ELSEVIER

Colloids and Surfaces

A: Physicochemicaland EngineeringAspects 136 ( 1998) 151- 154

COLLOIDS
AND
SURFACES

Kinetic study of the decomposition of hydrogen peroxide

catalysed by Co(lI) acetylacetonate supported on a
silica-propylpiperazine matrix
Severino F. Oliveira a,,, Jose G.P. Espinola ~, Wolfango Eloy S. Lemus b,
Antonio G. de Souza b, Claudio Airoldi b
Departamento de Quhlica, CCEN, UniversMade Federal da Paraiba, Caixa Postal 5093, 58059-900, Jo6o Pessoa,
Paraiba, Brazil
b blstituto de Quhnica, Universidade Esta&tal de Camphuts, C~;.,caPostal 6154, 13083-970 Camphlas, Silo Pauio, Brazil

Received 14 March 1997: accepted 19 September 1997

Abstract
The catalytic decomposition of hydrogen peroxide by Co( II )acetylacetonate supported on a propylpiperazine-silica
matrix (Co(II)(acac)-PPS) was studied in aqueous media. The results showed that the reaction was first order in
H202. It was found that the reaction rate was pH dependent with a maximum at around pH = 8. Activation parameters
were determined in the temperature range 30-45 C. The low value obtained for the activation energy is in accordance
with the proposed free-radical mechanism. ~c) 1998 Elsevier Science B.V.
Keywords: Catalytic decomposition; Hydrogen peroxide; Propylpiperazine: Silica gel

I. Introduction
The decomposition of hydrogen peroxide in the
presence of homo- and heterogeneous catalysts has
been widely investigated not only with a view to
gain understanding of its basic nature but also due
to its relevance in biological processes [1-4].
However, in spite of these several studies, there is
still no definitive understanding of the true mechanisms involved. There are reports in the literature
of various other works concerning the effect of
transition metals on the decomposition of H202
under alkaline conditions [5-9]. It has been shown
that catalytic decomposition of H,,O2 by ferric ions
in solution can be first or second order with respect
* Corresponding author.
0927-7757,'98/$19.00 ~_31998ElsevierScience B.V. All rights reserved.
I'll S0927-7757( 97 I00318-X

to the peroxide concentration [5,6] whereas supported metal catalysts decompose H202 by first
order kinetics [8,9]. The present work was undertaken with the hope of obtaining further insight
into the mechanism of catalytic decomposition of
HzO 2. More specifically, we report here the results
of the influence of a "third-generation" catalyst-Co ( II ) (acac)--chemisorbed on propylpiperazinefunctionalised silica gel (PPS), which was prepared
and used as described below.

2. Experimental
2.1. Preparation o f the catalyst

The PPS matrix was prepared, as previously

reported [10,11], from 30 g of silica gel 60 (surface

152

S.F. Oliveira et al. / ColloMs Surfitces A." Physicochem. Eng. Aspects 136 (1998) 151-154

area=284 mZ/g, Merck), previously washed with

a 1:1 (v/v) mixture of HNO3-HCI to eliminate
metallic impurities. The silica was then refluxed
with 30 g of chloropropyltrimethoxysilane in toluene for 12 h. The resulting solid, silica-chloropropyl, was filtered, washed first with ethanol and
subsequently with benzene in a soxhlet until complete removal of unreacted chloropropyltrimethoxysilane. It was once again washed with ethanol,
dried under vacuum and reacted with 0.05 mol of
peperazine in toluene under reflux for 12 h. The
PPS obtained was filtered, washed and vacuum
dried. Kjedahl nitrogen analysis of the PPS
revealed the existence of 0.84 mmol of adsorbent
sites per gram of the matrix.
The chemisorption of Co(ll)(acac) (Aldrich)
on the matrix was effected by suspending 4 g of
the PPS in 0.2 dm 3 of a chloroform solution of the
complex (0.01 mol/dm 3) for 4 h with vigorous stirring. The resulting solid catalyst, Co (11)(acac)PPS,
was filtered, washed repeatedly with CHCI 3 and
dried under vacuum.
Analysis for the metal content of C o ( l I )
(acac)-PPS, carried out by atomic absorption
spectroscopy, revealed the presence of 0.12 mmol
of the chemisorbed complex per gram of the PPS
matrix. Prior to use, the catalyst was freed of any
impurities by thorough washing with double-distilled water. Also, it was verified that the catalytic
activity, of the product tbrmed, remained unaltered
with time in subsequent experiments.

2.2. Hydrogen peroxide decomposition

A stock solution of approximately 0.2 mol/dm 3
of H202 was prepared from 30% H202 (Merck,
A.R. grade) and standardized iodometrically using
sodium thiosulfate [3]. H202 solutions in the concentration range 0.05-0.15 mol/dm a were prepared
from this stock solution for use in the kinetic rims.
The reaction medium was buffered at a pH of 8.6.
This pH was chosen after a series of trial experiments performed in the pH range 6.0-9.0. The
buffer solutions in the pH range 7.8-9.0 were
prepared from solutions of borax and HC! whereas
those between 6.0 and 7.8 were made up of citric
acid and disodiumhydrogenphosphate.
Tests carried out with the PPS matrix alone

(without the chemisorbed Co (II) (acac) complex)

proved to be catalytically inactive towards H202
decomposition. In the majority of the experiments
20 cm 3 of the peroxide solution (0. l mol/dm 3) was
used per 0. l g of the catalyst. The reactions were
performed in a 25 cm 3 vessel, jacketed for circulation of water and immersed in a thermostated
water bath with a magnetic stirrer. A graduated
glass column served to measure the volume of the
liberated 02. The reaction temperatures were in
the range 30-45C.

3. Results and discussion

The rate of decomposition of H202 in contact

with PPS-Co(II)(acac) was determined by measuring the volume of 02 liberated as a function of
time, starting with an initial concentration of
0.1 mol/dm a of the peroxide and 0.1 g of the
catalyst.
Typical carves for the decomposition process
are shown in Fig. I. The rate constant, k, was
calculated by the expression
In clc-x =k wt,
where
is the
time t
Based

(1)

c is the initial concentration of H202, (--x)

concentration of undecomposed H202 at
and w is the weight of the catalyst in grams.
on the constancy of the k values obtained,

2.1,1,@8I
~1'4 I
1,0
0'8I
1,2

0,8

0,4
0,2

O,O0:q

2O

40

60

Fig. !. Illustration of the In{c/c-x) time curves of

H20,(0.1moi/dm 3) in the presence of 0.1g of the
Co( I1 ){acac)-PPS at various temperatures.

S.F. Oliveira et al. / CoiloMs Surfaces A: Physicochen~. Eng. Aspects 136 (1998) 151-154

153

Table 1
Rate constants (per 0.1 g dry catalyst) and activation parameters for the decomposition of H20 2 (0.1 moi/dm 3)

Temperature ~C

k (perg of catalyst) 104S-l

Ea (kJ mol -~)

30
35
40
45

1.266
1.855
2.738
3.938

.
.
57.81
.
.
.
.

AH* ~kJ mol -t )

.

it was concluded that the reaction is first order in

H202. The k values (for pH = 8.6) at temperatures
in the range 30-45C are presented in Table l.
Calculations based on kinetic runs with varying
initial concentrations of the peroxide gave a
reaction order of 0.76.
The dependence of the rate constant on pH was
studied in the pH interval 7.0-9.0. The results are
shown in Fig. 2. The observed increase in the rate
with increasing pH in the range 7.0-8.2 can be
explained if it is assumed that the anion HOE
combines more easily with the anchored complex
than the undissociated peroxide molecule to
form an intermediate peroxide, [Co(II)(acac)
PPS-O2H]. The observation that the reaction
order (0.76), obtained from runs with varying
initial concentrations of the peroxide, is lower than
that calculated for runs with a fixed initial concentration as a function of time would seem to support
this view. Another fact corroborating this assumption is that the re-use of the catalyst in a new

.
55.29
.
.

AG* (kJ mol -l )

AS* (J deg-I mol -l)

.
86.~4
.
.

.
.

-103.00

experimental run led to modified results for both

the reaction rate and order [ 12].
In experiments conducted by adding hydroquinone to t~e reaction medium there was a significant
reduction in the quantity of the oxygen released
in the decomposition process. The reduction
increased proportionally to the increase in the
amount of the hydroquinone added. This may be
taken as evidence for the occurrence of free radicals
during the catalytic decomposition of H202 in
contact with Co(II ) (acac)-PPS [ 13 ]. Further support for this conclusion comes from the relatively
low value found for the activation energy.
Based on these results and considering that in
the process of decomposition of H202 in homogeneous [14,15] and heterogeneous [16] media both
ions and free radicals may be involved simultaneously the following mechanism is proposed for
the C o ( I I ) ( a c a c ) - P P S catalysed reaction studied
here:
H,O~-

O , H - + H +.

(2)

fast

cat - H20 + O2H - ~ cat. - O2H - + H20,

(3)

fast

cat-OEH ~

intermediate product

slow

(active specime)~
fast
,to

cat. + 2 O H - + O 2 ,

(4)

2OH - + 2H ~ 2H2 O,

(5)

fast

cat. + H 2 0 ~
I

7,0

L5

8.0

e,5

9.0

c a t - H20.

(6)

fast

Based on the mechanism outlined, the rate equation can be written as:
Fig. 2. Dependence of the initial reaction rate on pH for
Co( II )(acac) -PPS catalysed decomposition of H2Oz.

dx/dt = k [ c a t -

OEH - ].

(7)

154

S.F Oliveira et al. / Colloids Smfaces A." Physk'ochem. Eng. Aspects 136 (1998) 151-154

severe alkaline conditions which renders it useful

in industrial processes where hydrogen peroxide is
utilized as a bleaching agent.

From Eqs. (2)-(4), we have

K, = [O2H -][ H ]/[ H202]
and

Acknowledgment

K2 = [ c a t - O 2 H - ] [ H 2 0 ] / [ c a t - H20][O2H-].

The authors thank PADCT and UFPB for

financial support and CNPq for fellowships.

Thus, the rate equation (Eq. (7) becomes

dx/dt=kKtK,[cat-H20][H202]/[H+].

(8)

This signifies that the reaction rate is directly

proportional to the quantity of the catalyst and
the H202 concentration and inversely proportional
to the concentration of H +
The activation energy E, was determined from
the Arrhenius equation. The variation in the
enthalpy of activation, AH*, is less than ER by a
quantity equal to RT (Table 1 ). AH* is a measure
of the height of the energy barrier relating to the
intra- and intermolecular bond strength which
should be overcome in the attainment of the
transition state. The variation of the free energy
of activation for the reaction, AG*, was calculated
from the Eyring equation [17] to be 86.0 kJ/mol,
which is in accordance with the values reported
for the H 2 0 2 decomposition catalysed by
Co(lI)-ammine complex in the presence of
Dowex-50W ion-exchange resin[12]. The variation
of entropy of activation, AS*, was obtained from
the relation
AG* = AH* - TAS*

(9)

and the resulting high value is suggestive of a

charged and rigid transition state [18].
An interesting feature of the heterogeneous catalyst employed in the present work is that, in
addition to its ease of separation from the reaction
medium, it is highly resistant to attack under

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