Effect of Different

Counterions of the
Manganese Salt as Catalyst
on the Kinetics of
Resorcinol-Based Belousov
Zhabotinsky Reaction
NADEEM B. GANAIE, GHULAM M. PEERZADA, ISHFAQ A. SHAH
Post Graduate Department of Chemistry, University of Kashmir, Srinagar 190 006, India
Received 31 January 2012; revised 27 October 2012; accepted 8 November 2012
DOI 10.1002/kin.20769
Published online in Wiley Online Library (wileyonlinelibrary.com).

ABSTRACT: Kinetic studies on the BelousovZhabotinsky (BZ) system with various metal ions
as catalysts have been carried out for a long time, but the effect of counteranions associated
with the metal ion solution used as the catalyst in the BZ reaction has not been explored.
Thus, we have chosen some metal salts as catalysts having the metal ion (Mnn+ ) but with
various anions to study the role of different anionic moieties of catalyst on the oscillatory
behavior of the resorcinol-based BZ reaction system. It is found that organic-type anionic
moieties marginalize the role of organic substrates in the reaction system. On the other hand,
the inorganic counterions of the catalyst show salting out effects, thereby increasing the ionic
strength, which affects the mobility (diffusion) of the ions in our system performed under batch
C 2012 Wiley Periodicals, Inc. Int J Chem Kinet 112, 2012
conditions. 

INTRODUCTION
The BelousovZhabotinsky (BZ) reaction [15] is
an extensively well-studied oscillating chemical reaction. It includes different chemical systems, all of

Correspondence to: Nadeem B. Ganaie; e-mail: nadeemganaie@

rediffmail.com. Ghulam M. Peerzada; e-mail: peerzada_gmp@
yahoo.co.in.
Contract grant sponsor: CSIR, New Delhi, India.
Contract grant sponsor: UGC, New Delhi, India.
C 2012 Wiley Periodicals, Inc.


which contain the bromate ion and an organic substrate in strongly acidic solution and have two major
classes such as catalyzed and uncatalyzed. The catalyzed system contains the metal ion as the catalyst
and an aliphatic organic substrate, which is oxidized
and brominated by the bromate ion as the metal ion
cycles between two oxidation states, such as Ce(IV)
and Ce(III). The uncatalyzed system contains more reactive aromatic compound (mainly phenol and aniline
derivatives) without any metal ion. However, the source
of the redox potential oscillations is not very clear in
uncatalyzed systems.

GANAIE, PEERZADA, AND SHAH

The catalyzed BZ reactions comprising Mn2+ [6],

Ce [7], Fe(phen)3 2+ [8], or Ru (bipy)3 2+ [9,10] as
catalysts have been studied extensively. Ferroin, originally used by Belousov as a redox indicator to enhance
the color changes in the cerium-catalyzed system, was
used by Zhabotinsky as the catalyst. By contrast, the
oscillating chemical reaction catalyzed by the macrocyclic complex of Cu(II) and Ni(II) involving lactic
acid, malonic acid, and pyruvic acid has been rarely
reported in the literature [1117]. Generally, the bromide ion acts as a control intermediate switching the
system between an oxidized and a reduced state, corresponding to low and high bromide ion concentrations,
respectively. The basic mechanism of the oscillations is
now well established by Field, Koros, and Noyes [18]
(FKN mechanism), in which Br ions play the role of
a control intermediate [19]. Some of the key reactions
of the detailed and systematic FKN mechanism, which
are necessary for oscillations to occur, are depicted as
under

EXPERIMENTAL

3+

2H+ + BrO
3 + Br HBrO2 + HOBr
+
HBrO2 + HBrO2 HOBr + BrO
3 +H

HOBr + Br + H Br2 + H2 O

Br + HBrO2 + H+ 2HOBr
HBrO2 +
n+

BrO
3

(1)

The reagents used were resorcinol (Himedia Laboratories, Mumbai, India; AR), potassium bromate (Merck,
Mumbai, India; LR), manganese(II)sulfate monohydrate (Aldrich, St. Louis, MO, USA; AR), sulfuric acid (Merck; LR), manganese(II)acetate (Aldrich;
AR), manganese(II)carbonate (Qualigens/Fischer Scientific, Mumbai, India; LR), manganese(III) acetate dihydrate (Aldrich; AR), manganese(II) bromide (Aldrich; AR), manganese(II) sulfide (Aldrich;
AR), manganese(II) chloride tetrahydrate (Thomas
Baker, Mumbai, India; AR), manganese(II) formate (Aldrich; AR), manganese(II) nitrate tetrahydrate (Aldrich; AR), manganese(II) phthalocyanine (Aldrich; AR), manganese(III) acetylacetonate
(Aldrich; AR), manganese(III) fluoride (Aldrich; AR).
All the reagents used were analytical-grade chemicals with a high degree of purity. The solutions
of the desired chemicals were prepared in 1.3 mol
L1 sulfuric acid using deionized double-distilled
water.

(2)

Procedure

(3)

The reaction system comprising resorcinol, inorganic

bromate, and a manganese-based salt as the catalyst
in 1.3 mol L1 sulfuric acid solution was kept in the
reaction cell into which a platinum electrode was immersed as an indicator electrode. The calomel (SCE)
reference electrode was kept in another reaction cell
containing 2.5 104 mol L1 solution of potassium
chloride. The two reaction cells (half cells) were connected through a salt bridge and then hooked to an
Orion 4 star, pH/ISE ion analyzer (Cole Parmer, Mumbai, India) to observe change in potential (mV) in the
reaction system with time (s) at regular intervals of
10 s. The two cells were used to avoid the interaction
of chloride ion from the SCE with the reaction mixture, as the former is a strong competitor for bromide
ion. The desired thermostatic conditions of the reaction
system under investigation were maintained using an
Advantec TBS451PA water bath (Cole Parmer) with
a precision of 0.1 C. All the experiments were performed several times under identical conditions to have
the reproducible results.

(4)

+ H Br2 O4 + H2 O

(5)

Br2 O4 2BrO2

(6)

+ BrO2 + H M

(n+1)+

+ HBrO2

Materials

(7)

The FKN mechanism is the outcome of an extensive

study performed on the thermodynamics and kinetics
of the basic quasi-elementary reaction steps involved in
the BZ reaction. However, the role of counterion moiety associated with the metal salt as the catalyst is not
reported extensively in the literature, although Lee and
Jwo [20] studied the behavior of [Mn2+ ]/[Mn3+ ] using a combination of Ce4+ and Mn(CH3 COO)2 . Also,
the complex behavior of Fe2+ and Ru2+ with different
ligands such as pyridine, bipyridine, and phenanthroline and batho(SO3 )2 with Fe2+ was monitored to understand the effect of complexation on the oscillatory
characteristics [21].
The motive of the present investigation is to study
the effect of different counterions of organic as well
as of inorganic nature associated with manganese ion
solution as the catalyst on the oscillatory characteristics of the resorcinol-based BZ system in 1.3 mol L1
sulfuric acid as aqueous acid medium.

RESULTS AND DISCUSSION

Ten reaction systems were prepared for comparative
study of the role of different anionic moieties of the
metal salts based on the manganese ion as the catalyst. Resorcinol and inorganic bromate were kept at
International Journal of Chemical Kinetics

DOI 10.1002/kin.20769

EFFECT OF COUNTERIONS ON BELOUSOVZHABOTINSKY REACTION

constant concentrations in all the reaction systems. As

such 10 different manganese salts were chosen, having different anions (organic/inorganic), and each salt
was used in one reaction system. The reaction systems
were studied at 30 0.1 C, and 1.3 mol L1 sulfuric acid was used as the medium throughout. In the
first instance, an attempt was made to choose the metal
ion for which good trials of the reaction systems were
made with Mn2+ , Ce3+ , Ce4+ , and Fe(phen)3 2+ ions
as catalysts in the form of most stable salts, and it was
observed that prominent oscillations are apparent with
Mn2+ ion as compared to the other metal ions [22,23].
Thus, Mn2+ ion was chosen as the catalyst and 10 manganese salts varying in the nature of anionic moieties
were used later to study the effect of the anionic moieties associated with the manganese ion as the catalyst
on the oscillatory characteristics of the reaction systems. It is worth mentioning that the concentration of
the manganese ion was kept constant in all the different
manganese salts used while selecting the concentration
range of different manganese salts in 10 reaction systems. It is quite pertinent to mention here that stirring
was not suitable for our reaction system because of the
occurrence of precipitation during the progress of the
reaction. Thus, the study was performed in an unstirred
batch reactor under closed conditions. It is well known
that manganese(II) sulfide is easily oxidized in the air,
manganese(III) fluoride and manganese(III) acetate are
instantaneously hydrolyzed, formate is oxidized, phthalocyanine is recrystalized, and acetylacetonate is
also hydrolyzed after some time once its solution is
prepared. The salient features of a chemical oscillator
are described in terms of various parameters such as
induction period (tin ), time period (tp ), amplitude (A),
frequency(v), and number of oscillations (n). These
parameters are estimated from the oscillatory profile
drawn by plotting potential (mV) versus time (s). The
time period and amplitude is taken as the average of the
time (s) and potential jump (mV) for six consecutive
oscillations in the profile, respectively. The number of
oscillations (n) is taken as equal to the total number of
periodic cycles in the oscillatory profile for a particular
period of time. Similarly, the frequency is calculated
as the reciprocal of time period, whereas the induction
period (tin ) is taken as the time taken up to the appearance of first oscillation after the mixing of bromate
(oxidant) to the reaction mixture containing organic
substrate and catalyst. The results obtained with various anionic moieties of the catalyst are depicted and
discussed.

Sulfide Ion
Figure 1a gives the potential (mV) versus time (s)
plot for the system containing [MnSO4 H2 O] = 4
International Journal of Chemical Kinetics

DOI 10.1002/kin.20769

103 mol L1 , [BrO3 ] = 0.1 mol L1 , [Resorcinol]

= 0.0225 mol L1 at 30 0.1 C, wherein some unexpected results in terms of dual frequency and amplitude
for the oscillations are observed. It is found that after
a definite induction period peculiar to aromatic substrates, there is a high-frequency region up to 830 s
with time period of about 70 s and amplitude of 90 mV
followed by a low-frequency region with a decrease in
the amplitude up to 50 mV. Considering this as the reference system and changing the concentration of sulfide ions, keeping the initial concentrations of the other
reagents constant as presented in Table I, the oscillatory
parameters show an unusual behavior. With an increase
in [S2 ], the induction period increases with the exception at 0.66 103 mol L1 . However, there is first a
decrease and then an increase in the high-frequency
region as well as the number of oscillations up to
1.00 103 mol L1 , after which chaotic behavior
is observed. It is also observed that there is a gradual
decrease in the number of oscillations as compared to
the reference system, whereas the amplitude first shows
an increase for both high- and low-frequency regions at
lower [S2 ] and then a gradual decrease with increasing [S2 ]. The effect of sulfide ion as a counterion has
been confirmed by inserting 500 L of CuSO4 solution just after the induction period is over (Fig. 1d),
which resulted in the removal of [S2 ] as CuS (), and
hence there is an increase in oscillatory parameters as
is found in the reference system. The results obtained
above are justified on the basis of the fact that manganese(II) sulfide dissolved in aqueous sulfuric acid
evolves H2 S gas and the S2 is a strong competitor for
HOBr in acid media as per the FKN mechanism.
S2 + HBrO3 + 2H+ S() + HBrO2 + H2 O (8)
S2 + Cu2+ CuS()

(9)

In addition to the above reaction (8), the S2 will also

influence the kinetics of the reaction steps 1, 3, and 5,
of the FKN mechanism as shown above.

Effect of Fluoride
Table II shows the effect of [F ] on the oscillatory
parameters for the resorcinol-based system. The oscillations start after an induction period (Fig. 2). It
was observed that with an increase in [F ], there is a
first increase up to 0.04 103 mol L1 and then a decrease and then again an increase after 0.08 103 mol
L1 of [F ] for both the induction period as well as
high-frequency regions, whereas the time period and
the amplitude show the reverse trend. This ambiguous

GANAIE, PEERZADA, AND SHAH

1200

1200

1100

1100

1000

1000

(b)

Redox potential (mV)

(a)
900

900

800

800

700

700
0

500

1000

1500

2000

2500

3000

3500

1200

500

1000

1500

2000

2500

3000

3500

1200

500 L CuSO4
1100

1100

1000

1000

(c)

(d)

900

900

800

800

700

700
0

500

1000

1500

2000

2500

3000

3500

500

1000

1500

2000

2500

3000

3500

Time (s)

Figure 1 Potential (mV) versus time (s) plots showing the effect of [sulfide] containing [Mn2+ ] = 4 103 mol L1 ,
[BrO3 ] = 0.1 mol L1 , [resorcinol] = 0.0225 mol L1 at 30 0.1 C: (a) 0 mol L1 , (b) 0.03 mol L1 , (c) 0.16 mol L1 ,
(d) 0.16 mol L1 .
Table I Effect of [S2 ] on the Oscillatory Parameters of the Systems Containing the [Mn2+ ] = 4 103 mol L1 ;
[BrO3 ] = 0.1 mol L1 , [Resorcinol] = 0.0225 mol L1 at 30 0.1 C
Metal Salt
Composition
MnSO4 2 mL
Mn(II)sulfide 2 mL
MnS 1.5 mL + MnSO4
0.5 mL
MnS 1.0 mL + MnSO4
1.0 mL
MnS 0.5 mL + MnSO4
1.5 mL
MnS 0.25 mL + MnSO4
1.75 mL
MnS 0.15 mL + MnSO4
1.85 mL

[S2 ] ( 103
mol L1 )

Induction
Period, tin (s)

High-Frequency
Region (s)

Time Period,
tp (s)

Number, n

Amplitude,
A (mV)

0
1.33
1.00

140
580
350

830
Chaotic
Chaotic after 900 s

70, 230
90
90

>20
>15
>14

90, 50
38
70

0.66

210

800

110, 220

>16

70, 90

0.33

295

600

100, 225

>13

100

0.16

200

740

70, 170

>16

118, 78

0.10

140

800

70, 230

>17

110, 97

behavior can be attributed to the direct role of F in

the FKN mechanism as well as the increase in the initial [Mn3+ ]/[Mn2+ ] ratio due to the added Mn3+ ion.
This behavior is also justified since F ion is more reactive than Cl and Br . It is also observed that with

an increase in [F ], the oscillatory parameters move

close to the reference resorcinol system; this is the reason for choosing the lower concentrations of the F as
counterion. The number of oscillations shows a decreasing trend with a decrease in [F ].
International Journal of Chemical Kinetics

DOI 10.1002/kin.20769

EFFECT OF COUNTERIONS ON BELOUSOVZHABOTINSKY REACTION

Table II Effect of [F ] on the Oscillatory Parameters of the Systems Containing the [Mn] = 4 103 mol L1 ;
[BrO3 ] = 0.1 mol L1 , [Resorcinol] = 0.0225 mol L1 at 30 0.1 C
Metal Salt
Composition

[F ] ( 103
mol L1 )

Induction
Period, tin (s)

High-Frequency
Region (s)

Time Period
tp (s)

Number, n

Amplitude,
A (mV)

1.33
0.02

165
140

800
640

76.6, 210
96.6, 247.5

>20
>16

52.6, 70
61.5, 76.3

0.04

200

700

60, 245

>16

59, 88.3

0.06

120

450

67.5, 243.3

>19

77.6, 76

0.08

150

600

67.5, 260

>19

63.3, 99.3

Mn(III) fluoride 2 mL
Mn(III) fluoride 0.03 mL +
MnSO4 1.97 mL
Mn(III) fluoride 0.06 mL +
MnSO4 1.94 mL
Mn(III) fluoride 0.09 mL +
MnSO4 1.91 mL
Mn(III) fluoride 0.13 mL +
MnSO4 1.87 mL

1200

Redox potential (mV)

1100

1000

900

800

700
0

500

1000

1500

2000

2500

3000

3500

Time (s)

Figure 2 Potential (mV) versus time (s) plots for the systems containing [MnF3 ] = 4 103 mol L1 , [BrO3 ] =
0.1 mol L1 , [resorcinol] = 0.0225 mol L1 at 30 0.1 C.

centrations of other reagents constant. Phthalocyanine

is an organic substance and shows poor solubility in our
system under normal conditions and hence the salt was
dissolved by heating the solution. As seen with other
inorganic counterions studied above, the oscillations
start after an induction period, with no appearance of
dual-frequency regions and amplitudes. The induction
period decreases with a decrease in [Phthalocyanine]
from 1.33 103 to 0.16 103 mol L1 . The salt
solutions used were freshly prepared. However, the
induction period decreases and the number and amplitude of oscillations show an increase when the salt
solutions were allowed to stand undisturbed for some
time leading to the formation of supernatant liquid,
which was eventually used. The increase in oscillatory parameters with the supernatant liquid can be due
to the activation of the organic counterion in aqueous
acid medium for bromination, by which the limiting
bromosubstrate concentration is attained quickly.

Effect of Nitrate
From Table III, it is found that by increasing [NO3 ] in
the reaction system while keeping the concentrations
of other reagents constant, there is a decrease in the
induction period, whereas the time period and amplitude of oscillations increase. The number as well as
the frequency in the high region for oscillations remains constant for the nitrate containing systems with
an overall decrease in the number of oscillations than
the reference system. This behavior can be attributed to
the combined effect of nitrate and sulfate ions as counterion moieties. However, it is observed that the time
period of oscillations following the high-frequency region remains constant while changing initial [NO3 ].

Effect of Phthalocyanine
Figure 3 depicts the behavior of oscillations for the system containing varying [Phthalocyanine] keeping conInternational Journal of Chemical Kinetics

DOI 10.1002/kin.20769

Effect of Formate
Table IV shows the effect of [HCOO ] ion on the oscillatory behavior of our reaction system. It was observed
that with an increase in [HCOO ], the induction period
decreases, whereas the high-frequency region and time
period show first a decrease and then an increase. There
is also an increase in the number of oscillations with an
increase in [HCOO ], which may be attributed to the
role of formate ion as a cosubstrate in the reaction and
thus competing with the bromination reaction, thereby
causing the limiting concentration to attain rapidly.

Effect of Acetate
Mn3+ salts are unstable in aqueous acid media and
get reduced to Mn2+ ion in the solution after some
time. Thus, the salt solutions were freshly prepared for
investigation. Both Mn2+ and Mn3+ salts of acetate ion

GANAIE, PEERZADA, AND SHAH

Table III Effect of [NO3 ] on the Oscillatory Parameters of the Systems Containing the [Mn2+ ] = 4 103 mol L1 ;
[BrO3 ] = 0.1 mol L1 , [Resorcinol] = 0.0225 mol L1 at 30 0.1 C
Metal Salt
Composition

[NO3 ] ( 103
mol L1 )

Induction
Period, tin (s)

High-Frequency
Region (s)

Time Period,
tp (s)

Number, n

Amplitude,
A (mV)

1.33
0.66

180
240

850
850

105, 290
82.5, 290

>16
>16

80, 92.6
63.6, 83

Mn(II) nitrate 2 mL
Mn(II) nitrate 1 mL +
MnSO4 1 mL

acetate ion constant. As reported in Table V, oscillations start after an induction period for both the oxidation states of manganese. However, using some initial
[Mn3+ ], which causes a decrease in [Mn2+ ]/[Mn3+ ],
increases the induction period, the number as well
as the high-frequency region for oscillations, whereas
there is a decrease in the amplitude of oscillations. The
experiment was also performed using the supernatant
fluid obtained from the manganese(III) solution kept
overnight. This reveals that the oscillatory parameters
move nearer to the Mn2+ system, confirming the instability followed by the reduction to Mn2+ solutions in
aqueous acid media.

1200
1100
1000

(a)

900

Redox potential (mV)

800
700
1200 0

500

1000

1500

2000

2500

3000

3500

1100
1000
900

(b)

800
700
1200 0

500

1000

1500

2000

2500

3000

3500

1100
1000
900

(c)

800
700
0

500

1000

1500

2000

2500

3000

3500

Time (s)

Figure 3 Potential (mV) versus time (s) plots showing

the effect of [phthalocyanine] containing [Mn2+ ] = 4
103 mol L1 , [BrO3 ] = 0.1 mol L1 , [resorcinol] =
0.0225 mol L1 at 30 0.1 C: (a) 1.33 mol L1 (supernatant), (b) 1.33 mol L1 , and (c) 0.16 mol L1 .

Effect of Acetylacetonate
Table VI pertains to the effect of [acetylacetonate] as
counterion for the Mn3+ ion. Again, owing to the instability of Mn3+ ion in aqueous acid media, freshly
prepared solutions were used. The oscillations start
after an induction period for the systems containing
[acetylacetonate] lower than 2.66 103 mol L1 .

were used to compare the oscillatory behaviors with

different oxidation states of manganese, keeping the

Table IV Effect of [HCOO ] on the Oscillatory Parameters of the Systems Containing the [Mn2+ ] = 4 103 mol
L1 ; [BrO3 ] = 0.1 mol L1 , [Resorcinol] = 0.0225 mol L1 at 30 0.1 C
Metal Salt
Composition

[HCOO ] ( 103
mol L1 )

Induction
Period, tin (s)

High-Frequency
Region (s)

Time Period,
tp (s)

Number, n

1.33
0.66

110
140

1050
740

77.5, 295
65, 215

>19
>17

61, 47
69, 76.3

0.33

150

820

80, 235

>17

54.3, 85.6

Mn(II) formate 2 mL
Mn(II) formate 1 mL +
MnSO4 1 mL
Mn(II) formate 0.5 mL +
MnSO4 1.5 mL

Amplitude,
A (mV)

Table V Effect of [CH3 COO ] on the Oscillatory Parameters of the Systems Containing the [Mn] = 4 103 mol L1 ;
[BrO3 ] = 0.1 mol L1 , [Resorcinol] = 0.0225 mol L1 at 30 0.1 C
Metal Salt
Composition
Mn(III) acetate 2 mL (4 days)
Mn(III) acetate 2 mL (fresh)
Mn(II) acetate 2 mL
Mn(III) acetate 2 mL
(supernatant)

[CH3 COO ]( 103

Induction High-Frequency Time Period,
Amplitude,
Period, tin (s)
Region (s)
tp (s)
Number, n A (mV)
mol L1 )
1.33
1.33
1.33
1.33

120
120
150
170

500
600
900
640

65, 197.50
60, 226
60, 227.50
62, 127.50

International Journal of Chemical Kinetics

>16
>16
>20
>19

83, 88
52, 88
67.6, 80
74, 70

DOI 10.1002/kin.20769

EFFECT OF COUNTERIONS ON BELOUSOVZHABOTINSKY REACTION

Table VI Effect of [Acetylacetonate] on the Oscillatory Parameters of the Systems Containing the [Mn] = 4
103 mol L1 ; [BrO3 ] = 0.1 mol L1 , [Resorcinol] = 0.0225 mol L1 at 30 0.1 C
Metal Salt
Composition

[Acetylacetonate]
( 103 mol L1 )

Induction
Period, tin (s)

Time Period,
tp (s)

Number, n

Amplitude,
A (mV)

1.33
2.66
0.66

1000
905
350

30
**
100, 270

<10
1
>19

8.75
**
35

0.33

180

90,228

>16

50, 80

Mn(III) acac 0.004 M, 2 mL

Mn(III) acac 0.008M, 2 mL
Mn(III) acac 0.004 M, 1 mL +
MnSO4 0.004 M, 1 mL
Mn(III) acac 0.004 M, 0.5 mL +
MnSO4 0.004 M, 1.5 mL
**, No oscillations seen.
1200

1200

1100

1100

1000

1000

(a)

900

800

Redox potential (mV)

(b)

900

800

700

700
0

500

1000

1500

2000

2500

3000

3500

1200

1200

1100

1100

1000

1000

900

500

1000

1500

2000

2500

3000

3500

3000

3500

900

(c)

(d)
800

800

700

700
0

500

1000

1500

2000

2500

3000

3500

500

1000

1500

2000

2500

Time (s)

Figure 4 Potential (mV) versus time (s) plots showing the effect of [acetylacetonate] as counterion using Mn(acac)3 containing
[Mn] = 4 103 mol L1 , [BrO3 ] = 0.1 mol L1 , [resorcinol] = 0.0225 mol L1 at 30 0.1 C: (a) 0.33 mol L1 , (b)
1.33 mol L1 , (c) 2.66 mol L1 , and (d) 0.66 mol L1 .

The prominent increase in the induction period as compared to the reference system is because of delaying the
limiting bromosubstrate concentration, caused by the
bromine scavenging effect of acetylacetonate. The increase in [acetylacetonate] is responsible for increased
bromine scavenging activity of acetylacetone, marked
with minimal oscillations observed at 1.33 and 2.66
103 mol L1 (Figs. 4b and 4c) with lesser amplitude and number of oscillations. However, the decreasing concentration of acetylacetonate results in the
International Journal of Chemical Kinetics

DOI 10.1002/kin.20769

appearance of dual-frequency regions and amplitude of

oscillations. It is mentioned that some minimal oscillations have been observed for the systems containing
higher concentrations of acetylacetonate in the absence
of main substrate, i.e., resorcinol. This is a prelude
to the aforesaid statement [22] that organic species
used as counterions can avoid the use of organic substrates in the catalyzed BZ system. However, this is in
contradiction to the bromine-scavenging role of acetylacetonate [24].

GANAIE, PEERZADA, AND SHAH

Table VII Effect of [CO3 2 ] and Temperature on the Oscillatory Parameters of the Systems Containing the [Mn2+ ] =
4 103 mol L1 ; [BrO3 ] = 0.1 mol L1 ; [Resorcinol] = 0.0225 mol L1
[CO3 2 ] ( 103 Induction High-Frequency Time Period,
Amplitude,
Period, tin (s)
Region (s)
tp (s)
Number, n A (mV)
mol L1 )

Metal Salt
Composition
MnCO3
MnCO3
MnCO3
MnCO3
MnCO3
MnCO3
MnCO3

30 C, 2 mL
1.5 mL + MnSO4 0.5 mL
1 mL + MnSO4 1 mL
0.5 mL + MnSO4 1.5 mL
25 C
35 C
40 C

1.33
1.00
0.66
0.33
1.33
1.33
1.33

150
220
170
190
355
100
60

1200

1200

1100

1100

1000

1000

900

85, 215
88, 430
87.5, 366
95, 300
90, 230
275
47.5, 382.5

84, 100
75, 100
42.5, 85
49.25, 100
82
77
73

>17
>18
>16
>15
>12
>16
>18

900

(a)

800

Redox potential (mV)

900
2000
1500
700
900
900
900

(c)

800

700

700
0

500

1000

1500

2000

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3500

1200

1200

1100

1100

1000

1000

(b)

900

500

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3500

(d)

800

700

700
0

500

1000

1500

2000

2500

3000

3500

500

1000

1500

2000

2500

3000

3500

Time (s)

Figure 5 Potential (mV) versus time (s) plots showing the effect of temperature on the system containing [MnCO3 ] = 4
103 mol L1 , [BrO3 ] = 0.1 mol L1 , [resorcinol] = 0.0225 mol L1 : (a) 25 0.1 C, (b) 30 0.1 C, (c) 35 0.1 C, and
(d) 40 0.1 C.

Effect of Carbonate
Table VII depicts the behavior of [CO3 2 ] on the oscillatory parameters. The oscillations start after an induction period, without showing any regular trend in induction and time periods. However, the high-frequency
regions and number of oscillations first increase and
then continuously decrease after 0.66 103 mol L1 ,
whereas the amplitude shows a gradual decrease and
subsequent increase. The dissolution of carbonate in

aqueous acid medium is associated with release of

CO2 , so freshly prepared solutions were used to prevent escape of higher amounts of CO2 to determine the
effect of dissolved CO2 in the reaction system. As we
know that dissolved gases can be removed by either
stirring or heating, the latter method was chosen for
the reaction containing [MnCO3 ]0 as 1.33 103 mol
L1 , keeping initial concentrations of other reagents
constant but at different temperatures (Fig. 5). It is
International Journal of Chemical Kinetics

DOI 10.1002/kin.20769

EFFECT OF COUNTERIONS ON BELOUSOVZHABOTINSKY REACTION

Table VIII Effect of [Cl ] on the Oscillatory Parameters of the Systems Containing the [Mn2+ ] = 4 103 mol L1 ;
[BrO3 ] = 0.1 mol L1 , [Resorcinol] = 0.0225 mol L1 at 30 0.1 C
[Cl ]( 103
Induction
High-Frequency Time Period,
Amplitude,
Period, tin (s)
Region (s)
tp (s)
Number, n
A (mV)
mol L1 )

Metal Salt
Composition
MnCl2
MnCl2
MnCl2
MnCl2

2 mL
0.5 mL+ MnSO4 1.5 mL
0.25 mL+ MnSO4 1.75 mL
0.15 mL+ MnSO4 1.85 mL

1.33
0.33
0.16
0.10

**
90
1060
970

**
**
1600
**

**
**
90, 230
85, 200

**
2
>11
>16

**
60
88, 60
40

**, No oscillations seen.

observed that there is a steady increase in the rate of

the reaction, attributed to a decrease in the induction
period. The time period showed very unusual results
due to the evolution of CO2 creating an inhomogeneous behavior. Thus, no regular trend is observed in
the time period, amplitude, and number of oscillations.
It is to be noted that the high-frequency region remains constant at different temperatures. The presence
of carbonate as well as acetylacetonate as counterions
decreases the number of oscillations in these reaction

Effect of Chloride
It is known that the presence of chloride ions in the
reaction system competes with the bromide-mediated
reaction steps as proposed in the FKN mechanism;
therefore there is a decrease in oscillatory parameters.
This effect was confirmed by varying [Cl ] used as the

1200

1200

1100

1100

1000

Redox potential (mV)

systems as compared to the reference system under

investigation.

1000

(a)

(b)

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900

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700

700
0

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1000

1500

2000

2500

3000

3500

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1500

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3500

(c)
900

900

800

800

700

700

500

1000

1500

2000

2500

3000

3500

(d)

500

1000

1500

2000

2500

3000

3500

Time (s)

Figure 6 Potential (mV) versus time (s) plots showing the effect of [chloride] containing [Mn2+ ] = 4 103 mol L1 ,
[BrO3 ] = 0.1 mol L1 , [resorcinol] = 0.0225 mol L1 at 30 0.1 C: (a) 1.33 mol L1 , (b) 0.10 mol L1 , (c) 0.33 mol L1 ,
and (d) 0.16 mol L1 .
International Journal of Chemical Kinetics

DOI 10.1002/kin.20769

10

GANAIE, PEERZADA, AND SHAH

Table IX Effect of [Br ] on the Oscillatory Parameters of the Systems Containing the [Mn2+ ] = 4 103 mol L1 ;
[BrO3 ] = 0.1 mol L1 , [Resorcinol] = 0.0225 mol L1 at 30 0.1 C
[Br ]( 103
Induction
High-Frequency Time Period,
Amplitude,
Period, tin (s)
Region (s)
tp (s)
Number, n
A (mV)
mol L1 )

Metal Salt
Composition
MnBr2
MnBr2
MnBr2
MnBr2
MnBr2

2 mL
0.15 mL + MnSO4 1.85 mL
0.30 mL + MnSO4 1.70 mL
0.50 mL + MnSO4 1.50 mL
1.0 mL + MnSO4 1.0 mL

1.33
0.10
0.20
0.33
0.66

1200
255
230
200
660

**
690
550
**
1400

93
50, 160
80, 153.30
100
100, 170

10
>21
>16
14
>18

40
26, 62.3
38, 65
30
40, 50

**, No oscillations seen.

1200

1200

1100

1100

1000

1000

900

(a)

(b)

900

800

Redox potential (mV)

800
700
700
600
0

500

1000

1500

2000

2500

3000

3500

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1200

1100

1100

1000

1000

900

500

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900

(c)

800

800

700

700

600

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3500

3000

3500

(d)

600
0

500

1000

1500

2000

2500

3000

3500

500

1000

1500

2000

2500

Time (s)

Figure 7 Potential (mV) versus time (s) plots showing the effect of [bromide] containing [Mn2+ ] = 4 103 mol L1 ,
[BrO3 ] = 0.1 mol L1 , [resorcinol] = 0.0225 mol L1 at 30 0.1 C: (a) 0.33 mol L1 , (b) 1.33 mol L1 , (c) 0.10 mol L1 ,
and (d) 0.20 mol L1 .

counterion for Mn2+ as shown in Table VIII. It was

found that a decrease in [Cl ] up to 0.16 103 mol
L1 has an inhibitory effect on oscillatory parameters
such as the time period and amplitude (Fig. 6), after which chaotic behavior is observed. The presence
of the prolonged induction period clearly shows the
Cl inhibition and control on the bromination process
of the BZ reaction. Hence, by controlling the [Cl ] we
can easily control the temporal behavior of oscillations,
which in turn control the HOBr/Br couple [25]. Chaos

in an open chemical system may be defined as an aperiodically varying composition determined by the intrinsic dynamics of the system rather than by noise or external influences, which depends sensitively on the initial
conditions, i.e., two chaotic systems that differ even infinitesimally in their initial conditions evolve in time so
as to diverge exponentially from one another. Chaotic
behavior typically emerges from periodic oscillation
as the control parameter is varied, often by a perioddoubling route [26], in which alternate extrema become
International Journal of Chemical Kinetics

DOI 10.1002/kin.20769

EFFECT OF COUNTERIONS ON BELOUSOVZHABOTINSKY REACTION

11

slightly larger or smaller at a series of critical values

of the parameter until a limit point, where the behavior
becomes aperiodic, i.e., chaotic. Every chaotic trajectory contains an infinite number of unstable periodic
paths, and it has been suggested that one should be able
to control chaos by applying very small, carefully
selected perturbations to a chaotic system to stabilize a
chosen periodic behavior [27]. This approach has been
put into practice successfully in the BZ system [28].

Effect of Bromide
The use of KBr earlier in the BZ reaction confirmed
the role of Br ion as the control intermediate for the
oscillatory process [29]. Here, we have used Br as
the counteranionic moiety of the Mn2+ ion solution for
observing this trend, which showed interesting results.
From Table IX, it is observed that with an increase in
initial [Br ], the induction and time periods increase
except at 1.33 103 mol L1 . However, the highfrequency region, number, and amplitude of oscillations do not vary regularly. It is found that with 0.20
and 0.66 103 mol L1 [Br ], the oscillatory parameters are very prominent (Fig. 7). In fact, these
concentrations coincide with the intermediate Br concentration, which acts as positive feedback for this
reaction, whereas with other concentrations it will act
as negative feedback causing a decrease in oscillatory
parameters.

Figure 8 Diffusion patterns showing discrete regions for

the system containing 2 mL each of [Mn(NO3 )2 ] = 4
103 mol L1 , [BrO3 ] = 0.1 mol L1 , [resorcinol] =
0.0225 mol L1 at room temperature after addition of one
drop of 0.025 mol L1 of ferroin solution. [Color figure
can be viewed in the online issue, which is available at
wileyonlinelibrary.com.]

SUMMARY
To design a new chemical oscillator, the choice of counterion associated with a metal ion to be used as the
catalyst is inevitable. The organic and inorganic counterions show diverse behaviors, i.e., decreasing and increasing trends, respectively. Thus, the control can be
associated with some of these species, which are somehow involved in some reaction steps as proposed in the
FKN mechanism. The present work clearly shows that
organic counterions can act as cosubstrates (formate,
acetate) and even sometimes as substrates (acetylacetonate), whereas inorganic counterions directly increase
the ionic strength of the medium, besides acting as control (chloride, bromide, fluoride), and cause for noisy
behavior (carbonate, sulfide) due to release of gases
and hence leading to inhomogeneity in the oscillatory
system. The inhomogeneity can be observed as irregular trends with respect to various oscillatory parameters. The presence of varied counterions in different
systems is the cause for variation in diffusion patterns,
which requires a more detailed study. The concentric
regions appear due to addition of ferroin on a thin layer
of the reaction system (in Petri dishes with 100 mm diInternational Journal of Chemical Kinetics

DOI 10.1002/kin.20769

Figure 9 Diffusion patterns showing diffused regions for

the system containing 2 mL each of [Mn(CH3 COO)2 ] = 4
103 mol L1 , [BrO3 ] = 0.1 mol L1 , [resorcinol] =
0.0225 mol L1 at room temperature after addition of one
drop of 0.025 mol L1 of ferroin solution. [Color figure
can be viewed in the online issue, which is available at
wileyonlinelibrary.com.]

ameter and 3 mm solution thickness) because of the

increase in local ionic strength due to the addition of
inorganic counterions (Fig. 8), whereas an increase in
the hydrophobic nature due to the addition of organic
counterions is the cause for diffused patterns (Fig. 9).

12

GANAIE, PEERZADA, AND SHAH

The authors are thankful to the Head, Department of Chemistry, University of Kashmir, Srinagar, India, for providing
infrastructure to undertake the investigation.

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International Journal of Chemical Kinetics

DOI 10.1002/kin.20769