Indian Journal of Chemistry

Vol. 41 A, March 2002, pp. 532-536

A kinetic study of the chemical oscillating
system comprising mannitol-acetone-
bromate-H
2
S0
4
Shi -Gang Shen' , Han-Wen Sun, Jin-Huan Shan
& JL'n-li Liu
Col lcge of Chemical and Envi ronmental Science, Hebei
University. Baoding 071002. P. R. China
Rl'Cl!il'ed 24 Ma.l' 2001; r el 'ised 16 OClUbl.'r 2001
A new type of chemical oscill at ing system compris ing
lll<lnni tol -acetone- bromate-I-(lS04 has been studied by the
potential method. The initial concentrati on range of the
rcactant s in the osci llating system and affecting factors
ila\'c been examined. The empirical equati on of the
induction period and oscill ating cycle with the
concentrati ons of the reactan ts and temperature has been
obta ined. The apparent acti vati on parameters corresponding
to the induction period, oscillating cycle and oscill ating
li fe, E" E
p
, E, are 45.1 4 kJ mol" , 60.20 kJ mol" and 67.30
k.I mol", respecti ve ly. The oscil lating characteri sti c and
possi bl e oscill ation mechani sm have been analyzed.
A chemical oscill at ing reaction is self-organi zing
phenomenon when the react ion sys tem is far away
from the equilibrium state. It is also called the
chemical clock, which is similar to the biological
clock. When the chemical reaction is far away from
the equilibrium, the concentration of some
substances in the reaction system exhibits a regular
change with time, a kind of self-regulating function
similar to what happens in an organism. During the
last ten to twenty years, vitamin C, glucose, pyruvic
acid, fructose, amino acid, lactose and malic acid
have been reported" s to be very important reaction
substrat es in oscillating reactions; they also play an
important part in the synthesis of cell substances in
life
9
. As a dehydrator and diuretic, mannitol has
been used clinically for curing many diseases. In
thi s paper we report a new experimental
investigation of the bromate oscillator uSing
mannitol and acetone as the mixed orgal11c
substrates . The temperature effects on the
oscillations of thi s system and the relation of the
oscillati on peri ods with the substrate concentrations
have been studi ed in detail. The period of oscillations
is related to the chemical mechanism through the rate
equations. Therefore, the osci ll ating characteristi c and
possible oscillati on mechanism have been anal yzed.
Experimental
Analytical grade mannitol, manganous sulphate,
sulphuri c acid and acetone were used in the
experiments. Analytical grade potassi um bromate was
recrystalli zed from doubl y deionized water. The water
used in the experiments was doubl y deioni zed.
Experiments were performed ill a thermostat (the
temperature was controlled up to 0. 1 K). The
overall volume of the soluti on was 50 mL. Sulphuric
acid, mannitol , manganous sulphate and acetone were
added successively under stirring by a magnet ic
agitator. When the temperatur of the reaction
mixture became constant ( 0.1 K), the solut ion of
potass ium bromate thermostate, at the same
temperature was instantl y transferred into the mi xt ure
as the last addi ti on. The oscillating curves of the
potential versus time were recorded using a tabl e x-t
recorder. Smooth bri ght platinum was empl oyed as
indicator electrode and a 217-Type SeE was used as
the reference electrode together with ( I mol dm
1
sulphuric acid) liquid junction having a sintered silica
di sc at the end dipping in the reaction mixture. Since
only the characteristic of the oscillating curve wi th
time was considered in the present work, E was in
arbitrary units. The typical traces of potential
oscillations was shown in Fig. 1.
Results and discussion
Oscillatillg phenomenoll
Table 1 gives the initial concentration range of the
reactants and temperature range in the chemical
oscillating system of mannitol-acetone-bromate-
H
2
S0
4
.
The typical oscillating conditi on is: [Act]o = 1.02
mol dm
3
, [MA]o = 0.0188 mol dm-
J
, [Br03' ]O= 0.0675
mol dm
3
, [Mn
2
+]o = 0.00250 mol dm-
3
, [H
2
S0
4
]o =
2.58 mol dm-
3
, T = 298 0.1 K. In the concentration
range li sted in Table I, the colour of the soluti on
changed from pink (the colour of Mn
2
+) to brown, and
at the same time the potential of the system went up
rapidly after addition of KBrO] solution. After a
period of induction, the potenti al decreased rapidl y,
NOTES
533
Table I- The initi al concentrati on range of the reactants and temperature range
in the oscill ating system (Concentrati on unit : mol dn'-')
IActlo
0. 17-4. 0
1. 02
1.02
1. 02
1. 02
1.02
...
..
"
..
[MAlo IBrO,' lo
0.01 88 0.0675
0.009-0.05 I 0.0675
0.01 88 0.Q38-0.1 35
0.01 88 0.0675
0.0188 0.0675
0.01 88 0.0675
[Mn
2
+1o [H
2
S041
0
T/K
0.0025 2.58 298
0.0025 2.58 298
0.0025 2. 58 298
0.0001 25- 0.0250 2.58 298
0.0025 1. 30- 4. 10 298
0.0025 2.58 293-323
Time,s
Fig. I-The osci11ating curve of the potential with time [System: [Actlo = 1.02 mol dm'), [MAlo = 0.0188 mol dm') mol dm", [8r0.1'10=
0.0675 mol dm" , [Mn
2
+10 = 0.00250 mol dm
3
, [H
2
S0
4
1
0
= 2.58 mol dm
3
, temp.=298 0. 1 K].
and the system exhibited a periodic oscillation
between brown and pale yellow. In the latter stage,
the solution colour became light, and the oscillating
cycle did not change much during the whole
oscillating process. With time, the oscillating
amplitude began to show a trend of slow increase, and
after a period of stable amplitude, the amplitude
began to decrease gradually until the oscillation
stopped.
The effect of temperature and the apparent activation
parameters
The mannitol-acetone-bromate-H
2
S0
4
chemical
oscillating system is very sensitive to temperature
changes. When the temperature increased, the
induction period tieS), oscillating cycle tp(s), and
oscillating life tt(s) decreased regularly.
A very good linear relationship was obtained
when fitting In(t; ts), In(tp ts) and In(tt" s) with I'K
(shown in Fig. 2), the linear correlation coefficients
are greater than 0.995, and the corresponding linear
equations are:
In(t;" s) = -E/RT + A;
In(tp"s) = -Er/RT + AI'
In(tl"s) = -E,/RT + A,
in which A;, AI' and A, are the intercept of the line,
E;/R, Ep/R and E,/R are the slopes of the fitting line,
respectively. Compared with the Arrhenius equation
In(k) = EAIRT + A, (; -', tp l, and t, -' are very similar to
E -5 A
c
-6 -----------=
-7
3.05 3.10 3.15 3.20 3.25 3.30 3.35 3.40 3.45
Fig. 2- The plot of In(f1s) with rlK A: In(tj ls) with rlK: 8 :
In(tp ls) with rl K; C: In(t, " s) with rl K. [System: [Act]o = 1. 02
mol dm-\ [MAlo = 0.0188 mol dm
3
, [8r03' ]0= 0.0675 mol dm" .
[Mn
2
+]o = 0.00250 mol dm-
3
, [H
2
S0
4
]O = 2.58 mol dn'-' ]
the reaction rate constants, but E; , Ep and E, should be
con-esponding to the activation parameters, which are
called the apparent activation parameter in thi s paper,
and their values are E; = 45. 14 kJ mol" , Ep = 60.20 kJ
mol", and E, 67.30 kJ mol", respectively. The results
are in good agreement with the investi gations of An
et al.
6
, who obtained practically the apparent energy
of activation (Ep=61.03kJ mol") for the BZ oscill ating
system containing H
2
S0
4
, BrO}', lactic acid, acetone
and Mn
2
+.
534
INDIAN J CHEM. , SEC. A, MARCH 2002
Tli e e./j'eClS o./,tli e reactallt cOll celltratioll
It is found from the experiment that both the
induction period tieS) and the oscillation cycle tp(s) of
the chemical osci lIati ng reacti on are affected by the
concentrati ons of the reactants; In(t/s) and In(t,,/s)
have good linear relationship with In([Act] omor'
dm'}, In([MAl
o
mor' dm' ), In([BrOJ' ]o mor' dm\
In([Mn2+]o mor' dm\ and In([H
2
S0
4
]0 mor' dm' ) in
the concentrati on range as shown in Table I. Their
linear relationships can be expressed as:
In(t;ls) = ai+bi In([Act]o mor' dm' ) +Ci In([MA]o mor'
dm' ) +d
i
In[Br03' ]0 mor ' dm
3
)
+ ei InClMn2+]u mor' dm' ) + f; mol" dm' )
In(t is) ,= ap+bp +Cp In([MA]o
mol dnl') +dp In[BrO, ]0 mol dnl' )
+ ep In([Mn
2
+]0 mor ' dm' ) + fp In[H
2
S041o mol " dm\
I
Based on the experi rnental data (whi ch are
composed of 37 experimental data, each represents
the average of three parall el experimental results), the
correlati on coefficients in the above two formulae can
be determined by plural linear fitting: ai = 6.88, b
i
=
-0.48, Ci = - 1.1 5, d
i
= 1.03, ei = -0.18, fi = -2.94; ap =
5.10, bp = -0.55, cp = -1.48, dp = 0.93, ep = 0.70, 1'1' =
- 1.28. The plural linear correlati on coeffici ents are
0.999 and 0.998, respect ively. Therefore, the
relationship of the inducti on peri od ti eS) and
oscillating cycle tp(s) with the initial concentrati on of
the reactan ts can be ex pressed as:
t ,(s )=969[ Act ]O,OA8 [M A ]0, ' ,' 5 [B 1'0
3
']0 'OJ [ M n
2
+]o,O.'8
dm'J)'
72
s
tp(s)=
[M n2+]o070[1-I
2
S04h ' 2s(mol dm" ) '68
s
It can be seen from the above relationship, that
increasing IAct] o, IMA 10 and can increase
the rate and shorten induct ion peri od tieS) and
oscillati on cycle tp(s); Increas ing IMn
2
+Jo can shorten
the induction peri od tieS) and elongated the oscillating
cycle tp(s); Increasing [BrO, ' ]0 can elongate the
inducti on period tieS) and oscill ating cycle tp(S) .
The j illl ctions of reactants
Keeping ot her reaction conditions constant , water
was added in place of acetone. It was found that
adding potass ium bromate soluti on produced large
quantiti es of Br2. The system colour changed to
brown and gave off a browil gas. After the induction
peri od, the potenti al decreased without going up, and
the brown colour did not disappear, and no oscillating
react ion took place. The existence of an induction
period demonstrates that the accumulati on process of
HBrOz exists in the oscillating In acidic
medium, under the catalyt ic condit ion of Mn2+, an
oxidati on-reduction react ion takes place between
BrO, ' and MA producing Br2 which causes the
soluti on colour to change to brown. The existence of
large amount of Br2 prevented the accumulation of
HBr02. The brown colour di sappeared qui ckly after
adding acetone and the osci llati on took place. When
nitrogen was rapidl y bubbled through the system with
no acetone added, some osci lIati ons were observed.
So one of the main functi on of acetone is to eliminate
excess ive of Br2 and to produce Br' simultaneously,
I. e.,
Br' can be oxidized by BrO,' , which is favourable
fo r the acc umulati on of 1-1 Br02, so this is an
oscill ati on switch. Increasing the amount of acetone
increased the accumulati on, and the inducti on peri od
became shorter. Thi s accelerated the whol e oscillating
process, and the osci lIati ng cycle became short er.
Keeping the other conditions constant, adding
small amount of bromoacetone shortened the
inducti on period. It indi cates that the accumulati on of
bromoacetone is very important during the induction
period. Bromoacetone was partl y oxidized by Mn'+ to
produce Br', which was favourabi e for the
accumul at ion of HBr02 and shortened the inducti on
period. The reaction process is as foll ows:
Mn
3
+ +CH, COCI-I
2
Br--;;" Mn
2
+ +fBr'+Oxidati on
Product I .. . (2)
In the same way, water was added in the system
repl acing MA. The soluti on colour changed to pink
aft er adding bromate soluti on. The potenti al did not
decrease after the first increase and no oscillating
reaction took place. Then MA was added agai n, the
soluti on colour changed to brown, and the oscill ati ng
phenomenon took place. It indi cated that Mn
2
+ was
regenerated through reduction of Mn
3
+ by MA, i.e.,
Mn]+ + MA --;;.. Mn
2
+ + Oxidation product II ... (3)
If without MA, [Mn' +] (or pot enti al) did not
decrease, no oscill at ing reaction could take place.
Moreover, if MA was added again after the oscillati on
stopped, the oscill ati on reacti on took place again. This
indi cates that MA was consumed in the reaction and
could not be regenerat ed, whi ch acted as the reaction
NOTES
535
substrate. MA played the role of the reductant and
participated in the formation of Br2 at the same time.
So with the increase in the initial concentration of
MA, the rate of regeneration of Mn
2
+ through the
reduction of Mn
3
+ by MA increased, and the induction
period t;(s) and oscillating cycle tp(s) became shorter. .
On replacing Mn2+ by water, though no oscillation
occurred, the solution colour changed to light-brown
gradually. This indicates that though there is no Mn2+
as catalyst, Br03' can partly oxidize MA. This is
because alcohol is more easily oxidized than acid
6
.
7
.
This reaction shown as processes E in the following
section is the side reaction of the oscillating reaction,
consumes part of MA. In the presence of Mn2+, Br03'
and MA reacted rapidly to produce Br2, so that the
colour of the solution changed rapidly to brown. Here
Mn
2
+ plays the catalytic role, which is shown In
mechanism in the following section.
Br2 produced was removed in reaction (I) to
produce B( at the same time. The B( thus formed can
be oxidized by Br03' which is favourable for the
accumulation of HBr02. The reaction process 10 took
place as process A.
At the beginning of the reaction (the induction
period), the concentration of B( is very low. The
catalytic process takes place predominately. With the
increase in the concentration of Mn2+, it may cause
Reaction (II) and (10) proceed very fast and more Br2
is produced. This further causes reaction (1) to
produce more B( and then reaction (4) accelerates the
accumulation of HBr02. The time to reach the critical
value o( the oscillation is very short, so the induction
period t;(s) becomes shorter with the increase in
[Mn
2
+]o. At the beginning of the oscillation, Mn
3
+
returns to Mn
2
+ through reactions (3) and (2). When
[Mn2+]o is large, though the rate of reaction (3)
becomes faster, every oscillation reaction consumes
large amount of MA, causing [MA] to become lower;
and during each cycle the time of Mn
3
+ changing to
[Mn2+] becomes longer with the increase in [Mn
2
+]o;
so the oscillating cycle tp(s) becomes longer with the
increase in fMn
2
+]. When Br03' is not in the reaction
system, the solution colour does not change, and no
oscillating phenomenon takes place. If Br03' is added
at the last stage of the oscillating process, the
oscillation restarts. This indicates that in the
oscillating system, Br031 is consumed and not re-
formed. Without the catalysis of Mn2+, BrO)' can still
oxidize part of MA and consume part of MA,
(Process E) . So, on increasing the concentration of
Br03', more MA is consumed. Therefore, with the
increase in [Br03' ], the induction period t;(s) and the
oscillating cycle tp(s) become longer.
The effect of the radical inhibitor
Keeping other conditions constant, acrylonitrile
was added into a reaction system, the oscillation
stopped immediately. Also on adding ethanol into the
reaction system, the oscillation stopped immediately
after a few oscillations. Acrylonitrile and ethanol are
both radical inhibitors; it indicates that radicals are
involved in the oscillation reaction. It is reported \(J
that the possible radical reaction process may take
place as process B.
Discussion of the oscillating mechanism
Based on the above discussions, it is proposed that
the system may undergo the following five
processes I 1.12:
Process A:
.. . (4)
HBr0
2
+ B(+ W HOBr . .. (5)
... (6)
. .. (I )
Process B:
... (7)
... (8)
... (9)
4Mn
3
++HOBr+HBr0
1
... (II ) ,
Process C: Mn
3
+ transformed to Mn
2
+ through reacli ons (3)
and (2)
Process D: B( was regenerated by reactions ( I) and (2)
Process E: BrO)' oxidized MA through reactions (4) , (5) and ( 10)
shown as follows:
1I2Br2+0xidation Product I .. . ( 10)
The existence of the induction period indicates that
the mechanism is an automatic catalytic process
dominated by Br02" produced in reaction (8) during
Process B. The catalyst is HBr02. B( plays the role of
kinetic control. The multitude of [Br'] determined the
rate of the self-catalytic oxidization. When fBr' ] is
536
INDI AN J CHEM. , SEC. A, MARCH 2002
large enough, Process A dominates, and Process B is
inhibited, which causes the formation rate of Br02to
become slower. The outcome of Process A is to make
Process B dominating by removi ng B( from system.
The proceeding of Process B results in [Mn
3
+] in
Reaction (9) increasing constantly, which causes
Process C to proceed leading to regeneration of Mn
2
+.
At the same time, B( is formed through Process D.
These processes go round and round, the oscillating
phenomenon of [B(] or [Mn
3
+]/[Mn
2
+] begins to take
place.
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