13294 J. Phys. Chem.

1994,98, 13294-13299

Reactivity of the Mn(II1) and Mn(IV) Intermediates in the Permanganate/Oxalic Acid/

Sulfuric Acid Reaction: Kinetic Determination of the Reducing Species

V. Pimienta, D. Lavabre, G. Levy, and J. C. Micheau*

Luboratoire des IMRCP, URA au CNRS 470, Universitg Paul Sabatier, F-31062 Toulouse, France
Received: July I S , 1994; In Final Form: September 29, 1994@

UV/visible spectrophotometric analysis of the permanganate/oxalic acid reaction in sulfuric acid demonstrated
the presence of two intermediates: bis(oxalato)manganate(III) and a soluble Mn(IV) compound. Their relative
proportions were found to depend on the initial concentrations [H2C204]0 and [H2S04]0. The proportion of
bis(oxalato)manganate(III) was highest for a rise in [H2C204]0, while those of the soluble Mn(IV) compound
increased for a simultaneous fall in [H2C204]0 and [H2S04]0. A kinetic study together with a quantitative
study of the effects of displacement of the equilibria of dissociation of the two diacids showed that, from a
kinetic point of view, oxalate ion was the reducer of Mn(II1) and molecular oxalic acid that of Mn(1V).

I. Introduction
The reaction between permanganate and oxalic acid in sulfuric
acid medium (KMn04/H2C204/H2SO4) is regarded as the
archetype of autocatalytic reactions. It has features which have
intrigued researchers for more than a century.’ For example,
an increase in initial concentration of sulfuric acid speeds up
the reaction, whereas an increase in the concentration of oxalic
acid slows it down2 More recently, several authors have shown
that this reaction is bistable in a CSTR at low oxalic acid
con~entration.~~~ These findings and the development of new
oscillating reactions based on the chemistry of manganese have
rekindled interest in this rea~tion.~
It is characterized by two principal processes:
Mn(VII) - Int
Int - Mn(II)
where “Int” represents one (or several) reaction intermediate-
(SI.
Among all the possible intermediates, bis(oxalat0)manganate-
(111), [Mn(C204)2]- (referred to here as is the most widely
recognized.6~~However, using UV/visible spectro~copy,~~~ we UJ
Q
D
demonstrated the presence of a second intermediate containing 0.5

manganese in oxidation state IV. The intermediate “Int” is in

fact a mixture of various proportions of III2 and Mn(1V).
The present study was designed to determine the nature of
the entities involved in the reduction of Mn(II1) to Mn(I1) and
Mn(IV) to Mn(II1). Consideration of the redox potentials
indicates that the electrons are provided by oxalic acid, although
it is not obvious whether they stem from the nondissociated
molecule H2C2O4, the hydrogenooxalate ion HCzO4-, or the
oxalate ion C2042-. We thus made a kinetic analysis of the
auxiliary reactions {Mn(III)/H2C204/H2S04} (referred to here
as RIII) and {Mn(IV)/H2C20&32S04} (referred to here as RIV)
using different initial concentrations [H2C204]0 and [H2S04]0
in order to take into account quantitatively the dissociation
equilibria of these two diacids in aqueous solution.
n. Characterization of Intermediates
(1) UVNisible Spectroscopic Analysis of Intermediates.
The changes in absorbance between 300 and 700 nm were
recorded continuously in a diode array spectrophotometer.
@ Abstract published in Advance ACS Abstracts, November 1, 1994.
0022-3654/94/2098- 13294$04.50/0
0.0 I 40 80
time (s)
Figure 1. (A) Three-dimensional Whisible spectrum recorded during
reaction 3 (stoichiometric ratio, see Table 1). (B) Extraction of single-
wavelength kinetics from the three-dimensional spectrum: (a) 320 nm;
(b) 560 nm; (c) 456 nm (isosbestic point).
Figure 1A shows two spectral zones:
(a) Between 490 and 650 nm, the characteristic peak complex
of MnO4- ions collapses without deformation, as only perman-
ganate absorbs significantly in this region. The corresponding
wavelengths are said to be pure, as they can be used to follow
the change in concentration of permanganate at any instant. The
kinetics at 560 nm, represented in Figure lB(b), shows the
autocatalytic nature of the disappearance of MnO4- ions.
(b) Between 300 and 400 nm, a transient absorbance is
observed, which passes through a maximum and then falls until
the reaction mixture is completely bleached (Figure lB(a)). This
0 1994 American Chemical Society
Reactivity of the Mn(II1) and Mn(IV) Intermediates
1200
A Bis(oxalato)manganate(III) (I&) and x as a Function of
800
::
W 1
400
I to the half-life of permanganate during the reaction. Note the shift of
400 450 500
wavelength (nm)
la, I relative initial concentrations [H2Cz04]0 and [H2S04]0 (Table
"350 400 450 500
wavelength (nm)
Figure 2. (A) Overall spectra of intermediates obtained after subtrac-
tion of the spectrum of permanganate using formula 3 (see Experimental
Section). The indices 1, 2,3, and 4 refer to the initial concentrations
listed in Table 1. Since these spectra changed over time, they were
chosen to correspond to around 40% disappearance of the initial
permanganate. The spectra shown by solid lines were reconstructed
numerically from relationship 2; they fit perfectly the experimental
spectrum. The values of a are given in Table 1, and the calculated
spectrum of x is plotted in Figure 2B. (B) Spectrum of I& from an
authentic sample. The spectrum of x = Mn(1V) was derived by
numerical analysis of the four intermediate spectra, 1-4, using formula
4.
corresponds to the appearance and disappearance of one or more
reaction intermediates.
An isosbestic point is observed at 456 nm (Figure lB(c)),
but only at the start of the reaction. At this wavelength, we
assumed that €Int m E ~ Q - . We have discussed the validity of
this assumption in an earlier paper,1° and it appears to be well
justified in this case. During this phase, the conservation of
matter is approximated by the overall equation (1):
[Mn04-], - [Mn04-] = [Int] (1)
However, for [H~C204]0ranging from 1.25 x to 0.2
mol-L-', there is a shift in isosbestic point between 456 and
450 nm, indicating that the intermediate must comprise at least
two chemically distinct species in variable proportions.
The overall spectrum of the intermediates (gint) is obtained
after subtraction of the permanganate spectrum (Figure 2).
Assuming that there are only two intermediates, the value of
the molar extinction coefficient of Int (€int) is governed by a
relationship of the following type:
where € 1 is~known,
~ a represents the relative proportion of IIIz,
and (1 - a) is that of the second intermediate, another
compound of Mn (referred to here as x); the spectrum of x and
a were calculated numerically. The value of a depends on the
J. Phys. Chem., Vol. 98,No. SO, 1994 13295
TABLE 1: Relative Proportion of
[ H z C ~ Oand
~ ] ~[HzSO& (in m0l.L-l) in the Reaction
Intermediate Observed during the PermanganatdOxalic
Acid Sulfuric Acid Reactiod
no. [HzCz041o [H2S0410 tin %X
0.2 0.27 240
As,
450 91 9
2 0.025 0.27 220 452 69 31
3 0.0013 0.27 80 456 40 60
4 0.0013 0.09 180 456 32 68
[Mn04-]0 = 5 x mol.L-'. The values of tln (in s) correspond
the isosbestic point (Aisos) as a function of initial concentrations.
1).
Examination of spectrum 1 in Figure 2A, for which [HzC204]0
= 0.2 mo1.L-' and [H2S04]0= 0.27 mol-L-' (a = 0.91), shows
that, in this case, the intermediate consists almost exclusively
-
of III2. The first step of the reaction can thus be schematized
by W 111, as suggested by Adler et aL6 However, in their
study, in which the concentration of oxalate ion was high, they
only detected Mn(II1).
Spectra 2 and 3 were obtained for a lower [HzCZO~IO: a falls
progressively to a value of 0.40; for spectrum 4, where
[H2C204]0 and [H2S04]0 are both low, a = .32; the overall
spectrum of the intermediates is effectively constituted by 68%
of compound x. Its exact structure could not be readily
determined since (i) it could not be isolated and (ii) its spectrum
did not resemble that of any known species of manganese in
any oxidation state between VI1 and II. A partial identification
was made on searching the literature and by successive
elimination.
(2) Identification of the Second Intermediate, x. Mn(V1)
and Mn(V) were ruled out, as they are highly unstable in acid
medium." Furthermore, their spectra display peaks at 600 and
660 nm, respectively.12 With respect to Mn(III), various
complexes with oxalate ions have been described,13J4 such as
mono(oxalato)manganese(III) ([Mn(C204)]+, referred to here as
IIIl) and tris(oxalato)manganate(III) ([Mn(C204)3I3-, referred
to here as III3). The intermediate IIIl is unstable and is not
readily observed experimentally. Species 1113, however, is
readily isolated, but only at much higher concentrations of
oxalate ions than those employed in the present experiments. It
exhibits a peak at 510 nm.
We thus concluded that the second intermediate was a Mn-
(IV)species. This oxidation state is commonly involved in the
oxidation of organic compounds by permanganate. The spectra
of such species depend on the nature of the reducing agent and
the experimental conditions (acidity of the solution, presence
or absence of stabilizing ions such as phosphate). None of the
spectra are identical, which complicates the attribution to a
chemically defined species.15-17 Nevertheless, the spectra
display the same general shape, with a decreasing absorption
between 300 and 600 nm with a shoulder whose position ranges
from 375 to 475 nm. They are attributed to either a soluble
species of Mn(N), which could be HZMn03," or colloidal
Mn02.18 In our experiments, it was attributed to a soluble
species of Mn(IV), as the solution was completely clear and
because Rayleigh scattering was not verified.
111. Determination of the Actual Reducing Agent of Each
Intermediate
The following experiments were designed to obtain a qualita-
tive analysis of these two intermediates' reactivity during the
complete permanganate/oxalic acidsulfuric acid reaction. The
13296 J. Phys. Chem., Vol. 98, No. 50, 1994
actual reducing agents were determined with the aid of two
auxiliary reactions.
(1) Reactivity of I&. With some modification and simpli-
fication, the mechanism described by Taube13may be employed
to interpret the reactivity of III2. This mechanism involves the
equilibria of complexation of Mn(1II) with oxalate ions (steps
A and B). In addition, these ions also donate electrons: the
two complexes of Mn(III) (In1 and III2) spontaneously decom-
pose to give Mn(I1) (steps C and D):
I11+ c,o,2- =111, (A)
111, + c,o,2- 111,
f (B)
111, - I1 + c0,'- + CO, (C)
111, - I1 + c,o,2- + c0,'- + CO, (D)
The effect of inhibition by oxalic acid, which is observed in
the complete reaction (see Table 1, experiments 1, 2, and 3)
can be explained by assuming that the rate of reduction of
complex III1 (step C) is higher than that of II12 (step D). As
[H2C204]0 increases, the concentration of oxalate ions rises, the
proportion of III2 increases by displacement of the equilibria A
and B, and so the proportion of IIIl falls with a reduced rate of
disappearance of Mn(II1).
To account for the accelerating effect of H2SO4 (see Table
1, experiments 3 and 4),the equilibria of dissociation of the
two diacids (steps E, F, G, and H) must be taken into
consideration.
H,C204 HC,04- -I-H+ pK,, = 1.3 (E)
HC204- f Cz0,2- + Hf pK, = 4.3 (F)
H2S04f HS04- + H+ pK, = -9 (GI
HS0,- f S
O
:
- + H+ pKa4 = 2 (H)
Calculation of the concentrations of each species at equilib-
rium shows that an increase in H2SO4 shifts the equilibria of
dissociation of HzCzO4 toward an increase in molecular
[H2C204] (nondissociated) and a decrease in [HC204-] and
[C2042-]. Complex IIIl is thus favored by the shift in equilibria
E and F, and the rate of disappearance of Mn(III) increases.
We show in section lII.3 that this interpretation is quantitatively
correct.
(2) Reactivity of Mn(n7). Inspection of Table 1 shows that
the proportion of Mn(1V) falls (i) as [H2Cz04]0 increases
(experiments 3, 2 , and 1) and (ii) as [H2S04]0 increases
(experiments 4 and 3). Between experiments 4 and 3, the effect
of acceleration by sulfuric acid leads to a faster formation of
the intermediate. Since under these conditions the relative
proportion of Mn(IV) falls, one can assume that sulfuric acid
speeds its disappearance.
The effect of an increase in [HzC204]0, at constant [HZSO~IO,
(experiments 3, 2, and 1) does not allow identification of the
actual reducer of Mn(IV), since under these conditions [H2C2041,
[HC204-1, and [C2042-] all increase along with [HZCZO~~O. On
the other hand, as we have seen above, the addition of sulfuric
acid at constant oxalic acid concentration (experiments 4 and
3) gives rise to a different effect: [HzCZO~] increases, while
[HC204-] and [ C ~ 0 4 ~ decrease.
-]
If as mentioned above one assumes that the acceleration of
the reduction of Mn(1V) by sulfuric acid is simply induced by
shifting the dissociation equilibria of oxalic acid, the reducer is
Pimienta et al.
t
I
0
-u
N
,I
0.0
O.C.3-X
0.oeXyII
OoecoO 2oe-04 400-04
kI2C2041,
Figure 3. (A) Chart used for RIII to determine the concentration at
equilibrium of oxalate ion [CZO~~-], for a mixture of [H&204]0 from
0 to 0.25 mo1.L-1 and [HzSO& from 0.022 to 0.18 mol-L-'. The
horizontal lines correspond to situations for which the oxalate concen-
tration at equilibrium [C204*-], is kept constant. (B) Chart used for
RIV for the determination of [HzC~04], for a mixture of [HzCZO~IO
from 1.4 x m0l.L-l to 6 x m0l.L-I and [&SO&, from 5.6
x to 0.09 mol.L-'. The horizontal lines correspond to situations
for which the concentration of molecular oxalic acid at equilibrium
[HzCzO& is kept constant. Each point labeled with a letter (a, b, ...)
gives the experimental conditions for each auxiliary reaction.
the species whose concentration increases as [HzC204]0 and [Hz-
SO410 both increase together. This is true only for molecular
oxalic acid, H2C204.
Kinetic study of the two auxiliary reactions RIII, {Mn(III)/
HzC20&2S04), and RIV,{ M ~ ( I V ) / H Z C Z O ~ / H for ~ S ~dif-
~},
ferent values of the initial concentrations [H2C20410 and
[H2S04]0provides a quantitativevalidation of these assumptions.
(3) Kinetic Analysis of the Two Auxiliary Reactions RIII
and RIV. If the two diacids are both present in solution, the
equilibria E-H are set up, and each of the two potential reducing
species attain concentrations [ C Z O ~ ~and - ] ~[H2C204le4,re-
spectively. We have calculated numerically these concentrations
from the values of PKAfor the different initial concentrations
[HzCzOalo and [H2S04lo.
Different pairs of initial concentrations [H~C204]0and [Hz-
SO410 can be determined by tracing horizontal lines on Figure
3A, all giving rise to the same concentration of oxalate ions at
equilibrium: [C2042-],. Figure 3A was thus employed to study
the degradation of III2 (auxiliary reaction RIII). Similarly,
Figure 3B was employed to obtain the conditions required to
maintain [H2C204], in the case of Mn(IV) (auxiliary reaction
FUV). It can be seen from Table 2 that the concentrations of
all the other species depend on [HzCz04]0and [HzS04]0except
one, namely, the species voluntarily kept constant.
Although IIIz is readily obtained from commercial com-
pounds, we were not able to synthetize any compounds of Mn-
(IV) with a UV/visible spectrum resembling the one observed
in our experiments. Nonetheless, MnOz derived from the
Reactivity of the Mn(II1) and Mn(IV) Intermediates J. Phys. Chem., Vol. 98, NO.50, I994 13297
+ [HZSO~IO~
TABLE 2: Calculated Equilibrium Concentrations of Six Mixtures of [H~CZO~IO
[HzCZO~IO [H~SO~IO [HzCz041q [HCz04-leq [ C Z O ~ ~ - I ~[HzS041eq
~ [HS04-1ul [so42-1w [Hf1e4
no. mol%-' mo1.L-l mo1.L-l mol%-' mol%-' mo1.L-l mol.L-' mo1.L-l mol%-'
d 2.4 x 2.2 x 1.0 x 1.4 x 1.7 x 6.9 x lo-" 1.7 x lo-' 5.2 x 4.1 x lo-'
e 6.3 x 4.5 x 3.7 x 2.6 x 1.7 x 3.0 x 3.9 x 6.3 x 7.8 x
f 1.9 x lo-' 9.0 x 1.4 x 10-' 5.2 x lo-* 1.7 x 1.2 x lo-" 8.3 x 7.1 x 1.5 x lo-'
k 4.5 x 2.2 x 1.5 x low4 2.9 x 5.0 x 4.6 x 1.6 x 6.7 x 2.9 x
1 3.1 x 4.5 x 1.5 x 1.6 x 1.5 x 1.9 x 3.6 x lo-' 8.6 x 5.4 x lo-'
m 2.4 x 9.0 x 1.5 x 8.5 x 4.2 x lo-* 8.0 x 8.0 x lo-' 1.0 x lo-* 1.0 x lo-'
Experiments d, e, and f (from Figure 3A) produce a constant concentration of oxalate ions, while experiments k,1, and m (from Figure 3B) are
for constant molecular oxalic acid. Note the changes in concentrations of all the other species. The validity of these values was verified by
experimental determination of pH. In all cases, the difference between experimental and calculated values did not exceed 0.03 pH units.
using MnO2 from the Guyard reaction as a source of Mn(1V).
6.00-03
I Complex 1112 is the direct product of the reduction, although
under our experimental conditions it did not accumulate due to
the very low concentration of oxalate ions. The MnO2 spectrum
decayed without deformation. The observed kinetics were first
order and could be also characterized by a value of Kobs. Figure
4B shows that we obtained almost identical values of Kobs
(within experimental error) for all the kinetics corresponding
to the same value of [HZC~O~], whatever the concentrations
of the other ions.
(4) Discussion. Our results throw light on the mechanism
of these reactions and may help decide among various hypoth-
eses proposed to date:
(i) In a recent study of the Mn(III)/H2C204 reaction in sulfuric
1.e-01r---- 1
acid medium, Adamsikova et al.*O observed either an accelera-
tion of the reduction with increase in [HS04-] or a slowing
down with increase in [Sod2-]. They proposed the intervention
of a further complex, [Mn(C204)(HSO4)], to account for the
accelerating effect of HS04-.
Our results indicate that the effect of displacement of the
dissociation equilibria of the two diacids should also be taken
into account. By calculating the concentrations of each species
at equilibrium, it can be seen that addition of HS04- induces a
fall in [C2042-], and hence an increase in the IIIl/III2 ratio,
which in turn increases kobs. It can also be seen that addition
of S042- leads to an increase in [C~04~-]; the IIIl/III2ratio drops
and so does kobs. Thus, from sole consideration of the
displacement of the dissociation equilibria, the two effects
observed can be interpreted qualitatively without involving a
further complex. However, we could not rule out involvement
of such a complex, as our experimental conditions were
somewhat different from those of Adamsikova et al. Under
our conditions, there is no effect of HS04-, as, for example, in
reactions d, e, and f the kobs are very close, whereas the
corresponding values of [HSOd-], ranged from 1.7 x to
8.3 x mol-L-', a more than 4-fold difference.
(ii) With respect to the reduction of Mn(IV), further light
can be thrown on the results of Bradley et a1.21 on the
mechanism of the Mn(IV)/HzC204/H2S04 reaction. These
authors proposed a prior adsorption of the reducer on the surface
of colloidal MnOz, although they did not determine its exact
nature (H2C204, HC204-, or C20&). Our results, along with
those of Bradley, indicate that the reduction of the intermediate
Mn(IV) in the permanganate/oxalic acid reaction in sulfuric acid
medium occurs in the following two reaction steps:

Mn(1V) + H2C204 f [Mn(IV).H2Cz04] (1)

[Mn(IV).H2Cz04] - Mn(II1) + C0,'- -I-C 0 2 f 2H' (J)

In the first step (I), Mn(IV) associates with molecular oxalic

acid. The higher the value of [H2C204], the more the equilib-
rium will be shifted in favor of association. During step J, this
13298 J. Phys. Chem., Vol. 98, No. 50, 1994
complex decomposes, and Mn(IV) is reduced to Mn(1II) with
molecular oxalic acid as electron donor.
Kinetic study of the two auxiliary reactions {Mn(III)/H2C204/
HzSO~}and {M~(IV)/HZCZO~/H~SO~} for different values of
the initial concentrations [ H Z C Z O ~and
] ~ [H2S04]0 provides a
quantitative validation of these assumptions.
IV. Conclusion
Multiwavelength analysis of the permanganate/oxalic acid
reaction in sulfuric acid detected the presence of two intermedi-
ates: bis(oxalato)manganate(III) (III2) and a soluble Mn(IV)
compound. Two separate auxiliary reactions were developed
to study the reactivity of these intermediates. Although LTI2
could be obtained directly, the Mn(IV) species could not be
identified experimentally, and its reactivity was thus modeled
using MnOz obtained by the Guyard reaction. MnOz had a
reactivity toward the oxalic acidsulfuric acid mixtures compa-
rable to that of the Mn(1V) intermediate.
Various mixtures of the two diacids were prepared whose
initial concentrations were chosen to produce a constant
concentration of the reducing species (molecular HzC204 or
C Z O ~ ~at- )equilibrium. The proportions of the two diacids were
selected from appropriate charts. The kinetic study using
auxiliary reactions showed that, from the kinetic point of view,
the reducer of IIIz was the oxalate ion, whereas that of Mn(IV)
was molecular oxalic acid. This difference in reactivity between
III2 and Mn(IV) can account for the variations in relative
proportions of these two intermediates in the permanganate/
oxalic acid reaction. The role of sulfuric acid is restricted to
the displacement of the dissociation equilibria of oxalic acid.
The concentrations of oxalic and sulfuric acids that we
employed in the auxiliary reactions were within the domain of
concentrations in which the dynamic features of the overall
permanganate/oxalic acidsulfuric acid reaction are observed
(acceleration by sulfuric acid, inhibition by oxalic acid, bista-
bility in a CSTR). The use of charts rather than a large excess
of reagent ensures that the processes demonstrated were those
that actually take place in the complete reaction KMnOd
H2CzO4/HzS0 4 .
V. Experimental Section
(1) Preparation of Solutions. All the solutions were
prepared from commercial compounds: KMnO4 (M = 158.03);
MnS04*H20(M = 169.02); Mn(CH3COO)3*2H20(M= 268.1);
HzSO4 ( M = 98.07); HzCz04-2H20 (M = 126.07). They were
dissolved in double-distilled water and used immediately. A
set of experiments were carried out in no more than 2 days.
The solution of permanganate was acidified, [H2S04] = 0.02
mol*L-', to limit formation of Mn02.
(2) Reduction of Mn(II1) (Auxiliary Reaction RIII).
Mn(CH3C00)3*2HzOwas dissolved in a mixture of oxalic and
sulfuric acids whose concentrations [H~CZO~IO and [H2S04lo
were obtained from Figure 3A. [Mn(CH3C00)3.2HzO]o = 6
x IOb3 mo1.L-l.
(3) Reduction of Mn(IV) (Auxiliary Reaction RIV). MnO2
was prepared by the Guyard method:
2H20 4- 2Mn0,- + 3Mn2+ = 5Mn0, + 4H+
The Mn02 prepared was used immediately. [MnOzlo = 7.5
x m0l-L-I; the concentrations [HzCz041o and [H2S0410
were obtained from Figure 3B.
(4) Recording Kinetics. The reagents were mixed directly
in quartz cuvettes (2 mL with 1 cm optical path length). The
measurements were made in a diode array spectrophotometer
Pimienta et al.
1 I
h
ln
0
-f
time(s)
Figure 5. First-order fitting of two auxiliary reactions. RIII: experi-
ment h, l o b s = 456 nm; Abs scale 0-1.2; time scale 0 - 1 m s; kobs =
4.6 x s-'. RIV: experiment I , &bs = 400 nm; Abs scale 0-0.6;
time scale 0-50 s; kobs = 1.3 x lo-' s-l.
(HP 8451), the temperature was maintained at 25 "C, and the
solution was stirred continuously.
(5) Data Processing. (a) Spectra of Intermediates: Subtrac-
tion of Permanganate Spectrum. The overall absorbance of the
intermediates was calculated from relationship 3:
Ab$(int), = Absp - Abs"-,(Abs:60/Absz) (3)
Over the duration of the isosbestic point, the equation of
conservation of mass, [Int] = [Mn04-]0 - [Mn04-], gives the
total concentration of the intermediates. Dividing Abs(int) by
[Int] gives the overall spectrum of the intermediates €int in
mol-'*L-cm-' (units of molar extinction coefficient).
(b) Calculation of Spectrum of Mn(N). The permanganate
spectrum was subtracted for n (=4) different experiments
observed at m different wavelengths. This gives rise to nm
+
equations of type 2, in which there are n m unknown variables
(n values of a and m values of E ~ W ) )This
. set of equations
can be resolved by an iterative procedure minimizing term 4:
n m
(c) Calculations Assuming First-Order Kinetics. The absor-
bance over time of a first-order reaction is given by the following
equation:
Abs = (Abs,, - Abs,)e-k"bs' + Abs, (5)
The values of the parameters kobs and Abs, were obtained
by minimization of the residual error (RE) using a nonlinear
optimization program of the Powell type?
where n is the number of experimental points; Abs,dci is given
by relationship 5 . In our case, Abs, was always 0. Examples
of first-order fittings of auxiliary reactions RIII and RIV using
eq 5 are shown in Figure 5 .
(d) Calculations of Equilibrium Concentrations. Values
shown in Table 2 were obtained by numerical integration using
the Runge-Kutta procedure. Each equilibrium constant was
split into two individual elementary rate processes.
To obtain the corrected value [Cz042-],, of oxalate ions in
auxiliary reaction RIII, the dissociation equilibria of the two
diacids and the dissociation equilibria of Mn(II1) (K(A)= 2.5 x
Reactivity of the Mn(II1) and Mn(1V) Intermediates
10' mol-'.L; K(B)= 4 x lo6 mo1-I-L) were computed together
with the dissociation equilibrium of acetic acid (pK, = 4.5).
References and Notes
(1) Harcourt, A. V.; Esson, W. Philos. Trans. R. SOC. London 1866,
156, 193.
(2) Malcolm, J. M.; Noyes, R. M. J. Am. Chem. SOC.1952,74,2769-
75.
(3) Reckley, J. S.; Showalter, K. J . Am. Chem. SOC.1981,103,7012-
3.
(4) de Kepper, P.; Ouyang, Q.;Dulos, E. In Nonequilibrium Dynamics
in Chemical Systems; Vidal, C., Pacault, A,, Eds.; Springer-Verlag: Berlin,
1984; pp 44-9.
( 5 ) (a) Nagy, A.; Treindl, L. Nature 1986 320,344-5. (b) de Kepper,
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