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. References Zhao X Z, Zhao H X, Xu Y T & Zang Y R, HI/axil e TOlI gbao, 30( 1985) 586. 2 Li H X, Liu M. Wang S X, Xu H H & Fu C J, Acta PhysChilll Sillica, 6( 1990)609. 3 Lu C H. Xu Z Q, XU J D & Ni S S. Hll axll e TOlI giJao. 2( 1992) 30. 4 Shen S G, Zhao J G, San J H & Dang G S. J.f-l elJl:'i Ulli versity, 5( 1995) 21. 5 Yuan C L, Li Z X & Wang J C, Acta Phv-Chilll Sill icu. 10(1994) 87. 6 An C J, Zhuang L, Liu Y & Lin Z X. 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