Colloids and Surfaces A: Physicochem. Eng.

Aspects 225 (2003) 145
/152

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Coagulation of colloidal manganese dioxide by divalent

cations
Joaquin F. Perez-Benito *
Departamento de Quimica Fisica, Facultad de Quimica, Universidad de Barcelona, Marti i Franques, 1, 08028 Barcelona, Spain

Received 6 February 2003; accepted 6 June 2003

Abstract

The coagulation of colloidal MnO2 by several divalent cations, both in the absence and presence of a complexing
ligand (L-histidine), has been studied. The efficiency as coagulating agents increases in the order Mg2 B/Ni2 B/
Zn2 B/Cu2 B/Co2 B/Mn2 . For a given cation, the coagulating efficiency increases with increasing pH and with
increasing temperature, and decreases with increasing concentration of L-histidine. Apparent values for the equilibrium
constants of complexation of divalent cations by L-histidine have been obtained. The apparent equilibrium constant of
formation of the complex increases in the order Mg2 B/Mn2 B/Zn2 B/Cu2 B/Ni2 . The value corresponding to
Co2 could not be determined because L-histidine acted as a catalyst for the reduction of colloidal MnO2 by that
cation.
# 2003 Elsevier B.V. All rights reserved.

Keywords: Colloid coagulation; Divalent cations; Equilibrium constants; L-Histidine; Manganese dioxide

1. Introduction [3] and Mn(II) [4]. Now, the results of a study on

The reduction of permanganate ion by thiosul-
fate ion in aqueous solution under stoichiometric
conditions leads to a manganese dioxide sol that
remains perfectly transparent for at least several
years [1]. This has allowed the use of that sol in
kinetic studies on the reactions of colloidal MnO2
with reductants such as formic acid [2], oxalic acid
* Fax: /34-93-402-1231.
E-mail address: j.perez@qf.ub.es (J.F. Perez-Benito).
0927-7757/03/$ - see front matter # 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0927-7757(03)00321-2
the coagulation of colloidal MnO2 by divalent
cations are presented. Given the high sensitivity of
the colloidal MnO2 particles to the presence in the
solution of free divalent cations, the coagulation of
colloidal MnO2 may be used to determine the
apparent equilibrium constants for the complexa-
tion of those cations by bulky ligands. The amino
acid L-histidine has been selected as an appropriate
ligand because of the biological importance of the
coordination of L-histidil residues with metal ions
for the formation of many enzymes [5
/8] and
other metalloproteins [9].
146 J.F. Perez-Benito / Colloids and Surfaces A: Physicochem. Eng. Aspects 225 (2003) 145
/152
2. Experimental
2.1. Materials and methods
The solvent was water previously purified by
deionization, distillation and circulation through a
Millipore system. Na2S2O3 ×/5H2O was purchased
from Panreac, L-histidine from Fluka, NaOH
from Carlo Erba, and all the other chemical
compounds (KMnO4, MgSO4 ×/7H2O, MnSO4 ×/
H2O, ZnSO4 ×/7H2O, CuSO4 ×/5H2O, NiSO4 ×/6H2O
and CoSO4 ×/7H2O) from Merck. The pH measure-
ments were done with a Metrohm 605 pH-Meter
using a glass
/calomel combined electrode. The
coagulation experiments were done in an Erlen-
meyer-type flask containing 50 ml of solution and
provided with an external compartment through
which thermostatized water was continuously
circulated. The solutions were stirred for 5 min
using a magnetic bar at a constant rate and, after
that, the absence or presence of precipitate was
checked by visual inspection against a light focus.
In total, 203 coagulation experiments were done,
and in each experiment 1
/11 trials with different
concentrations of a given divalent cation had to be
made to find the value of the minimum concentra-
tion required for the precipitation of MnO2 to take
place.
2.2. Preparation of the colloid
A dark-brown colloidal MnO2 (5.00/104 M)
solution was prepared by reducing KMnO4 with a
stoichiometric amount of Na2S2O3 according to
the reaction:
2
8MnO4 3S2 O3 2H

2
0 8MnO2 6SO4 H2 O
A 2-l volumetric flask was filled with water to
around 4/5 of its capacity. Twenty milliliters of
Na2S2O3 (1.88 /102 M) solution were added.
Then, 5 ml of KMnO4 (0.200 M) solution were
slowly added and the mixture was diluted till 2 l
with more water. Each addition was followed of
homogenization by gentle shaking. The colloidal
solution so prepared remained perfectly transpar-
ent, and 10-ml aliquots from it were taken when
required. Successive preparations of the colloid by
the same method led to a fairly good reproduci-
bility of the measurements. The characterization of
the colloidal particles prepared by the above
method has been previously reported [1,3].
3. Results
3.1. Coagulating efficiency of each divalent cation
The efficiency as coagulating agents increased in
the order Mg2 B/Ni2 B/Zn2 B/Cu2 B/
2 2
Co B/Mn . The minimum concentration of
each divalent cation required to provoke the
coagulation of colloidal MnO2 depended on the
cation ionic radius [10]. In the case of the transi-
tion-metal divalent cations the coagulating con-
centration decreased as the ionic radius increased,
but the experimental value corresponding to
Mg2 was much higher than that expected from
its ionic radius. A much better correlation was
found when the coagulating concentration was
plotted against the pH of the corresponding
solution, since the coagulating concentration of
each divalent cation increased as the pH increased
too (Fig. 1).
For a given divalent cation, the coagulating
concentration decreased as the pH of the solution
(1)
Fig. 1. Dependence of the concentration of MSO4 required for
the coagulation of colloidal MnO2 (1.00/10 4 M) on the pH
of the corresponding solution at 25.0 8C.
 J.F. Perez-Benito / Colloids and Surfaces A: Physicochem. Eng. Aspects 225 (2003) 145
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Fig. 2. Dependencies of the concentrations of NiSO4 (bottom,
[NaOH]/0
/5.00/10 4 M), MgSO4 (top, [NaOH]/0
/
1.75/10 4 M) and ZnSO4 (inset, [NaOH]/0
/2.00/10 4
M) required for the coagulation of colloidal MnO2 (1.00/
10 4 M) on the pH at 25.0 8C.
increased (Fig. 2). In that study, the pH was
changed by addition of NaOH. The introduction
of a new cation (Na) in low concentration had a
negligible effect on the coagulation of the colloid,
since divalent cations are roughly two orders of
magnitude more efficient as coagulating agents of
colloidal MnO2 than monovalent cations [1]. The
coagulating concentration for a given divalent
cation also decreased with increasing temperature
(Table 1).
Table 1
Dependence of the concentration of ZnSO4 required for the
coagulation of colloidal MnO2 on the temperature
Temperature (8C) [ZnSO4] (10 4 M)
15.0 2.319/0.12
20.0 2.199/0.12
25.0 1.869/0.05
30.0 1.809/0.05
35.0 1.819/0.01
[MnO2]/1.00/10 4 M, pH 5.069/0.05.
147
3.2. Determination of apparent equilibrium
constants
The complexation of a given divalent cation
(M2) by L-histidine can be represented by the
equation:
M2 l-histidine ? C (2)
where C is the corresponding complex, whose
apparent equilibrium constant of formation is:
[C]
Kc  2
(3)
[M ][L  histidine]
In the case of Cu2, the formation of a complex
with L-histidine can be easily observed due to the
appearance of a deep blue color when the latter is
added to the solution.
The total concentrations (free/complexed) of
metal ion and amino acid can be expressed as:
[M2 ]T [M2 ]] (4)
[l-histidine]T [l-histidine]] (5)
and, from Eqs. (3)
/(5) it can be deduced that:
Kc [M2 ]
[M2 ]T [M2 ] [Lhistidine]T
1  Kc [M2 ]
(6)
2
Thus, provided that the free cation (M ) is
much more efficient than the complex (C) for the
coagulation of colloidal MnO2, an addition of L-
histidine to the solution should result in an
increase of the minimum (total) concentration of
metal ion required for that coagulation. This has
been confirmed by the experiments (Figs. 3
/5).
Besides, provided that the concentration of diva-
lent cation really acting as a coagulating agent
(that of the free cation, [M2]) be constant, the
total coagulating concentration, [M2]T, should
increase linearly as the value of [L-histidine]T
increases. Actually, the experimental [M2]T vs.
[L-histidine]T plots showed a downward-concave
curvature, but the value of Kc for each metal ion
could be determined from the intercept and slope
of the tangent to the curve at [L-histidine]T /0.
The deviation of the curve from the expected linear
behavior was only slight in the case of Cu2 (Fig.
148 J.F. Perez-Benito / Colloids and Surfaces A: Physicochem. Eng. Aspects 225 (2003) 145
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Fig. 3. Dependence of the total concentration of MgSO4

required for the coagulation of colloidal MnO2 (1.00/10 4
M) on the total concentration of L-histidine at pH 5.44
/7.75
and 25.0 8C. The discontinuous line is the tangent to the curve
at [L-histidine]T /0.

5, top), intermediary for Zn2 (Fig. 4, top), and

more pronounced in the cases of Mg2 (Fig. 3),
Mn2 (Fig. 4, bottom) and Ni2 (Fig. 5, bottom).
Fig. 5. Dependence of the total concentration of NiSO4
(bottom, pH 5.02
/6.18) and CuSO4 (top, pH 4.51
/5.97)
required for the coagulation of colloidal MnO2 (1.00/10 4
M) on the total concentration of L-histidine at 25.0 8C. The
discontinuous lines are the tangents to the curves at [L-
histidine]T /0.

The values of Kc increased in the order Mg2 B/

Mn2 B/Zn2 B/Cu2 B/Ni2 (Table 2). In the
case of the Zn(II)
/histidine complex, the value of
Kc was determined at several temperatures, and a
slight increase of Kc with increasing temperature
was found (Table 3), the corresponding thermo-
dynamic parameters being DH8 /179/5 kJ mol1
and DS 8/1189/18 J K 1 mol1.
The values of Kc obtained are only apparent,
since by this method it is not possible to discrimi-
nate between the contributions of the acidic and

Table 2
Apparent equilibrium constants for the formation of complexes
of several divalent cations with L-histidine at 25.0 8C

Cation Ionic strength (10 3 M) pH Kc (103 M1)

Fig. 4. Dependence of the total concentration of MnSO4 Mg2 1.70 5.44 0.109/0.01
(bottom, pH 4.29
/7.57) and ZnSO4 (top, pH 5.13
/6.45) Mn2 0.54 4.29 0.419/0.13
required for the coagulation of colloidal MnO2 (1.00/10 4 Zn2 0.98 5.13 1.369/0.18
M) on the total concentration of L-histidine at 25.0 8C. The Cu2 0.85 4.51 2.079/0.20
discontinuous lines are the tangents to the curves at [L- Ni2 1.12 5.02 2.589/0.53
histidine]T /0.
 J.F. Perez-Benito / Colloids and Surfaces A: Physicochem. Eng. Aspects 225 (2003) 145
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Table 3
Dependence of the apparent equilibrium constant for the
complexation of Zn2 by L-histidine on the temperature
Temperature (8C) Kc (103 M 1)
15.0 0.899/0.05
20.0 1.019/0.10
25.0 1.369/0.18
30.0 1.449/0.20
35.0 1.349/0.18
Ionic strength/(1.049/0.09)/10 3 M, pH 5.069/0.05.
basic forms of the ligand (L-histidine). Thus, Kc
must be considered as the over-all (depending on
pH) equilibrium constant, whereas the true equili-
brium constants corresponding to the formation of
metal complexes with the acidic (Ka) and basic
(Kb) forms of the ligand would be independent of
pH.
The value of Kc for Co2 could not be
determined by the coagulation method, given
that, although in the absence of additives it could
not react with colloidal MnO2 (at pH 4.4
/4.6),
upon addition of L-histidine Co2 caused the
reduction of MnO2 to Mn2 (at pH 7.0
/7.3).
4. Discussion
4.1. Coagulation of the colloid
The finding that Mg2 was much less efficient
than the other five divalent cations studied (Ni2,
Zn2, Cu2, Co2 and Mn2) as a coagulating
agent for colloidal MnO2 is consistent with a
previous report according to which divalent ca-
tions from alkaline-earth metals (such as Mg2,
Ca2 and Ba2) are less efficient coagulating
agents for colloidal MnO2 than divalent cations
from transition-metals [1].
It can be inferred from the experimental results
that the ionic radius of the cation is one of the
factors contributing to its efficiency as a coagulat-
ing agent, but the fact that the correlation is not
very good suggests that other factors must also
affect its coagulating activity. The results can be
rationalized if we assume that the coagulating
efficiency of a given cation is the consequence of
149
the combination of two different types of interac-
tion with the colloidal particles: (i) electrostatic
forces depending on the physical properties of the
cation (charge and size), and (ii) covalent bondings
depending on the chemical properties of the cation
(availability of molecular orbitals capable of
accepting other electrons).
The electrostatic forces explain that divalent
cations are much more efficient as coagulating
agents for colloidal MnO2 than monovalent ca-
tions and that, for identical electrostatic charge,
the bigger (less solvated) cations are more efficient
than the smaller (more solvated) ones [1].
The formation of chemical bondings between
the metal ions and the colloidal particles might be
a consequence of the existence of the following
equilibrium:
(MnO2 )n H2 OM2
? (MnO2 )n MOH H (7)
where a water molecule covalently bonded to an
MnO2 molecule belonging to the surface of a
colloidal particle acts as an ion exchanger, so that
a divalent cation is incorporated into the colloidal
particle and a proton is released. As a conse-
quence, the negative electrostatic charges of the
MnO2 colloidal particles that keep them in aqu-
eous solution as a stable sol [1,3,11] are partially
neutralized, resulting in an increase of their rate of
coagulation. According to Eq. (7), the metal ions
more efficient in the formation of chemical bond-
ings with the MnO2 colloidal particles (such as
Mn2) would release more protons than those less
efficient in that formation (such as Mg2), thus
explaining the correlation found in Fig. 1. As a
general rule, the experimental results suggest that
divalent cations from transition-metals are more
efficient in the formation of chemical bondings
with colloidal MnO2 than those from alkaline-
earth metals.
The existence of the equilibrium depicted in Eq.
(7) is consistent with a report on the release of H
by colloidal MnO2 upon adsorption of Mn2 [12].
In that study, it was found that the affinity of
colloidal MnO2 for the adsorption of the transi-
tion-metal ions Mn2 and Zn2 was much higher
150 J.F. Perez-Benito / Colloids and Surfaces A: Physicochem. Eng. Aspects 225 (2003) 145
/152

than for the adsorption of the alkaline-earth metal
ions Mg2 and Ca2.
For a given cation, the efficiency as a coagulat-
ing agent increased as either the pH (see Fig. 2) or
the temperature (see Table 1) increased. The effect
of pH can be easily explained by Eq. (7), since an
addition of NaOH to the solution would shift the
equilibrium to the right, thus resulting in a
decrease of the minimum concentration of M2
required to provoke the coagulation of colloidal
MnO2. This is consistent with the report that the
adsorption efficiency of Mn2 on colloidal MnO2
increases with increasing pH [12]. For the adsorp-
tion of divalent cations on colloidal hydrated
Fe(III) oxide it was also found that the adsorption
efficiency increases with increasing pH [13,14]. The
effect of temperature can be explained by the
increase in the frequency of collisions between
colloidal particles caused by the increase of
temperature, so that a lower concentration of the
metal ion is again required for the coagulation.
the [M2]T vs. [L-histidine]T plot would decrease
accordingly. In fact, the finding that the curvature
of the [M2]T vs. [L-histidine]T plot was more
pronounced for Zn2 (Fig. 4, top) than for Cu2
(Fig. 5, top) agrees well with the report that the
stabilities of the four complexes of Zn2 with n /
1
/4 L-histidine ligands are very similar, whereas in
the case of Cu2 the binding of the first L-histidine
ligand makes much more difficult the binding of
additional ligands [15]. However, if Kc is deduced
from the tangent to the curve at [L-histidine]T /0,
it is assured that the value of the apparent
equilibrium constant so determined is referred to
the complex with only one L-histidine ligand.
The Kc values have been correlated with the
second ionization potentials (IP) of the metallic
elements (M) in the gas phase [16] and with the
standard reduction potentials (E 8) of the metal
ions (M2) in aqueous solution at 298 K [10]. The
value of Kc increased as both IP (Fig. 6, bottom)
and E 8 (Fig. 6, top) increased, but a much better

4.2. Complexation of metal ions by L-histidine

The finding that the [M2]T vs. [L-histidine]T

plots showed a downward-concave curvature (see
Figs. 3
/5) can be explained as a consequence of
the decrease of the coagulating concentration of
each metal ion as the pH increased (see Fig. 2).
Due to the basicity of L-histidine, addition of this
amino acid to the solution resulted in an increase
of the pH. Hence, as [L-histidine]T increased the
solution pH increased, and the concentration of
free cation, [M2], required for the coagulation of
colloidal MnO2 decreased, resulting in a decrease
of the slope of the [M2]T vs. [L-histidine]T plot
(see Eq. (6)).
Another factor that might also contribute to the
curvature of those plots is the possibility of
formation of complexes of M2 with more than
one L-histidine ligand. If, for simplicity’s sake, we
assume that the apparent equilibrium constants of
formation of complexes have an infinite value, the Fig. 6. Correlations between the IP (bottom) and the standard
slope expected for each [M2]T vs. [L-histidine]T reduction potential at 298 K (top) with the logarithm of the
apparent equilibrium constant of complexation of M2 by L-
plot would be 1/n , where n /1
/4 is the number of
2 histidine. IP corresponds to the process M(g) 0/M2 
(g) /2e . E 8
L-histidine ligands coordinated to a single M 2 
corresponds to the process M(aq)/2e 0/M(s). The experimen-
ion [15]. Thus, since the value of n would increase tal conditions corresponding to the Kc values are given in Table
as the value of [L-histidine]T increases, the slope of 2.
 J.F. Perez-Benito / Colloids and Surfaces A: Physicochem. Eng. Aspects 225 (2003) 145
/152
correlation was found with E 8 (correlation coeffi-
cient 0.95) than with IP (correlation coefficient
0.86). The existence of both correlations indicates
that the electron affinity of the metal ion M2 is a
key factor contributing to the value of Kc. The
electron-donating group of the ligand is likely the
nitrogen-containing imidazole ring of L-histidine
[17
/22]. This would explain the intensification of
the blue color of Cu2 (similar to that produced
by NH3 ligands) caused by the coordination with
L-histidine.
The order of stabilities of the five M2-histidine
complexes whose apparent equilibrium constants
have been determined (see Table 2) follows the
Irving
/Williams series [16,23
/25], the only excep-
tion being the Ni2 complex, whose Kc value
would be expected to be lower than that for Cu2
according to that series. This discrepancy might be
caused by the fact that the Kc value for Cu2 was
determined under experimental conditions (pH
4.51) slightly more acidic than those correspond-
ing to Ni2 (pH 5.02). Since protonation of the
imidazole ring of L-histidine might cause a de-
crease of its affinity toward the metal ion, this
might explain that Kc(Cu2) B/Kc(Ni2).
4.3. Reduction of the colloid
The finding that Co2 is capable of reducing
colloidal MnO2 under neutral conditions (pH 7.0
/
7.3), provided that L-histidine is present in the
medium, is remarkable given that it is well known
that MnO2 is a good oxidizing agent only in
strongly acidic solutions. In fact, very few chemical
species are able to cause the reduction of MnO2 in
neutral solutions. This clearly indicates that L-
histidine catalyzes the MnO2
/Co2 reaction by
complexing Co2, so that the electron-donating
effect of the nitrogen-containing imidazole ring
provokes a notable decrease of the Co(III)
/
histidine 0/Co(II)
/histidine reduction potential as
compared with that corresponding to the free ions
(Co3 0/Co2). In fact, the same effect is known
to be caused by the coordination of NH3 ligands to
Co3 and Co2 [10].
151
4.4. Biological implications
The results reported here might present some
relevance with respect to biological problems such
as the toxicity of some metal ions. The toxicity of
Ni(II) compounds is well described [26]. Given the
high affinity of Ni2 to coordinate with L-
histidine, at least some of its toxic effects might
be a consequence of the replacement of either
Cu2 or Zn2 (or other ionic oligoelements) by
Ni2 in some enzymes and metalloproteins, re-
sulting in a distorted structure and ill functioning
of the protein.
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