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Pimienta 1994
Pimienta 1994
1994,98, 13294-13299
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
450 91 9
2 0.025 0.27 220 452 69 31
400
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
I to the half-life of permanganate during the reaction. Note the shift of
400 450 500 the isosbestic point (Aisos) as a function of initial concentrations.
wavelength (nm)
-
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
"350 400 450 500 [H2C204]0 and [H2S04]0 are both low, a = .32; the overall
wavelength (nm) spectrum of the intermediates is effectively constituted by 68%
Figure 2. (A) Overall spectra of intermediates obtained after subtrac- of compound x. Its exact structure could not be readily
tion of the spectrum of permanganate using formula 3 (see Experimental determined since (i) it could not be isolated and (ii) its spectrum
Section). The indices 1, 2,3, and 4 refer to the initial concentrations did not resemble that of any known species of manganese in
listed in Table 1. Since these spectra changed over time, they were any oxidation state between VI1 and II. A partial identification
chosen to correspond to around 40% disappearance of the initial
permanganate. The spectra shown by solid lines were reconstructed was made on searching the literature and by successive
numerically from relationship 2; they fit perfectly the experimental elimination.
spectrum. The values of a are given in Table 1, and the calculated (2) Identification of the Second Intermediate, x. Mn(V1)
spectrum of x is plotted in Figure 2B. (B) Spectrum of I& from an and Mn(V) were ruled out, as they are highly unstable in acid
authentic sample. The spectrum of x = Mn(1V) was derived by medium." Furthermore, their spectra display peaks at 600 and
numerical analysis of the four intermediate spectra, 1-4, using formula 660 nm, respectively.12 With respect to Mn(III), various
4.
complexes with oxalate ions have been described,13J4 such as
mono(oxalato)manganese(III) ([Mn(C204)]+, referred to here as
corresponds to the appearance and disappearance of one or more
IIIl) and tris(oxalato)manganate(III) ([Mn(C204)3I3-, referred
reaction intermediates.
to here as III3). The intermediate IIIl is unstable and is not
An isosbestic point is observed at 456 nm (Figure lB(c)),
readily observed experimentally. Species 1113, however, is
but only at the start of the reaction. At this wavelength, we
readily isolated, but only at much higher concentrations of
assumed that €Int m E ~ Q - . We have discussed the validity of
oxalate ions than those employed in the present experiments. It
this assumption in an earlier paper,1° and it appears to be well
exhibits a peak at 510 nm.
justified in this case. During this phase, the conservation of
We thus concluded that the second intermediate was a Mn-
matter is approximated by the overall equation (1):
(IV)species. This oxidation state is commonly involved in the
oxidation of organic compounds by permanganate. The spectra
[Mn04-], - [Mn04-] = [Int] (1) of such species depend on the nature of the reducing agent and
the experimental conditions (acidity of the solution, presence
However, for [H~C204]0ranging from 1.25 x to 0.2 or absence of stabilizing ions such as phosphate). None of the
mol-L-', there is a shift in isosbestic point between 456 and spectra are identical, which complicates the attribution to a
450 nm, indicating that the intermediate must comprise at least chemically defined species.15-17 Nevertheless, the spectra
two chemically distinct species in variable proportions. display the same general shape, with a decreasing absorption
The overall spectrum of the intermediates (gint) is obtained between 300 and 600 nm with a shoulder whose position ranges
after subtraction of the permanganate spectrum (Figure 2). from 375 to 475 nm. They are attributed to either a soluble
Assuming that there are only two intermediates, the value of species of Mn(N), which could be HZMn03," or colloidal
the molar extinction coefficient of Int (€int) is governed by a Mn02.18 In our experiments, it was attributed to a soluble
relationship of the following type: species of Mn(IV), as the solution was completely clear and
because Rayleigh scattering was not verified.
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 time(s)
to study the reactivity of these intermediates. Although LTI2 Figure 5. First-order fitting of two auxiliary reactions. RIII: experi-
could be obtained directly, the Mn(IV) species could not be ment h, l o b s = 456 nm; Abs scale 0-1.2; time scale 0 - 1 m s; kobs =
identified experimentally, and its reactivity was thus modeled 4.6 x s-'. RIV: experiment I , &bs = 400 nm; Abs scale 0-0.6;
using MnOz obtained by the Guyard reaction. MnOz had a time scale 0-50 s; kobs = 1.3 x lo-' s-l.
reactivity toward the oxalic acidsulfuric acid mixtures compa-
rable to that of the Mn(1V) intermediate. (HP 8451), the temperature was maintained at 25 "C, and the
Various mixtures of the two diacids were prepared whose solution was stirred continuously.
initial concentrations were chosen to produce a constant (5) Data Processing. (a) Spectra of Intermediates: Subtrac-
concentration of the reducing species (molecular HzC204 or tion of Permanganate Spectrum. The overall absorbance of the
C Z O ~ ~at- )equilibrium. The proportions of the two diacids were intermediates was calculated from relationship 3:
selected from appropriate charts. The kinetic study using
auxiliary reactions showed that, from the kinetic point of view, Ab$(int), = Absp - Abs"-,(Abs:60/Absz) (3)
the reducer of IIIz was the oxalate ion, whereas that of Mn(IV)
was molecular oxalic acid. This difference in reactivity between Over the duration of the isosbestic point, the equation of
III2 and Mn(IV) can account for the variations in relative conservation of mass, [Int] = [Mn04-]0 - [Mn04-], gives the
proportions of these two intermediates in the permanganate/ total concentration of the intermediates. Dividing Abs(int) by
oxalic acid reaction. The role of sulfuric acid is restricted to [Int] gives the overall spectrum of the intermediates €int in
the displacement of the dissociation equilibria of oxalic acid. mol-'*L-cm-' (units of molar extinction coefficient).
The concentrations of oxalic and sulfuric acids that we (b) Calculation of Spectrum of Mn(N). The permanganate
employed in the auxiliary reactions were within the domain of spectrum was subtracted for n (=4) different experiments
concentrations in which the dynamic features of the overall observed at m different wavelengths. This gives rise to nm
permanganate/oxalic acidsulfuric acid reaction are observed +
equations of type 2, in which there are n m unknown variables
(acceleration by sulfuric acid, inhibition by oxalic acid, bista- (n values of a and m values of E ~ W ) )This
. set of equations
bility in a CSTR). The use of charts rather than a large excess can be resolved by an iterative procedure minimizing term 4:
of reagent ensures that the processes demonstrated were those
that actually take place in the complete reaction KMnOd n m
H2CzO4/HzS0 4 .
V. Experimental Section
(c) Calculations Assuming First-Order Kinetics. The absor-
(1) Preparation of Solutions. All the solutions were bance over time of a first-order reaction is given by the following
prepared from commercial compounds: KMnO4 (M = 158.03); equation:
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
Abs = (Abs,, - Abs,)e-k"bs' + Abs, (5)
set of experiments were carried out in no more than 2 days.
The values of the parameters kobs and Abs, were obtained
The solution of permanganate was acidified, [H2S04] = 0.02
by minimization of the residual error (RE) using a nonlinear
mol*L-', to limit formation of Mn02.
optimization program of the Powell type?
(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 where n is the number of experimental points; Abs,dci is given
was prepared by the Guyard method: by relationship 5 . In our case, Abs, was always 0. Examples
of first-order fittings of auxiliary reactions RIII and RIV using
2H20 4- 2Mn0,- + 3Mn2+ = 5Mn0, + 4H+ eq 5 are shown in Figure 5 .
(d) Calculations of Equilibrium Concentrations. Values
The Mn02 prepared was used immediately. [MnOzlo = 7.5 shown in Table 2 were obtained by numerical integration using
x m0l-L-I; the concentrations [HzCz041o and [H2S0410 the Runge-Kutta procedure. Each equilibrium constant was
were obtained from Figure 3B. split into two individual elementary rate processes.
(4) Recording Kinetics. The reagents were mixed directly To obtain the corrected value [Cz042-],, of oxalate ions in
in quartz cuvettes (2 mL with 1 cm optical path length). The auxiliary reaction RIII, the dissociation equilibria of the two
measurements were made in a diode array spectrophotometer diacids and the dissociation equilibria of Mn(II1) (K(A)= 2.5 x
Reactivity of the Mn(II1) and Mn(1V) Intermediates J. Phys. Chem., Vol. 98, No. SO, 1994 13299
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