JOURNAL OF COLLOID AND INTERFACE SCIENCE 177, 288–297 (1996)

ARTICLE NO. 0034

A Kinetic Study of the Reduction of Colloidal

Manganese Dioxide by Oxalic Acid
JOAQUIN F. PEREZ-BENITO,* ,1 CONCHITA ARIAS,* AND ELISENDA AMAT†
*Departamento de Quimica Fisica, Facultad de Quimica, Universidad de Barcelona, Marti i Franques, 1, 08028 Barcelona, Spain; and
†Unidad de Fisicoquı́mica, Facultad de Farmacia, Universidad de Barcelona, Avenida Diagonal, s/n, 08028 Barcelona, Spain

Received May 15, 1995; accepted June 14, 1995

or reaction products in most permanganate oxidations (11,

A kinetic study of the reaction between colloidal manganese
dioxide and oxalic acid in aqueous acetate media (pH 4.3–5.1) is
reported. The reaction is autocatalytic and, in order to determine
the rate constants k1 and k2 corresponding, respectively, to the
noncatalytic and autocatalytic reaction pathways, the Mn(III)
formed as an intermediate was stabilized by addition of sodium
pyrophosphate. Joint iodimetric and spectrophotometric studies
indicated that the reduction of colloidal manganese dioxide follows
the sequence
R Mn ( IV ) R the reaction between colloidal manganese dioxide (in the
Mn(IV) r Mn(II) Mn(III) r Mn(II),
where R stands for the reductant. Both reaction pathways exhibit
acid catalysis, and the activation energies associated to k1 and k2
are 74.7 { 0.9 and 44.6 { 0.6 kJ mol 01 , respectively. The reaction
is accelerated by addition of manganese(II) sulfate, and k2 in-
creases with rising oxalate concentration, suggesting that MnC2O4
is the active autocatalyst. The possibility that Mn(III) might col-
laborate in the autocatalysis through a free-radical chain mecha-
nism is also pointed out. q 1996 Academic Press, Inc.
Key Words: autocatalysis; colloidal solution; kinetics; manga-
nese dioxide; oxalic acid.
12), being actively involved in the mechanism as autocata-
lysts in many cases (13, 14).
On the other hand, although the kinetic aspects of the
manganese–oxalate reacting systems have gained new inter-
est in the last decade due to their involvement in some oscil-
lating reactions (15–20), the reduction of colloidal manga-
nese dioxide by oxalic acid has received much little attention
(21–23) than its relative, the permanganate–oxalate reac-
tion (24, 25). We have now undertaken a kinetic study of
form of a perfectly transparent, aqueous sol) and oxalic acid
and found that it is in fact an autocatalytic reaction, whose
stoichiometry may be written as
MnO2 / H2C2O4 / 2H / Å Mn 2/ / 2CO2 / 2H2O. [1]
We think that the results presented here for the title reaction
might throw some light upon the common aspects of the
autocatalytic behavior exhibited by both the MnO2 –H2C2O4
and MnO 40 –H2C2O4 (26) reactions.

MATERIALS AND METHODS

INTRODUCTION
Preparation of the Colloidal Manganese Dioxide Sol
Manganese dioxide is a substance of certain importance
To prepare the colloid, 10 ml of KMnO4 (0.100 mol dm03 )
owing to its catalytic (1) and oxidizing (2–5) properties, but
and 20 ml of Na2S2O3 (1.88 1 10 02 mol dm03 ) aqueous
its applications are notably limited because of its insolubility
solutions were mixed together in a 2-liter volumetric flask,
under ordinary conditions (6). In recent years, however, the
and water was added until completion, the solution being
preparation of several forms of colloidal manganese dioxide
homogeneized afterwards by gentle stirring. The reaction
stable for long periods as brown or yellow, perfectly trans-
taking place under these conditions may be described by the
parent solutions, either in aqueous (7, 8) or organic (9)
stoichiometry
media, has made possible the kinetic study of its oxidizing
behavior in redox reactions by easily implemented, conven-
tional spectrophotometric methods (10). Moreover, the 8MnO 40 / 3S2O 20
3 / 2H
/
Å 8MnO2 / 6SO 20
4 / H2O.

transparent sols of manganese dioxide are also of importance [2]

because of their widespread participation as intermediates
Provided that the oxidant and reductant concentrations are
1
To whom correspondence should be addressed. used in stoichiometric ratio, a dark-brown solution is ob-

0021-9797/96 $12.00 288

Copyright q 1996 by Academic Press, Inc.
All rights of reproduction in any form reserved.

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 THE MnO2 –H2C2O4 REACTION 289
tained, remaining perfectly transparent at least for several
months (8, 10).

Colloid Characterization
The colloidal solution so prepared ([MnO2 ] Å 5.00 1
10 04 mol dm03 ) was characterized by means of a Malvern
autosizer 2.C, the results indicating that 90% of the colloidal
particles had a diameter comprised in the range 89–193 nm,
with a peak at 120 nm. The zeta potential (measured with
a Malvern zeta-sizer 4.C) was 047 { 3 mV. In addition,
coagulation experiments performed in a previous work (8)
indicated that the colloidal particles had a negative electro-
static charge, thus indicating that their stability in solution
was probably due to the fixation of some anions on the
colloid surface. The colloid’s UV–vis spectrum was re- FIG. 1. Average oxidation state of the manganese atom during the
corded with a Hitachi U 2000 UV–vis double-beam spectro- reduction of colloidal MnO2 (9.62 1 10 05 mol dm03 ) by Na2C2O4 (9.62
1 10 04 mol dm03 ), in the presence of HAc (0.504 mol dm03 ) –NaAc
photometer, and showed a large band covering the whole
(0.481 mol dm03 ) buffer, at pH 4.57 and 25.07C. Open circles: [Na4P2O7 ]
visible region of the spectrum, with absorbance uniformly Å 0; filled circles: [Na4P2O7 ] Å 4.77 1 10 03 mol dm03 .
decreasing with increasing wavelength, as well as a wide
maximum at 300–400 nm.
and Mn(III) were reduced by iodide ion to the Mn(II) state.
Other Reagents Then, the average oxidation state of manganese could be
obtained as
The solvent used was water previously purified by de-
ionization followed by double distillation ( the first time
5A351
from a potassium permanganate solution ) . The reductant OSav Å 2 / , [3]
used in the kinetic experiments was sodium oxalate ( al- 1351l[Mn]T
ways in a large excess with respect to MnO2 ) . To keep
the pH constant during the runs, an acetic acid ( HAc ) – where A351 and 1351 are the absorbance of the solution and the
sodium acetate ( NaAc ) buffer mixture was used ( pH 4.3 – molar absorptivity of triiodide ion at 351 nm, respectively, l
5.1 ) , since the reaction either in aqueous HClO4 or in the is the optical pathlength of the cuvettes (1 cm), and [Mn]T
presence of H3PO4 – NaH2PO4 buffer ( pH É 2 ) was too is the total manganese concentration present in the system
fast to be followed by conventional spectrophotometry. during the reaction.
Manganese ( III ) was stabilized in the solution by addition
of sodium pyrophosphate. When necessary, the ionic Kinetic Measurements
strength was kept constant with a large excess of sodium The progress of the reaction was followed by means of a
perchlorate. Other additives used in some of the experi- Varian Cary 219 UV–vis spectrophotometer provided with
ments were manganese ( II ) sulfate, gum arabic and EDTA a thermostatized cuvette holder. The wavelength chosen was
( tetrasodium salt ) . All the chemicals used were purchased 400 nm, taking into consideration that colloidal manganese
from Merck ( analytical quality ) . dioxide had a strong absorption there, and that neither man-
ganese(II) ion nor the oxalate and pyrophosphate complexes
Iodimetric Determinations of manganese(III) showed any appreciable absorption. The
pH’s of the solutions were determined by means of a Met-
In some experiments, the average oxidation state (OSav )
rohm 605 pH-meter provided with a glass–calomel combi-
of manganese during the MnO2 –H2C2O4 reaction was deter-
nation electrode.
mined by taking successive 2-ml aliquots of the reaction
mixture (buffered with HAc–NaAc and kept in a thermo-
RESULTS
static bath at 25.07C) and introducing them into 5-ml volu-
metric flasks containing an excess of solid potassium iodide.
Influence of Pyrophosphate
After dilution with water until completion, the solutions were
homogeneized and the iodine liberated was determined by The average oxidation state of manganese during the
UV–vis spectrophotometry [ lmax (I 30 ) Å 351 nm, 1351 Å 2.57 MnO2 –H2C2O4 reaction both in the absence and in the pres-
1 10 4 dm3 mol 01 cm01 ]. In accordance with many other ence of sodium pyrophosphate was determined by iodimetry.
previous works (27–29), it was assumed that both Mn(IV) We can see in Fig. 1 that when Na4P2O7 was not present the

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290 PEREZ-BENITO, ARIAS, AND AMAT

of Mn(II) increased, passed through a maximum, decreased,

FIG. 2. Fractions of Mn(IV) (open circles), Mn(III) (triangles), and
Mn(II) (filled circles) during the reduction of colloidal manganese dioxide
by sodium oxalate in the presence of sodium pyrophosphate. The experi-
mental conditions are given in the legend of Fig. 1.
average oxidation state decreased uninterruptedly from 4 to
2, whereas in the presence of an enough amount of that
additive the reduction took place until the oxidation state 3 in
a first stage. At that moment, the UV–vis spectrum showed a
small peak at 470 nm, thus confirming the presence in the
solution of a manganese(III) –pyrophosphate complex
(30). Under those conditions, the total reduction until the
final Mn(II) state took several hours.
Moreover, although the concentration of Mn(III) during
the reaction in the experiment performed in the absence of
pyrophosphate was too low to be determined, in the one
performed in the presence of that additive it was possible to
determine the fractions of the total manganese present in the
system during the reaction in the oxidation states II, III, and
IV ( fII , fIII , and fIV, respectively). To that end, the decay of
Mn(IV) was followed by spectrophotometry at 400 nm for
the same experimental conditions used in the iodimetric ex-
periment (Fig. 1, upper curve). Since at that wavelength
only Mn(IV) exhibits an appreciable absorption, the equa-
tions necessary to calculate the fractions of each manganese
species present in the system at each particular instant t are
and finally showed a slow increase. It is interesting to notice
that the final conversion of Mn(III) to Mn(II) seemed to
occur when Mn(IV) was not present in the system any
longer.
When the reaction was followed spectrophotometrically,
a small induction period was observed during which the
reaction rate showed a fast decrease. After that, the rate
started to increase in a typically autocatalytic manner, pass-
ing through a maximum and decreasing afterward (Fig. 3).
Addition of sodium pyrophosphate to the solution at the
beginning of the kinetic runs resulted in a clear acceleration
of the reaction, since an increase of the reaction rate both
at the minimum and the maximum of the rate vs. time plots
was observed, whereas the half-life period of the reaction
(t1 / 2 ) decreased (Fig. 4).
On the other hand, an attempt to study the effect on the
reaction of EDTA [a good complexing agent for both
Mn(II) and Mn(III)] failed because in the media of our
work colloidal manganese dioxide was reduced by that re-
actant even faster than by oxalic acid.
Determination of the Rate Constants
The most simple way of describing mathematically the
kinetic behavior of an autocatalytic reaction is to assume
that two reaction pathways (one noncatalytic and the other
autocatalytic) are involved, and that the kinetic orders of
the reactant in defect (in both pathways) and of the autocata-
lyst (in the autocatalytic pathway) are the unity. If, in addi-
tion, we assume that the concentration of autocatalytic prod-
uct at a particular instant t is directly proportional to the
decrease of the reactant concentration from the beginning

fII / fIII / fIV Å 1 [4]

OSav Å 2 fII / 3 fIII / 4 fIV [5]
[Mn IV ] A400
fIV Å Å 0 [6]
[Mn]T A 400

where A400 and A 0400 are the absorbances of the solution at

400 nm at time t and at the beginning of the reaction, respec-
tively.
It can be seen in Fig. 2 that the fraction of Mn(IV) de-
creased with time according to a sigmoid curve typical of
autocatalytic reactions. The fraction of Mn(III) increased
first and then started to decrease very slowly, whereas that
FIG. 3. Dependence of the reaction rate on time during the reduction
of colloidal MnO2 (1.00 1 10 04 mol dm03 ) by Na2C2O4 (1.00 1 10 03 mol
dm03 ), in the presence of HAc (0.525 mol dm03 ) –NaAc (0.500 mol dm03 )
buffer, at pH 4.60 { 0.01 and 25.07C. Open circles: [Na4P2O7 ] Å 0; filled
circles: [Na4P2O7 ] Å 4.96 1 10 03 mol dm03 .

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 THE MnO2 –H2C2O4 REACTION 291
took place in the presence of a concentration of sodium
pyrophosphate high enough, the rate-decreasing induction
period was followed by another period in which the autoca-
talysis did not disappear and Eq. [8] clearly holds.
This finding has allowed us to determine the rate constants
k1 and k2 from the intercept and slope of the linear portion
of the r/[MnO2 ] vs [MnO2 ]0 – [MnO2 ] plots, respectively.
To that end, the experiments were performed in the presence
of a pyrophosphate concentration high enough to stabilize
the autocatalysis after the minimum of those plots (see Fig.
5, upper curve). In each kinetic run, the reaction rate was
estimated at 5-s intervals as

FIG. 4. Dependence of the rate/[MnO2 ] ratios at the minimum (open

1 D A400
rÉ0 , [9]
circles) and the maximum (filled circles) of the rate vs time plots, and of 1400l Dt
the half-life period (triangles), on the concentration of Na4P2O7 for the
reduction of colloidal MnO2 (1.00 1 10 04 mol dm03 ) by Na2C2O4 (1.00
1 10 04 mol dm03 ), in the presence of HAc (0.525 mol dm03 ) –NaAc where D A400 is the change of absorbance of the reaction
(0.500 mol dm03 ) buffer, at pH 4.60 { 0.01 and 25.07C. mixture at 400 nm between the instants t and t / Dt, with
Dt Å 5 s, and 1400 is the molar absorptivity of colloidal
manganese dioxide at that wavelength.
of the kinetic run until that moment, we have the differential
rate law Experimental Errors
It should be noticed that both the accidental and systematic
d[MnO2 ]
rÅ0 errors increase very rapidly as the number of rate constants
dt to be determined in each kinetic experiment increases (34).
Å k1[MnO2 ] / k2[MnO2 ]([MnO2 ]0 0 [MnO2 ]) [7] In those reactions followed by spectrophotometry and where
two rate constants have to be determined in each experiment,
or else as is the case of autocatalytic reactions, one of the main
sources of errors (both accidental and systematic) is the
gradient between the temperature of the laboratory (external
r
Å k1 / k2 ([MnO2 ]0 0 [MnO2 ]), [8] temperature, Te ) and that at which the kinetic runs are per-
[MnO2 ] formed (internal temperature, Ti ). For instance, if Te õ Ti
the entrance of cool air into the cuvette holder of the spectro-
where r is the reaction rate at time t, [MnO2 ]0 and [MnO2 ] photometer at the beginning of the kinetic runs, and the
are the concentrations of colloidal manganese dioxide at the
beginning of the reaction and at time t, respectively, k1 is
the pseudo-first-order rate constant of the noncatalytic path-
way, and k2 is the pseudo-second-order rate constant of the
autocatalytic pathway.
Differential rate laws similar to Eqs. [7] and [8] have
been successfully used for the kinetic study of several auto-
catalytic permanganate reactions (31–33). Although, ac-
cording to the latter equation, an increasing linear relation-
ship would be expected when representing the ratio r/
[MnO2 ] against the difference [MnO2 ]0 – [MnO2 ], it can be
seen in Fig. 5 that, in the absence of sodium pyrophosphate,
once finished the rate-decreasing induction period, the ratio
r/[MnO2 ] increased a little but reached soon a rather station-
ary value where the autocatalysis seemed to disappear, so
that the kinetic behavior of the reaction can then be approxi-
FIG. 5. Dependence of the rate/[MnO2 ] ratio on the decrease of MnO2
mately described by a first-order rate law (horizontal stretch concentration during the kinetic runs in the absence (open circles) and
in the lower curve shown in Fig. 5). However, as can be presence (filled circles) of Na4P2O7 . The experimental conditions are given
seen in the same figure (upper curve), when the reaction in the legend of Fig. 3.

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292 PEREZ-BENITO, ARIAS, AND AMAT

TABLE 1
Values of the Rate Constantsa at Various Initial Concentrations of Colloidal Manganese Dioxideb

[MnO2]0c k1d k1e k1f k2d k2e k2f

1.00 7.1 { 0.2 4.5 { 0.1 12.7 { 0.3 26.8 { 0.5 19.2 { 0.6 88.1 { 1.3
1.20 6.6 { 0.2 4.0 { 0.1 11.4 { 0.1 24.4 { 0.6 17.9 { 0.2 81.1 { 0.5
1.40 5.9 { 0.1 3.5 { 0.1 12.2 { 0.8 23.4 { 0.1 17.2 { 0.1 72.5 { 1.0
1.60 5.2 { 0.1 3.3 { 0.1 11.5 { 0.8 22.5 { 0.2 15.9 { 0.1 67.5 { 1.8
1.80 5.1 { 0.2 3.2 { 0.1 12.2 { 0.1 20.9 { 0.1 14.7 { 0.2 60.1 { 0.5
2.00 4.6 { 0.1 3.1 { 0.1 11.1 { 0.7 20.1 { 0.1 13.8 { 0.1 57.5 { 0.7

a
Rate constant k1 is given in 1004 s01 and k2 in dm3 mol01 s01.
b
[HAc] Å 0.525 mol dm03, [NaAc] Å 0.500 mol dm03, [Na4P2O7] Å 9.92 1 1003 mol dm03, pH 4.64, 25.07C.
c
In 1004 mol dm03.
d
[Na2C2O4] Å 2.00 1 1003 mol dm03; [gum arabic] Å 0.
e
[Na2C2O4] Å 2.00 1 1003 mol dm03; [gum arabic] Å 0.388 g dm03.
f
[Na2C2O4] Å 1.00 1 1002 mol dm03; [gum arabic] Å 0.388 g dm03.

subsequent increase of the temperature of that compartment
to reach that of the thermostatic bath connected to it (Ti ) as
the reaction progresses, result in considerable errors in the
determination of both k1 (experimental value õ real value)
and k2 (experimental value ú real value). On the contrary,
when Te ú Ti the entrance of hot air into the cuvette holder
at the beginning of the runs results in experimental values
of k1 and k2 too high and too low, respectively. To minimize
this problem, the temperature of the laboratory was con-
trolled to keep the gradient ÉTe 0 TiÉ as low as possible
(average differences: 0.57C for the experiments performed
at 25.07C, and 3.07C for those corresponding to the determi-
nation of the Arrhenius parameters).
Another source of systematic errors that should be taken
into consideration is that related with the colloidal nature of
one of the reactants (the oxidant); in that respect, since the
reactivity of manganese dioxide is expected to change as
the reaction progresses due to the decrease of the colloidal
particles’ size, the values given in the present work for rate
constant k2 have to be considered as mean values of that
magnitude.
Two independent determinations of each (k1 , k2 ) couple
of values were done, the reproducibility of rate constant k1
being lower than that of k2 , although the accidental errors
associated to the determination of both k1 and k2 were rather
low, as indicated by the corresponding average standard de-
viations (2.9 and 1.2%, respectively). Some attempts were
also made to measure the value of the initial rate correspond-
ing to each kinetic run, but the sharp decrease of the reaction
rate during the induction period (see Figs. 3 and 5) prevented
us from extrapolating reproducible values of that magnitude.
Kinetic Data
Both rate constants k1 and k2 decreased as the initial con-
centration of colloidal manganese dioxide increased (Table
1). That decrease certainly reflects the existence of some
systematic errors in the determination of the rate constants
(see above), given that one of the basic tenets in chemical
kinetics is that, when the isolation method is applied, the
pseudorate constants obtained are independent of the initial
concentration of the reactant in defect. To minimize the
possible flocculation of the colloidal particles, the experi-
ments were repeated in the presence of gum arabic, since this
water-soluble polysaccharide is known to stabilize colloidal
manganese dioxide in solution (35), but no improvement
was observed. However, when the concentration of sodium
oxalate was increased, k1 values notably independent of
[MnO2 ]0 were obtained, although the decrease of k2 per-
sisted. It should be noticed that rate constants depending on
the initial concentration of the reactant in defect have been
obtained in many permanganate reactions (36, 37), and in
those with an autocatalytic character that dependence is espe-
cially notable in the case of k2 (14).
Both rate constants increased with rising oxalate concen-
tration in a nonlinear manner (Fig. 6), suggesting an ap-
proach toward a situation where the colloid surface is satu-
rated by the reductant adsorbed on it. Addition of gum arabic
resulted in a decrease of both k1 and k2 (see also Table 1),
probably due to a competition with the reductant for the
colloid surface. However, the inhibition effect caused by
gum arabic was much less pronounced than the one found
in a previous work for the reduction of colloidal manganese
dioxide by formic acid (10). An important feature of the
plots shown in Fig. 6 is that their extrapolation until zero
concentration of reductant yields positive intercepts, sug-
gesting that in the absence of oxalate some degree of reduc-
tion of colloidal manganese dioxide happened after addition
of the buffering agents.
By changing the concentrations of the two components
of the buffer mixture, keeping constant both the total acetate
concentration ([HAc] / [NaAc]) and the ionic strength
(with excess NaClO4 ), it was observed that both rate con-
stants exhibit acid catalysis (Fig. 7), but k1 was much more

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 THE MnO2 –H2C2O4 REACTION
FIG. 6. Dependence of rate constants k1 (open symbols) and k2 (filled
symbols) on the concentration of Na2C2O4 for its oxidation by colloidal
MnO2 (1.00 1 10 04 mol dm03 ), in the presence of HAc (0.420 mol dm03 ) –
NaAc (0.600 mol dm03 ) buffer and Na4P2O7 (4.96 1 10 03 mol dm03 ), at
pH 4.79 { 0.02 and 25.07C. Circles: [gum arabic] Å 0; triangles: [gum
arabic] Å 0.232 g dm03 .
sensitive toward the solution pH than k2 . In a series of experi-
ments where the concentration of NaClO4 was varied to
study the effect of the ionic strength, k1 increased with rising
perchlorate concentration to reach a maximum value and
decrease later when that concentration was increased further,
whereas k2 decreased uniformly (Table 2). Although addi-
tion of that electrolyte resulted in a decrease of the solution
pH, once corrected the values of the rate constants to com-
pensate for the pH variation, the dependences of k1 and k2
on the ionic strength at constant pH remained quite similar
to those exhibited by the experimental, uncorrected values.
Addition of manganese(II) sulfate (in concentrations not
high enough to produce appreciable changes in the ionic
strength of the solution) at the beginning of the kinetic runs
resulted in an increase of k1 (Fig. 8, up) and a decrease of
k2 (Fig. 8, down) but the former was much more pronounced,
so that the net effect was an acceleration of the reaction
(decrease of t1 / 2 ). The notable dependence of k1 on the initial
manganese(II) concentration could be quantitatively de-
scribed by a second-degree polynomial,
k1 Å a / b[Mn 2/ ]0 / c[Mn 2/ ] 20 , [10]
and the three experimental parameters involved (a, b, and
c) increased with rising reductant concentration (Fig. 9).
Finally, both rate constants fulfilled the Arrhenius law
(Fig. 10), the corresponding activation energies (Table 3)
indicating that the autocatalytic pathway (44.6 { 0.6 kJ
mol 01 ) was more favorable from an energetic viewpoint
than the noncatalytic one (74.7 { 0.9 kJ mol 01 ).
DISCUSSION
Noncatalytic Reaction Pathway
Given the dissociation constants of oxalic acid [pKa,1 Å
1.23 and pKa,2 Å 4.19 (38)], and that all the experiments
/ m4420$3910 12-22-95 14:36:44 coida
293
of the present work were made in the pH range 4.3–5.1
(Fig. 7), we can conclude that the reductant was present in
the solution predominantly in the form of oxalate ion. Taking
into consideration this fact along with the kinetic information
found for rate constant k1 , we propose for the noncatalytic
reaction pathway the following mechanism:
/
C2O 20
4 / H S HC2O 40 [11]
0 /
HC2O / H S H2C2O4
4 [12]
(MnO2 )n / H2C2O4 S (MnO2 )n 0 H2C2O4 [13]
slow
(MnO2 )n 0 H2C2O4
(MnO2 )n01 0 MnO / 2CO2 / H2O [14]
(MnO2 )n01 0 MnO / 2HAc r
(MnO2 )n01 / Mn 2/ / 2Ac 0 / H2O. [15]
Here (MnO2 )n stands for colloidal manganese dioxide. After
adsorption of oxalic acid on the surface of the colloidal particles
(Eq. [13]), the redox reaction takes place in the rate-determin-
ing step (Eq. [14]). Finally, in the last step (Eq. [15]) the
acid component of the buffer mixture dissolves the manga-
nese(II) oxide initially formed on the colloid surface.
According to the mechanism proposed, the noncatalytic
reaction pathway would be of first order in both colloidal
manganese dioxide and adsorbed oxalic acid and, due to the
saturation of the colloid surface at high reductant concentra-
tions, the k1 vs [Na2C2O4 ] plots are expected to show a
downward concavity (see Fig. 6). The assumption that mo-
lecular oxalic acid is the active reducing agent for Mn(IV)
is in agreement with the results reported by Pimienta et al.
FIG. 7. Dependence of rate constants k1 (open circles, slope 01.46 {
0.02) and k2 (filled circles, slope 00.67 { 0.03) on the pH for the reduction
of colloidal MnO2 (1.00 1 10 04 mol dm03 ) by Na2C2O4 (2.00 1 10 03 mol
dm03 ), in the presence of HAc–NaAc buffer ([HAc] / [NaAc] Å 5.04
1 10 02 mol dm03 ) and Na4P2O7 (4.96 1 10 03 mol dm03 ), at ionic strength
0.528 mol dm03 (NaClO4 ) and 25.07C.
AP: Colloid
294 PEREZ-BENITO, ARIAS, AND AMAT

TABLE 2
Values of the Rate Constants at Various Concentrations of Sodium Perchloratea

[NaClO4] k1b k2b k1c k2c

(mol dm03) pH (1004 s01) (dm3 mol01 s01) (1004 s01) (dm3 mol01 s01)

0.00 4.67 3.66 { 0.21 33.8 { 0.2 3.66 { 0.21 33.8 { 0.2
0.07 4.65 4.86 { 0.02 31.5 { 0.2 4.54 { 0.02 30.6 { 0.2
0.15 4.62 5.19 { 0.05 30.3 { 0.1 4.46 { 0.04 28.6 { 0.1
0.22 4.61 4.99 { 0.10 29.5 { 0.1 4.15 { 0.08 27.4 { 0.1
0.29 4.60 4.91 { 0.05 28.5 { 0.1 3.99 { 0.04 26.2 { 0.1
0.37 4.60 4.60 { 0.12 27.9 { 0.1 3.64 { 0.09 25.4 { 0.1
0.44 4.58 4.82 { 0.15 26.8 { 0.5 3.66 { 0.11 24.0 { 0.5
0.51 4.58 4.38 { 0.17 26.1 { 0.1 3.23 { 0.13 23.2 { 0.1
0.58 4.57 4.23 { 0.01 25.7 { 0.3 3.07 { 0.01 22.7 { 0.3
0.66 4.56 3.97 { 0.01 25.0 { 0.1 2.79 { 0.01 21.8 { 0.1

a
[MnO2]0 Å 1.00 1 1004 mol dm03, [Na2C2O4] Å 1.00 1 1003 mol dm03, [HAc] Å 0.105 mol dm03, [NaAc] Å 0.100 mol dm03, [Na4P2O7] Å 4.96
1 1003 mol dm03, 25.07C.
b
Experimental values.
c
Values corrected at constant pH (4.67).

(23), and it can explain the strong acid catalysis found for
rate constant k1 (Fig. 7). Moreover, the proposal of colloidal
MnO2 being reduced first to MnO instead of directly to Mn 2/
may explain the fact that in neutral or alkaline solutions most
reductants can provoke only a partial, superficial reduction of
colloidal manganese dioxide (12, 39, 40), since, once cov-
ered by an insoluble, irreducible MnO monolayer, the colloid
surface becomes passivated.
It should be noticed that Pimienta et al. (23) have pro-
posed that the reduction of Mn(IV) by oxalic acid yields
Mn(III) in a first step, instead of Mn(II). However, our
results indicate that at the beginning of the reaction Mn(II)
was predominant over Mn(III), thus suggesting that
Mn(IV) is directly reduced to Mn(II), and that Mn(III) is
formed by reaction between Mn(IV) and Mn(II) once the
latter becomes concentrated enough (see Fig. 2).
Autocatalytic Reaction Pathway
For the reaction pathway associated to rate constant k2 ,
we propose the following mechanism:

FIG. 8. Dependence of rate constants k1 (up) and k2 (down) on the

initial concentration of MnSO4 for the reduction of colloidal MnO2 (1.00
1 10 04 mol dm03 ) by Na2C2O4 , in the presence of HAc (0.525 mol dm03 ) –
NaAc (0.500 mol dm03 ) buffer, Na4P2O7 (4.96 1 10 03 mol dm03 ) and
gum arabic (0.387 g dm03 ), at pH 4.61 { 0.01 and 25.07C. [Na2C2O4 ] Å
1.00 (open circles), 2.00 (filled circles), 3.00 (open triangles), 4.00 (filled
triangles) and 5.00 (squares) 1 10 03 mol dm03 .
FIG. 9. Dependence of parameters a (open circles, in 10 05 s 01 ), b
(triangles, in dm3 mol 01 s 01 ) and c (filled circles, in 10 4 dm6 mol 02 s 01 )
on the concentration of sodium oxalate. The experimental conditions are
given in the legend of Fig. 8.

/ m4420$3910 12-22-95 14:36:44 coida AP: Colloid

 THE MnO2 –H2C2O4 REACTION
FIG. 10. Arrhenius plots for rate constants k1 (open circles) and k2
(filled circles) in the reduction of colloidal MnO2 (1.00 1 10 04 mol dm03 )
by Na2C2O4 (2.00 1 10 03 mol dm03 ), in the presence of HAc (0.525 mol
dm03 ) –NaAc (0.500 mol dm03 ) buffer and Na4P2O7 (4.96 1 10 03 mol
dm03 ), at pH 4.61 in the temperature range 14.7–34.87C.
Mn 2/ / C2O 20
4 S MnC2O4
(MnO2 )n 0 H2C2O4 / MnC2O4 S
H2C2O4 0 (MnO2 )n 0 MnC2O4
slow
H2C2O4 0 (MnO2 )n 0 MnC2O4
(MnO2 )n01 / 2[Mn(C2O4 )] / / 2OH 0
[Mn(C2O4 )] / r Mn 2/ / CO2 / CO 2r0
2CO 2r0 r C2O 20
4 .
Here adsorption of manganese(II) oxalate on the surface of
colloidal manganese dioxide (with oxalic acid previously
adsorbed, Eq. [17]) is followed by the reaction between
Mn(IV) and Mn(II) in the rate-determining step of this
pathway (Eq. [18]) to yield a mono(oxalato)manga-
nese(III) complex, whose unimolecular decomposition (Eq.
[19]) results in the formation of the reaction products and
a free radical. Finally, recombination of two of those radicals
(Eq. [20]) leads to partial recuperation of oxalate ion.
Our results seem to indicate that Mn(II) is the active
autocatalyst (at least in the predominant autocatalytic reac-
tion pathway), since Fig. 2 allows to infer the existence of
a reaction between Mn(IV) and Mn(II) to yield Mn(III).
Hence, the Mn(II) formed as reaction product contributes
to accelerate the destruction of colloidal manganese dioxide.
This was confirmed by the experiments performed in the
presence of manganese(II) sulfate, since addition of Mn 2/
to the system resulted in an acceleration of the reaction (see
Fig. 8).
More difficult to explain is the quadratic term in the equa-
/ m4420$3910 12-22-95 14:36:44
295
tion describing the dependence of rate constant k1 on the
initial concentration of manganese(II) ion (Eq. [10]). This
might indicate that the existence of Mn 2/ in the electrical
double layer surrounding the MnO2 colloidal particles favors
the rate-determining step of the autocatalytic reaction path-
way (Eq. [18]), probably by reacting with the two hydroxyl
ions formed in that step to yield Mn(OH)2 (or hydrated
MnO), thus preventing a decrease of the concentration of
hydrogen-ion (a catalyst for the reaction, as shown by Fig.
7) in the surroundings of the colloidal particles. However,
given the difficulty of obtaining precise values of the rate
constants (especially of k1 ), the possibility that the deviation
of the k1 vs [Mn 2/ ]0 plots (see Fig. 8, up) with respect to
the linear relationship was due to the existence of systematic
errors in the determination of k1 should not be excluded.
The possible existence of a reaction of the type MnO2 –
MnO in competition with the dissolution of MnO (Eq. [15])
should not be discarded either, although the known difficulty
for the reaction between the oxides of manganese(IV) and
manganese(II) to take place in the solid state (41) seems
[16] to indicate that the participation of the MnO2 –MnO reaction
in the autocatalytic pathway might be of minor importance.
In addition, according to the mechanism proposed, oxalate
has an active participation in the autocatalytic reaction path-
[17]
way (Eq. [18]). This is also in agreement with our experi-
mental results, since we have observed that rate constant k2
increases with rising oxalate concentration (see Fig. 6) in-
stead of being independent of that variable, as would happen
[18] if the autocatalytic pathway was due to a direct reaction
between Mn(IV) and Mn(II) to yield Mn(III) without the
[19] participation of oxalate. Moreover, Fig. 9 confirms that the
reductant plays an active role in the autocatalysis.
[20]
On the other hand, Fig. 7 indicates that, although both
reaction pathways present acid catalysis, the noncatalytic
reaction pathway is much more influenced by the pH than
the autocatalytic one. This might be a result of the participa-
tion of both oxalic acid and manganese(II) oxalate in the
rate-determining step of the latter pathway (Eq. [18]),
whereas in the one corresponding to the former (Eq. [14])
only oxalic acid is involved.
It should be noticed that the existence of [Mn(C2O4 )] /
(whose formation is proposed in Eq. [18]), as well as that
of other complexes of Mn(III), is well known (42–44),
TABLE 3
Arrhenius Parametersa
Rate constant ln Ab Ea (kJ mol01)
k1 22.2 { 0.4 74.7 { 0.9
k2 21.6 { 0.2 44.6 { 0.6
a
The experimental conditions are given in the legend of Fig. 10.
b
The Arrhenius preexponential factor (A) corresponding to rate constant
k1 is given in s01 and that corresponding to k2 in dm3 mol01 s01.
coida AP: Colloid
296 PEREZ-BENITO, ARIAS, AND AMAT
and that there are many proofs on the involvement of free
radicals (as the one whose participation is proposed in Eqs.
[19] and [20]) in the manganese–oxalate reacting systems
(45–49). Instead of recombination (Eq. [20]), other alter-
native for the destruction of those radicals would be
(MnO2 )n 0 H2C2O4 / CO 2r0 r
(MnO2 )n01 / [Mn(C2O4 )] / / CO2 / 2OH 0 . [21]
Notice that, if this alternative was correct, Eqs. [19] and [21]
would constitute a free-radical chain mechanism leading to
the disappearance of the colloid. In that case, accumulation
of Mn(III) in the system (see Fig. 2) would result in an
increase (through Eq. [19]) of the concentration of free
radicals available to reduce colloidal manganese dioxide, so
that Mn(III) would also participate [along with Mn(II)] in
the reaction as an autocatalyst. In fact, Jaky and Zrinyi (50)
have suggested that Mn(III) might be the active autocata-
lytic agent for the reduction of an Mn(IV) –phosphate solu-
ble complex by oxalic acid and other reductants.
Induction Period
Although it is difficult to ascribe the existence of a rate-
decreasing induction period at the beginning of the kinetic
runs (see Figs. 3 and 5) to a particular phenomenon, it might
be related with the time necessary for the adsorptions of
oxalic acid and manganese(II) oxalate on the colloid surface
to reach an equilibrium situation (Eqs. [13] and [17]). Other
possibility might be that the initial, sharp decrease of the
reaction rate was due to the covering of the colloidal particles
with an MnO monolayer (Eq. [14]) that would hinder the
access of the reductant to their surface. Moreover, if Eq.
[21] was correct, the induction period might be interpreted
as the time necessary to elapse in order to reach an Mn(III)
concentration high enough in the system (see Fig. 2).
Stabilization of Mn(III)
We have seen (Fig. 5, lower curve) that in the absence
of pyrophosphate the acceleration of the reaction disappears
very soon and a near-first-order situation is reached during
a certain period. This situation might be the result of a com-
pensation between the acceleration caused by the autocataly-
sis and the retardation caused by the dismutation of Mn(III),
2[Mn(C2O4 )] / / 2H2O r Mn 2/ / MnO2 / 2H2C2O4 ,
[22]
since in that process the rate-monitoring species (MnO2 ) is
partially recuperated. Given that pyrophosphate is known to
be an excellent stabilizing agent for Mn(III) (51), when
Na4P2O7 was added to the solution an acceleration of the
reaction was observed (see Figs. 3 and 4), and the autocatal-
/ m4420$3910 12-22-95 14:36:44 coida
ysis did not disappear (compare the two curves shown in
Fig. 5).
Comparison with Related Reactions
In a previous work (10), we have reported a kinetic study
of the reaction between colloidal manganese dioxide (pre-
pared under identical conditions than the one used in the
present work) and formic acid in perchloric acid aqueous
media. The main differences found between the MnO2 –
HCO2H and MnO2 –H2C2O4 reactions are that in the case of
formic acid the reaction was much slower under similar
conditions, did not show any appreciable autocatalysis and
there was no rate-decreasing induction period. The apparent
inexistence of autocatalysis in the MnO2 –HCO2H reaction
can be taken as additional evidence that oxalate ions are
necessary to facilitate the reaction between Mn(IV) and
Mn(II) (Eq. [18]). However, it should be also noticed that
the results shown in Fig. 7 seem to predict that if the acidity
of the solution is high enough (as in the study corresponding
to formic acid) the contribution of the autocatalytic reaction
pathway would be negligible with respect to that of the
noncatalytic one. The inexistence of a rate-decreasing induc-
tion period in the MnO2 –HCO2H reaction could be a conse-
quence of the fact that the MnO initially formed on the
colloid surface was rapidly dissolved due to the high acidity
of the medium, so that the colloid was not protected by an
irreducible MnO monolayer.
However, both the MnO2 –HCO2H and MnO2 –H2C2O4
reactions exhibit a strong acid catalysis, and this situation
contrasts with that found for the reduction of manganese
dioxide by malonic acid (52), for which no dependence on
[H / ] was observed.
Jaky and Zrinyi (50) have reported the existence of a
soluble Mn(IV) species in phosphoric acid aqueous media
whose reactivity toward HCO2H and H2C2O4 is very similar
to that of colloidal manganese dioxide, since only in the
second case autocatalysis was found. It is interesting to no-
tice that the UV–vis spectrum of that Mn(IV) –phosphate
species (apparently noncolloidal, according to ultracentrifu-
gal and electron microscopic studies) was very similar to
that of colloidal MnO2 (12), and that phosphate ions are
known to stabilize the MnO2 colloidal particles in aqueous
solution by fixation on their surface (6, 12).
Finally, mention should be made of the fact that there
might be a close relationship between the autocatalysis found
in the reactions of oxalic acid with permanganate ion (53)
and colloidal manganese dioxide. To this respect, a parallel-
ism can be established between the reactivities of the two
oxidants, since the MnO 40 –H2C2O4 and MnO2 –H2C2O4 reac-
tions are both markedly autocatalytic, whereas their related
the MnO 40 –HCO2H and MnO2 –HCO2H reactions present,
respectively, a slight autocatalysis (32) and no autocatalysis
at all (10). This might suggest that the autocatalysis found
AP: Colloid
 THE MnO2 –H2C2O4 REACTION
in the first couple of reactions is caused predominantly by the
reduction of either permanganate ion or colloidal manganese
dioxide by MnC2O4 (see Eq. [18]), which would confirm
the explanation proposed by Adler and Noyes (54) for the
autocatalysis observed in the permanganate–oxalate reac-
tion.
ACKNOWLEDGMENT
The authors thank Dr. J. Estelrich for the measurement of the zeta poten-
tial of the colloidal form of manganese dioxide used in this work.
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AP: Colloid