2 in fig. 1). The optical density reaches a peak value when the molar ratio of oxalate
to iron is just over unity and further addition of oxalate produces a decrease in optical
density (see fig. 2). Similar results were obtained by Bobtelsky, Chasson and Klein 11
by photometric titration. The high absorption (480-500 mp) is attributed to the monoxal-
ato-ferric complex and the fall in absorption to the progressive reaction of this complex
with more oxalate ions. On this basis a solution of potassium ferrioxalate in 0.1 N
acid (i.e. [oxalate]/[Fe3+]= 3) must contain considerable quantities of higher complexes
(see fig. 2). This is confirmed by the appearance of a weak absorption band at 650 mp
which is barely perceptible in the solution containing equimolecular proportions of
oxalate and iron (curves 2 and 3 in fig. 1). This band is intensifled slightly by the addition
of an excess of oxalic acid (curve 4 in fig. 1).
In neutral solutions of potassium ferrioxalate the absorption peak is shifted to 675 mp
(curve 5 in fig. 1) and is only slightly intensified by the addition of oxalate. The shapes
of the curves in fig. 1 and in particular the shift in absorption maximum and decrease
in absorption minimum on passing to neutral solution indicates that there is a third complex
(presumably trioxalato-ferric iron) present in the latter conditions. The results can be ex-
plained qualitatively in terms of a competition between H+ and Fe3+ for the oxalate ions :
+ +
H+ C2O42- HC204-,
+
Fe3+ C2042- @ [Fe(C204)l+,
+
[Fe(C204)1+ C2042- + [Fe(C204)21-,
+
[Fe(C204)21- C2042- + [Fe(C204)313-.
The acid solution recommended for actinometry 1 thus contains at least two ferric-
oxalate complexes, both of which, presumably, are photo-active. On the other hand in
the neutral oxalate solutions used by Allmand and Webb 3 the ferric iron was present
almost entirely as the trioxalato complex and the quantum efficiency of 1.18 found by
them can be attributed to the latter species.
To determine the quantum efficiency of the monoxalato-ferric complex, solutions of
potassium ferrioxalate were prepared containing added ferric sulphate. The optical
densities of these solutions at 490 mp are shown in fig. 3 which illustrates the progressive
reaction of the added ferric iron both with the bioxalato ferric complex and with the
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C . A. PARKER 1219
oxalic acid present in the unmodified acid potassium ferrioxalate solution. The curve
approaches asymptotically the slope corresponding to the optical density of ferric sulphate
solution and it is clear that when [Fe3+]/[oxalate]= 5/3,little further reaction with ferric
iron is taking place and the oxalate must be present almost completely as the monoxalato
complex.
The rates of photolysis (365-366 mp) of all five solutions were determined and were
corrected for the inner-filter effect of the “ free ” ferric iron present (the Iatter was deter-
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mined by electrode potential measurements-see table 4 and experimental section).

The results are shown in table 5 and indicate that after correction the quantum efficiency
is within experimental error, independent of the ferric iron added. The quantum efficiency
of the monoxalato complex (solution 5) is thus equal to the composite quantum efficiency
of the complexes present in the “standard” actinometer solution (solution 1) and is
also equal to the value found by Allmand and Webb for the trioxalato complex at 366 mp.

DISCUSSION
The dependence of the induced oxalate oxidation upon the ferrous iron con-
centration is similar to the effect observed in the oxidation of oxalate by Fenton’s
reagent 4 and suggests that a similar type of mechanism applies. Weiss 6 has 5 9

suggested that the first stage in the autoxidation of ferrous iron is the formation
of 02- by electron transfer :
Fe2+ 0 2+ + Fe3+ 02-. +
Energetic considerations 7 suggest that the equilibrium is normally far to the left
and that moderate concentrations of Fe3+ will be reduced by 02-. Complex
formation with phosphate or fluoride would favour an equilibrium shift to the
right and is in fact found to increase the autoxidation rate.S.9. 10 The results
in tables 1, 2 and 3 suggest that complexing with oxalate does likewise. We ma
thus represent the initial stage in the autoxidation process as follows :
+
Fe2+ 0 2 --Fe3+ ’ +
02-,
+
Fe3+ OH- t -
[Fe(OH)J2+, etc.,
+
neutral solution [Fe(C204)2]2- 0 2 + _-[Fe(C204)21- 02-, + (3)
{
---+

(with oxalate) [Fe(C204)2]- +

C2042- c-
[Fe(C204)313-, (4)
acid solution +
Fe2+ 0 2 - z F e 3 + 02-, +
{
(with oxalate) Fe3+ 4-C2042- t , -[Fe(C204)],+etc.,
(1)
(5)
The bioxalato ferrous ion has been represented as the active species in neutral
oxalate solution. That ferrous iron is strongly complexed under these conditions
is indicated by the solubility of the sparingly soluble ferrous oxalate in excess of
potassium oxalate and by the intense yellow colour of the solution. Double
oxalates of the type M2Fe(C204)2 are known 15 but it has not been determined
whether [Fe(C204)2]2- is the only species present in oxalate solution. The com-
plexing of ferrous iron is not, of course, essential to explain the increased rate of
oxidation.
In the absence of oxalate, reaction (1) is followed by further oxidation of Fez+
by 0 2 - involving HO2 and OH radicals (cf. Posner 12).
With this mechanism, the presence of oxalate may have the following effects :
(i) increase the stationary concentration of 0 2 - by ferric or ferrous complex
formation,
(ii) compete with Fez+ for the H02 and OH radicals with the production of
oxalate radical ion :
€302 + + H02- +
c204-,
2c204- --f f 2c02,
giving rise to induced oxidation of the oxalate (this reaction will account
for the induction of Eder’s reaction in the dark by Fez+ in the presence
of oxygen 13).
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1220 AUTOXIDATION OF OXALATE

This competition between Fe2+ and C2O42- explains the marked dependence of
oxalate consumption on the rate of addition of ferrous iron solution. In the
limit, with large [C2042-] and very small [Fe2+]all the HO2 radicals initially formed
would be reduced by oxalate and the consumption ratio A[C20$-][A[Fe2+]
would tend to 0.5. Applied to the autoxidation of the photochemically formed
Fe2+this mechanism could clearly account quantitatively for the double quantum
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yield of C02 observed by Livingston in the presence of oxygen.

The following additional reaction will almost certainly occur to some extent
both in the thermal and photochemical processes, and, if dominant, would lead
to a chain reaction. As a result in the photochemical reaction the quantum
yield of C02 could be more than doubled :
C2O4- + 0 2 --f 2C02 +
02-. (6)
Reaction (6) is said to be the cause of the inhibiting effect of oxygen in the Eder
+ + +
reaction 13 and in the Fe2+ H202 oxalate HgC12 reaction.4 The occur-
rence of reaction (6) in the photolysis of ferrioxalate would allow of the possibility
of decrease in ferrous iron yield and corresponding increase of C02 yield under
conditions where thermal autoxidation of ferrous iron is negligible. A slight
indication of such an effect is in fact observed in 0.1 N acid (e.g. expt. 7 and 8
in table 1). It should perhaps be mentioned at this stage that in considering the
effects of pH value, account must also be taken of the dissociation constant of
the semi-oxidized oxalic acid :
+ +
HC204 H+ c 2 0 4 - . (7)
Independently of the other factors considered, this would introduce a variable
effectin oxygenated solutions if the undissociated radical were less reactive towards
molecular oxygen than the oxalate radical ion.
Our present view of the photolysis of ferrioxalate in neutral solution may
therefore be summarized as follows :
hv
[Fe(C204)3I3--+ [Fe(C204>2I2--k c204-, (8)
(2204- + +
[Fe(C204)313- -+ 2C02 [Fe(C204)2l2- C2Q2- + (9)
C2O4- +C2O4- --+ 2C02 C2O42-. + (10)
In acid solution substantially the same reactions occur but with [Fe(C204)]+
and [Fe(C204)2]- as additional photo-active species, uncomplexed Fez+ as the
product and possibly HC2O4 as the intermediate radical. Some such reaction
as (9) must be invoked to explain quantum yields of ferrous iron greater than
unity at some wavelengths.193 Reaction (8) may, in accordance with Evans,
Santappa and Uri,14 be divided into two stages, e.g. in acid solution :
hv
Fe3+(C204)2- 7
primary dark
Fe2+(C204)-, (1 1)
back reaction
dissociation of
Fe2+(C204)- 3
excited complex
Fe2+ + C2O4-.
Secondary dark back reaction, as observed by Evans, Santappa and Uri in the
photodecomposition of [Fe(OH)]2+, does not appear to be significant with
[Fe(C204)]+ since no reduction of quantum efficiency was observed when ferrous
sulphate (up to 8 x 10-3 M) was added to the solution of 0-006 M ferrioxalate.
In the presence of oxygen both Fe2+ and C2O4- initiate chains which ultimately
result in a reduction in the yield of ferrous iron and an increase in the consumption
of oxalate. The extent to which this occurs depends upon the acidity of the
solution and the concentration of oxalate in the manner already described.
In the absence of oxygen the theoretical quantum yield of ferrous iron is 2.
The relative importance of reaction (10) and the primary dark back reaction in
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C. A . P A R K E R 1221
reducing this to the observed values (e.g. 1.18 at 365-366 mp 1) is indicated by the
results of some experiments on the effect of varying light intensity. It has been
found that with 0.006 M ferrioxalate in 0.1 N sulphuric acid the quantum yield
of Fez+ with 365-366 mp radiation is independent of light intensity over a wide
range (0.003-7 micro-einsteins/cm2 sec). Over this range of intensities therefore
it would appear that reaction (10) does not contribute to an appreciable extent.
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Experiments with still higher intensities are in progress and the results will be
reported in detail elsewhere. The relative importance of reaction (10) could
be confirmed by observing the effect on the quantum yield of the addition of re-
agents for C204- or HC204 (e.g. reagents for free radicals). Oxygen itself is,
of course, an unsuitable reagent owing to the autoxidation of ferrous iron already
discussed.

The author desires to express his thanks to Dr. E. J. Bowen for much helpful
advice. This paper is published by permission of the Admiralty.
1 Parker, Proc. Roy. SOC. A, 1953,220, 104.
2 Livingston, J. Physic. Chem., 1940, 44,601.
3 Allmand and Webb, J. Chem. Soc., 1929, 1518.
4 Weiss, Faraday SOC. Discussions, 1947, 2, 188.
5 Weiss, Symposium Sur Transferts Electronique en Solution et aux Electrodes (Paris,
1951).
6 Weiss, Naturwiss., 1935, 23, 64. 7 Uri, Chem. Rev., 1952, 50, 375.
8 Spoehr, J. Amer. Chem. SOC.,1924, 46, 1999.
9 Smith and Spoehr, J. Amer. Chem. SOC., 1926,48, 107.
10 Lamb and Elder, J . Amer. Chem. SOC., 1931, 53, 137.
11 Bobtelsky, Chasson and Klein, Anal. Chim. Acta. 1953, 8, 460.
l 2 Posner, Trans. Faraday Soc., 1953, 49, 382.
13 Cartledge, J. Amer. Chem. Soc., 1941, 63, 906.
14 Evans, Santappa and Uri, J. Polymer Sci., 1951, 7, 243.
15 Sidgwick, Chemical Elements and Their Compounds (Oxford University Press, 1950),
p. 1347.