Effect of Initial Substrate Concentrations and Temperature on the ...

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© 2013 The Chemical Society of Japan

Effect of Initial Substrate Concentrations and Temperature on the Oscillatory Behavior of Phloroglucinol-Based Belousov­Zhabotinsky Reaction Usma Gull, Ghulam Mustafa Peerzada,* Nadeem Bashir Ganaie, and Nisar Ahmad Dar Department of Chemistry, University of Kashmir, Srinagar J&K-190006, India Received August 15, 2012; E-mail: [email protected], nadeemganaie@rediffmail.com

The present study introduces the use of phloroglucinol (1,3,5-trihydroxybenzene) as organic substrate in BZ reaction for the first time. This work has been carried out to assess the influence of initial reagent concentrations on the behavior of phloroglucinol­bromate­ferroin-based BZ reaction in a stirred batch reactor. The oscillations are followed by observing the change in redox potential. Different oscillatory parameters like induction time (tin), time period (tp), amplitude (A), frequency (v), and number of oscillations (N) show different changes with respect to changes in the initial concentrations of organic substrate, bromate and sulfuric acid, and these observations have been explained on the basis of FKN mechanism. The behavior of the aforesaid system in different aqueous acid media has been reported and it is found that sulfuric acid is the best medium for studying the system as it shows a wide oscillatory window compared to that of nitric acid. In phosphoric and perchloric acids the system does not show any oscillatory behavior. Activation parameters of the reaction have been derived by studying the reaction over a temperature range of 15 to 40 « 0.1 °C. The effect of different catalysts on the oscillatory behavior has been studied and it is found that the system gives good oscillatory behavior with ferroin and Ce(III) whereas a poor response is seen when Mn(II) and Ce(IV) are used as catalysts.

The dimensions of nonequilibrium chemistry, especially the study of systems far from equilibrium, are growing continuously on account of interests in real systems such as living systems. The oscillatory chemical reactions are the best examples of systems far from equilibrium that display many unusual features. These chemical reactions have been widely studied in the areas of theoretical and experimental kinetics over last the few decades1,2 and have potential applications in various areas like physics, chemistry and biology. Biochemical reactions such as glycolytic oscillations and peroxidasecatalyzed oxidation of nicotinamide adenosine dehydrogenase (NADH) have generated considerable interest in this field.3­5 The Belousov­Zhabotinsky (BZ) reaction6­8 is one of the most studied oscillatory chemical reactions in both batch and CSTR modes which involves the oxidation of an organic substrate by bromate ion in acidic medium. The reaction can be catalyzed or uncatalyzed. The reaction is catalyzed by metal ions in free form e.g, Ce3+/Ce4+,1,9,10 Mn2+/Mn3+,11 as complexes [Ru(bpy)3]2+/[Ru(bpy)3]3+,12­15 [Fe(phen)3]2+/[Fe(phen)3]3+,16 or in the form of macrocyclic complexes.17,18 The famous FKN mechanism19 proposed by Field, Koros, and Noyes is of special interest in explaining the complex nature of BZ reactions. A simple mathematical 3-variable model20 formulated by Field and Noyes can describe many of the complex dynamic behaviors of the system including excitability,21,22 bistability,23 target or spiral pattern24,25 in a thin unstirred reaction layer, stirring effects,26,27 and chaos.28 The uncatalyzed bromate oscillators do not involve any metal ion catalyst and the organic substrate is usually a polyphenol or a polyaniline derivative29­31 which plays the role of catalyst as well. These bromate oscillators are explained by a slightly modified FKN mecha-

nism known as OKN mechanism given by Orban, Koros, and Noyes.32 Long-term behavior of BZ reaction in a closed reactor,33 self-oscillating gels driven by BZ reaction,34 and pulse-coupled oscillators35 are some of the recent advancements in this field. Tikhonova et al. (1978) were the first to consider the quantitative use of oscillatory reactions for analytical purposes.36 Thus, the introduction of pulse perturbation technique (APP) gave a new and vast dimension to the analytical investigation of BZ reaction. In the present study, the oscillatory behavior of the ferroincatalyzed BZ reaction using phloroglucinol (1,3,5-trihydroxybenzene) as organic substrate has been investigated. This substrate has not been used so far as organic substrate in BZ reaction. Its isomer pyrogallol (1,2,3-trihydroxybenzene)37­39 has been investigated in both catalyzed and uncatalyzed BZ reactions. Phloroglucinol has sufficient solubility in aqueous acid media and shows a broad oscillatory region with respect to initial reagent concentrations. Phloroglucinol itself or in combination with other substances as well as its derivatives have a vast array of activities like anticancer, antispasmodic, anti-inflammatory, antibacterial, antitumor, neuro-regenerative, and antioxidant properties.40­42 A detailed study of the reaction system has been carried out at 30 « 0.1 °C. An attempt has been made to study the dynamics of the reaction over a temperature range (15 to 40 « 0.1 °C) with respect to its effect on different oscillatory parameters like induction period (tin), time period (tp), amplitude (A), and number of oscillations (N). As medium has a profound effect in a BZ reaction,43 phloroglucinol-based BZ system has been studied in different aqueous acid media like nitric acid, sulfuric acid, perchloric acid, and orthophosphoric acid. A systematic study of the

Published on the web February 9, 2013; doi:10.1246/bcsj.20120217

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Experimental All chemicals used were of analytical grade. The reagents used were phloroglucinol (Himedia), potassium bromate (Merck), ferroin (Merck), ceric sulfate (Sd-fine), cerous sulfate (CDH), manganese(II) sulfate (BDH), sulfuric acid (Merck), nitric acid (Fischer Scientific), orthophosphoric acid (Merck), perchloric acid (Qualigens), sodium bromate (Merck), and potassium nitrate (Merck). Potentiometric measurements were carried out using an Orion 4 STAR digital multimeter. The indicator and reference electrodes used were platinum and SCE respectively. SCE was dipped in a half-cell containing 2.5 © 10¹4 mol L¹1 solution of potassium chloride and the platinum electrode was dipped in a half-cell containing the reaction mixture. The two half-cells were connected by a salt-bridge filled with agar gel prepared in potassium nitrate. The thermostatic conditions were achieved by using a water bath (ADVENTEC-SRS266PA) set up at desired temperature. Before mixing all the solutions were kept under thermostatic conditions for about 15 min in order to attain the desired temperature. Round bottom glass tubes of 100 mm © 25 mm size were used as reaction cells. Uniform stirring rate of 600 rpm was achieved with a magnetic stir bar (8 mm, Cole Parmer-04765­55) by using a compatible magnetic stirrer (ADVANTEC-SRS266PA) fitted with the water bath. All the stock solutions were made in aqueous acid medium except ferroin which was made in water. The stock solutions were stored overnight at room temperature (20 °C). The total volume of the reaction mixture used in each experiment was 9 mL (3 mL each of potassium bromate, metal catalyst, and phloroglucinol solutions) and the reaction was initiated by the addition of potassium bromate solution. Consecutive trials were taken to ensure the reproducibility of the results. Results and Discussion As the experiments in the present study have been performed under batch conditions, the observed chemical oscillations have a transient character. The reaction is allowed to proceed for 1­1.5 h and after a short induction period the system bifurcates into an oscillatory regime. During the induction period the reaction mixture is red and as the solution enters into the oscillatory regime it turns blue with the simultaneous quick increase in redox potential indicating the oxidation of Ferroin.44 ½FeðPhenÞ3 2þ  þ BrO2 • þ Hþ ! ½FeðPhenÞ3 3þ  þ HBrO2

ð1Þ

A typical oscillatory profile with optimum concentrations of reactants and the averaged oscillatory characteristics is given in Figure 1. The oscillatory characteristics of the system such as induction period, number of oscillations, amplitude, and time period are dependent on the initial conditions of the system (concentrations, temperature, etc.). Table 1 shows the influence of different concentrations of phloroglucinol on oscillatory parameters keeping concentra-

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oscillatory behavior with respect to different metal catalysts like ferroin, Ce(IV), Ce(III), and Mn(II) has been carried out in this work.

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Time/s Figure 1. Typical oscillating profile of the system containing [phloroglucinol] = 0.012 M, [ferroin] = 0.005 M, [BrO3¹] = 0.09 M, [H2SO4] = 1.5 M at 30 « 0.1 °C. Table 1. Variation in [Phloroglucinol] Having Other Species Such as [Ferroin]0 = 0.005 M, [KBrO3]0 = 0.09 M, [H2SO4]0 = 1.5 M at Temperature 30 « 0.1 °C [Phloroglucinol] /M 0.006 0.008 0.01 0.012 0.014 0.016

Induction Number of oscillations period N tin/s 85 11 130 20 280 20 345 22 395 26 440 22

Time Amplitude period A/mV tp/s 78.27 38.00 72.21 44.44 63.25 47.89 68.95 49.28 36.03 57.20 50.54 63.57

tions of other reagents constant at 30 « 0.1 °C. The data reveals that with increase in the concentration of phloroglucinol the induction period increases. When the concentration of phloroglucinol is increased, the rate of process C of the FKN mechanism i.e., oxidation of substrate may increase, thus it takes more time to accumulate the critical amount of bromo derivative of the substrate leading to increase in induction period. Time period increases with increase in concentration of phloroglucinol following the same reason as in induction time. The number of oscillations increase with increase in phloroglucinol concentration up to 0.014 M, with further increase in concentration leading to decrease in the number of oscillations. Table 2 shows the variation of oscillatory parameters at different concentrations of bromate while keeping concentration of other reagents constant. It is observed that with increase in concentration of bromate induction period decreases owing to the faster accumulation of bromo derivative of organic substrate.45 The time period of oscillations shows the same trend and is explained on the same grounds following the FKN mechanism,19,20 the overall process of which consists of the following three steps: ð2Þ BrO3  þ 5Br þ 6Hþ ! 3Br2 þ 3H2 O BrO3  þ HBrO2 þ 2Mred þ 3Hþ ! 2HBrO2 þ 2Mox þ H2 O ð3Þ 2Mox þ Substrate þ Bromo derivative ð4Þ ! fBr þ 2Mred þ other products

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Table 2. Variation in [Bromate] Having Other Species Such as [Ferroin]0 = 0.005 M, [Phloroglucinol]0 = 0.012 M, [H2SO4]0 = 1.5 M at Temperature 30 « 0.1 °C Induction period tin/s 795 425 345 305 230 195 105

[Bromate] /M 0.06 0.08 0.09 0.10 0.11 0.12 0.14

Number of oscillations N 7 25 22 25 25 >20 >20

Amplitude A/mV 63.28 51.40 67.00 54.84 63.88 43.82 44.95

Table 3. Variation in [Ferroin] Having Other Species Such as [Phloroglucinol]0 = 0.012 M, [KBrO3]0 = 0.09 M, [H2SO4]0 = 1.5 M at Temperature 30 « 0.1 °C

Time period tp/s 80.83 64.79 46.81 39.58 30.20 27.61 20.00

[Ferroin] /M 0.001 0.002 0.003 0.004 0.005 0.006

Induction period tin/s 455 370 365 355 345 335

Number of oscillations N 7 18 20 21 22 23

Amplitude A/mV 44.00 45.71 54.44 51.70 67.00 64.78

Time period tp/s 52.50 43.21 41.17 54.25 46.81 55.26

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Table 3 shows the effect of varying concentrations of metal catalyst (ferroin) on oscillatory parameters. It is observed that with increase in concentration of ferroin the induction period decreases although the decrease is not so sharp. This can be explained on the basis of the combined effect of processes B and C of the FKN mechanism, where the autocatalytic generation of HBrO2 is enhanced due to the presence of metal ion. The variation of various oscillatory parameters with phloroglucinol, bromate, ferroin, and sulfuric acid is shown in Figure 2. Table 4 shows a comparative trend of the effect of various acids like sulfuric acid, nitric acid, perchloric acid, and ortho-

phosphoric acid for the phloroglucinol­bromate­ferroin BZ system. After a thorough investigation it is found that sulfuric acid is the best medium to study this BZ system in terms of its good response of various oscillations attributes. The system shows oscillations over a wide range of sulfuric and 1.5 M sulfuric acid has been found most suitable to this effect. The induction period and time period decreases with increase in sulfuric acid concentration as [H+] has a crucial role in bromine generation which is evident from the FKN mechanism. Nitric acid shows a narrow oscillatory region with a few small amplitude oscillations as compared to sulfuric acid. This can be attributed to counter-ion effects. Because of the formation of precipitate of ferroin perchlorate,46 no oscillatory behavior is

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Concentration of acid /M 1.00 1.25 1.50 1.75 2.00 2.00 2.50 3.00 3.50 4.00

Acid H2SO4

HNO3

Induction period tin/s 1085 610 345 190 70 ®a) 535 355 85 20

Number of oscillations N 8 15 22 17 16 ®a) 6 14 9 3

Time period tp/s 230 126.42 46.81 33.92 25.83 ®a) 31 41.92 40.5 132.5

a) No oscillations are seen.

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Table 4. Variation in Oscillatory Parameters of Phloroglucinol­Bromate­Ferroin System with Different Aqueous Acid Media at Temperature 30 « 0.1 °C

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Table 5. Oscillatory Parameters at Different Temperatures for the System Consisting of [Phloroglucinol]0 = 0.012 M, [KBrO3¹]0 = 0.09 M, [Ferroin]0 = 0.005 M, and [H2SO4]0 = 1.5 M

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Time/s Figure 3. Comparison of various metal-catalyzed systems consisting of: (a) [ferroin] = 0.005 M, [phloroglucinol] = 0.012 M, [bromate] = 0.09 M, and [H2SO4] = 1.5 M; (b) [Mn(II)] = 0.005 M, [phloroglucinol] = 0.018 M, [bromate] = 0.15 M, and [H2SO4] = 2.0 M; (c) [Ce(IV)] = 0.002 M, [phloroglucinol] = 0.012 M, [bromate] = 0.12 M, and [H2SO4] = 2.0 M; (d) [Ce(III)] = 0.0005 M, [phloroglucinol] = 0.018 M, [bromate] = 0.2 M, and [H2SO4] = 2.0 M.

observed with aqueous perchloric acid as a medium. It is pertinent to mention here that sodium bromate was used instead of potassium bromate in perchloric acid medium to avoid precipitation of potassium perchlorate. With aqueous orthophosphoric acid as a medium the system does not show any oscillatory response and the ferroin remains in reduced form (red) during the course of the reaction indicating its lower tendency to get oxidized in this medium. Metal ion catalysts have profound effect on the oscillatory behavior of a BZ reaction.47,48 Figure 3 shows the potentiometric plots of ferroin-, Mn(II)-, Ce(IV)-, and Ce(III)-catalyzed phloroglucinol-based BZ systems at concentrations that yield a maximum number of oscillations. The concentration windows of various initial reagents differ significantly with use of the aforementioned metal catalysts. The system shows more number of oscillations with ferroin and Ce(III) as catalysts in comparison to that of Ce(IV) and Mn(II). Figure 4 shows

Temperature T/°C 15 20 25 30 35 40

Induction period tin/s 1960 1090 590 345 200 115

Number of oscillations N 11 11 21 22 19 17

Amplitude A/mV 66.72 58.10 47.61 67.00 49.68 74.94

Time period tp/s 152.5 85.55 76.66 46.81 44.72 22.94

the comparison of the dynamic behavior in systems with same initial conditions but using four different catalysts. These catalysts show different behavior as far as the number of oscillations is concerned. This can be attributed to their different redox potential values.49 As E° ([Fe(phen)3]3+/ [Fe(phen)3]2+) < E° (Ce4+/Ce3+) < E° (Mn3+/Mn2+), ferroin acts only as the oscillating catalyst and the catalyst is regenerated through the reduction of [Fe(phen)3]3+ by the radicals of phloroglucinol and other intermediates. Thus, when ferroin is used as catalyst the consumption of phloroglucinol is less resulting in the maximum number of oscillations. In the presence of Ce(IV) and Mn(II) the substrate is more quickly oxidized leading to lesser number of oscillations. Temperature plays an important role in the dynamics of BZ reaction. A number of studies are available about the influence of temperature on BZ reaction.50­54 Koros first reported the dependence of oscillatory frequency on temperature.55 Table 5 and Table 6 give the variation of oscillatory parameters with change in temperature ranging from 15 to 40 « 0.1 °C. With increase in temperature, it is observed that induction period and time period of oscillations decrease. This is because of the increase in the rate of formation of a critical amount of bromo derivative of substrate19 with the increases in temperature which leads to decrease in induction period. The decrease in induction time shows a linear relationship with temperature. Since, as

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Table 6. Oscillatory Parameters at Different Temperatures for the System Consisting of [Phloroglucinol]0 = 0.018 M, [KBrO3¹]0 = 0.2 M, [Ce3+]0 = 0.0005 M, and [H2SO4]0 = 2.0 M Temperature T/°C 15 20 25 30 35 40

Number of oscillations N ®a) 6 9 20 21 21

Induction period tin/s 845 485 155 75 40

Amplitude A/mV 58.50 62.87 49.75 48.8 31.84

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Figure 6. Potential (mV) versus time (s) plot showing variation of oscillatory parameters of the system containing [phloroglucinol] = 0.018 M, [BrO3¹] = 0.2 M, [Ce(III)] = 0.0005 M, and [H2SO4] = 2.0 M at temperatures: (a) 15, (b) 20, (c) 25, (d) 30, (e) 35, and (f ) 40 °C.

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Figure 5. Potential (mV) versus time (s) plot showing variation of oscillatory parameters of the system containing [phloroglucinol] = 0.012 M, [BrO3¹] = 0.09 M, [ferroin] = 0.005 M, and [H2SO4] = 1.5 M at temperatures: (a) 15, (b) 20, (c) 25, (d) 30, (e) 35, and (f ) 40 °C.

expected, the rate of reaction increases with the increase in temperature, the time period of oscillations decreases. The number of oscillations increase up to 30 °C and then decreases with further increase in temperature (Figure 5 and Figure 6). With increase in temperature up to 30 °C, the rate of reaction increases in accordance with the Arrhenius equation, therefore, the number of oscillations increases. The system being closed, at higher temperature it is driven more quickly to thermodynamic equilibrium,56,57 hence the number of oscillations decreases. The apparent values of thermodynamic parameters like enthalpy of activation (¦H#), entropy of activation (¦S#), and activation energy (Ea#) have been calculated (Table 7) using Eyring­Polyani and Arrhenius equations. Because of the complex nature of BZ reaction, these activation parameters cannot be attributed to any of the elementary reaction steps and provide information about the overall effect of temperature on the BZ reaction. The temperature dependence of induction time and time period of ferroin and cerium based BZ systems are reported in Figure 7. Conclusion This study illustrates that the catalyzed bromate­phloroglucinol BZ reaction is capable of producing temporal oscillations

¦H #/kJ mol¹1 ¦S #/kJ mol¹1 Ea#/kJ mol¹1

Oscillation parameters tin/s tp/s Ce(III) Ferroin Ce(III) Ferroin 119.14 82.42 65.27 48.53 0.104 ¹0.021 ¹0.064 ¹0.117 121.66 84.91 67.79 50.20

in a closed stirred system making it possible to use this system for exploring nonlinear dynamics. This new system is studied at varying concentration ranges of different reagents which lead to the establishment of optimal concentration of various reagents at which the system shows best oscillatory profile. The temperature dependence of various oscillatory parameters is studied and it is found that there is a decrease in induction period and oscillatory period of oscillations with increase in temperature. The system gives good response with aqueous sulfuric acid compared to that of nitric acid, whereas in orthophosphoric acid and perchloric acid the system does not show any oscillatory behavior owing to the formation of ferroin perchlorate in the latter. The system shows a dynamic behavior with respect to different metal-ions as catalysts with an expressive oscillatory behavior with ferroin and Ce(III) and poor responses with Mn(II) and Ce(IV) as catalysts due to their different redox potentials. This BZ system because of having structural resemblance with several biomolecules may have a role in studying interactive behavior in vitro using BZ system. The authors are highly thankful to University Grants Commission for providing financial support and also to the Department of Chemistry, University of Kashmir, Srinagar for providing infrastructural facilities to accomplish the work conveniently.

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Figure 7. Temperature dependence of (a) induction time and (b) time period of ferroin catalyzed system with [ferroin] = 0.005 M, [phloroglucinol] = 0.012 M, [bromate] = 0.09 M, [H2SO4] = 1.5 M and cerium-catalyzed system with [Ce3+] = 0.0005 M, [phloroglucinol] = 0.018 M, [bromate] = 0.2 M, [H2SO4] = 2.0 M. References 1 R. J. Field, F. W. Schneider, J. Chem. Educ. 1989, 66, 195. 2 K. Sriram, Chaos, Solitons Fractals 2006, 28, 1055. 3 H. Degn, L. F. Olsen, J. W. Perram, Ann. N.Y. Acad. Sci. 1979, 316, 623. 4 A. Goldbeter, S. R. Caplan, Annu. Rev. Biophys. Bioeng. 1976, 5, 449. 5 A. Goldbeter, Biochemical Oscillations and Cellular Rhythms: The Molecular Bases of Periodic and Chaotic Behavior, Cambridge University Press, London, 1996. 6 R. J. Field, M. Burger, Oscillations and Traveling Waves in Chemical Systems, Wiley Interscience, New York, 1985. 7 B. P. Belousov, Ref. Radiats. Med., Moscow 1959, 145. 8 A. M. Zhabotinsky, Dokl. Akad. Nauk SSSR 1964, 157, 392. 9 A. D. Karavaev, V. P. Kazakov, G. A. Tolstikov, V. V. Yakshin, N. L. Khokhlova, J. Anal. Chem. USSR 1986, 41, 42. 10 R. T. Echols, M. K. Carroll, J. F. Tyson, Anal. Proc. 1995, 32, 3. 11 A. I. Zhuravlev, V. M. Trainin, J. Biolumin. Chemilumin. 1990, 5, 227. 12 H. R. Weigt, Angew. Chem., Int. Ed. Engl. 1992, 31, 355. 13 V. P. Kazakov, A. D. Karavayev, S. R. Vakhidova, React. Kinet. Catal. Lett. 1991, 45, 199. 14 H. Saigusa, Chem. Phys. Lett. 1989, 157, 251. 15 A. D. Karavaev, V. P. Kazakov, React. Kinet. Catal. Lett. 1987, 34, 15. 16 K. B. Yatsimirskii, P. E. Strizhak, T. S. Ivaschenko, Talanta 1993, 40, 1227. 17 K. B. Yatsimirskii, L. P. Tikhonova, L. N. Zakrevskaya, Y. D. Lampeka, A. G. Kolchinskii, React. Kinet. Catal. Lett. 1982, 21, 381. 18 G. Hu, L. Chen, J. Zhang, P. Chen, W. Wang, J. Song, L. Qiu, J. Song, L. Hu, Cent. Eur. J. Chem. 2009, 7, 291. 19 R. J. Field, E. Koros, R. M. Noyes, J. Am. Chem. Soc. 1972, 94, 8649. 20 R. J. Field, R. M. Noyes, J. Chem. Phys. 1974, 60, 1877. 21 R. J. Field, R. M. Noyes, Faraday Symp. Chem. Soc. 1974,

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