A novel kinetic method for determination of trace amounts of cobalt ion was proposed and validated. The method is based on adding malic acid into classical Belousov-Zhabotinskii (B-Z) oscillating chemical system to ...A novel kinetic method for determination of trace amounts of cobalt ion was proposed and validated. The method is based on adding malic acid into classical Belousov-Zhabotinskii (B-Z) oscillating chemical system to form a double substrate one. The results showed that when the concentration of cobalt ion was in the range of 5.27× 10^-8 to 5.37 × 10^-12 mol L^-1, the change of the oscillating period was directly proportional to the negative logarithm of cobalt ion concentration. The sensitivity and precision of the developed method were quite satisfactory. The limit of detection was down to 5.20 × 10^-13 mol L^-1 which was a highest sensitivity found for determination of metal ions using oscillating chemical reaction so far. Some factors influencing the determination were also examined. The method has been successfully used to determine cobalt ion in vitamin B12 injection.展开更多
The oscillation behavior of a two-dimension lattice-gas Brusselator model was investigated. We have adopted a coarse-grained kinetic Monte Carlo (CG-KMC) procedure, where m×m microscopic lattice sites are group...The oscillation behavior of a two-dimension lattice-gas Brusselator model was investigated. We have adopted a coarse-grained kinetic Monte Carlo (CG-KMC) procedure, where m×m microscopic lattice sites are grouped together to form a CG cell, upon which CG processes take place with well-defined CG rates. Such a CG approach almost fails if the CG rates are obtained by a simple local mean field (s-LMF) approximation, due to the ignorance of correlation among adjcent cells resulting fl'om the trimolecular reaction in this nonlinear system. By proper incorporating such boundary effects, thus introduce the so-cMled b-LMF CG approach. Extensive numerical simulations demonstrate that the b-LMF method can reproduce the oscillation behavior of the system quite well, given that the diffusion constant is not too small. In addition, the deviation from the KMC results reaches a nearly zero minimum level at an intermediate cell size, which lies in between the effective diffusion length and the minimal size required to sustain a well-defined temporal oscillation.展开更多
A novel oscillating chemical reaction using ninhydrin as a single organic substrate was represented in this paper. It distinguished from the classically catalyzed BZ oscillating chemical reaction due to there was no a...A novel oscillating chemical reaction using ninhydrin as a single organic substrate was represented in this paper. It distinguished from the classically catalyzed BZ oscillating chemical reaction due to there was no active methene (CH2=) and/or enol structure in the ninhydrin molecule, which served as single organic substrate. This suggested that the substrates used in catalyzed BZ reaction were not always the organic compounds containing active methene (CH2=) and/or enol structure and bromination process in this kind of catalyzed chemical oscillating reaction was not also necessary.展开更多
The electrical oscillations across a liquid membrane in water/oil/water system was studied with octanol as oil phase by introducing two opposite charged surfactants in oil and aqueous phase, respectively. The sustaine...The electrical oscillations across a liquid membrane in water/oil/water system was studied with octanol as oil phase by introducing two opposite charged surfactants in oil and aqueous phase, respectively. The sustained and rhythmic oscillation was observed. To a certain extent, the features of the oscillation (e.g. induction time, frequency, life time and orientation of the pulse pikes) strongly depend on the property of surfactant, dissolved in octanol. The mechanism may be explained by the formation and destruction of dual-ion surfactant membrane accompanying with emulsification at the interface and considering the coupling effect of diffusion and associated reaction in the vicinity of the interface.展开更多
A new chemical oscillating reaction system involving the manganese(II)-catalyzed reaction among potassium bromate, acetone and tyrosine in acidic medium was described in this paper. The apparent activation energy of ...A new chemical oscillating reaction system involving the manganese(II)-catalyzed reaction among potassium bromate, acetone and tyrosine in acidic medium was described in this paper. The apparent activation energy of the induction period (Ein) and that of oscillation period (Ep) were calculated, Ein=110.61KJ/mol, Ep=159.41KJ/mol. The optimum concentration of each reactant was investigated and a steady chemical oscillating system was obtained.展开更多
A new Belousov-Zhabotinsky oscillator induced by Triton X-100 (a nonionic surfactant)with glucose as the organic substrate and Ce^(4+)as the catalyst has been reported in this paper.
In this paper we report a chemical oscillation catalyzed by [Ni(Me2[14]1,3-diene N4)]2+ (Me2[14]l,3-diene N4 denotes 2,3-dimethyl-l,4,8,ll-tetraazacyclotetradeca-1,3-diene) in BrO3--pyruvic acid-H2SO4 system.The domai...In this paper we report a chemical oscillation catalyzed by [Ni(Me2[14]1,3-diene N4)]2+ (Me2[14]l,3-diene N4 denotes 2,3-dimethyl-l,4,8,ll-tetraazacyclotetradeca-1,3-diene) in BrO3--pyruvic acid-H2SO4 system.The domain of the existence of the oscillation was obtained.The effects of initial concentration of the components on the oscillation were studied.The features of the oscillations were described in detail.We also examined the effects of Ag+,Hg2+,CCl4,free radical inhibitors,etc.on the osillations.展开更多
Based on a simple nonideal chemical reaction model, the closed system with reversible nonideal reactions and illumination is shown to be able to exhibit sustained oscillation. The essential points in the occurrence of...Based on a simple nonideal chemical reaction model, the closed system with reversible nonideal reactions and illumination is shown to be able to exhibit sustained oscillation. The essential points in the occurrence of such oscillations are the nonideality of reacting media, which gives rise to multiple chemical equilibria, and the energy flow through illumination and heat conduction, which gives rise to spontaneous transitions repeatedly between the multiple equilibrium states. During the oscillation, reacting media undergo only reversible chemical transformation and all irreversibilities are restricted to the coupling of the system to external world. This oscillation provides an example of the so-called endoreversible machine and a possible way to convert radiation energy of the light directly into mechanical energy.展开更多
Temporal oscillations of the bromate-4-aminophenol system have been studied in the presence of four different catalysts: tris(1,10-phenanthroline)iron(Ⅱ) sulfate (ferroin), Ce(Ⅲ), Mn(Ⅱ), and Fe(Ⅱ). Tr...Temporal oscillations of the bromate-4-aminophenol system have been studied in the presence of four different catalysts: tris(1,10-phenanthroline)iron(Ⅱ) sulfate (ferroin), Ce(Ⅲ), Mn(Ⅱ), and Fe(Ⅱ). Transient temporal oscillations were observed in the four catalyzed systems when the reactions were conducted in a stirred batch reactor. The induction time was prolonged by the presence of ferroin, but it was shortened in the Ce(Ⅲ)- and Mn(Ⅱ)-catalyzed systems. On the other hand, the number of peaks was significantly decreased in the presence of ferroin. The development of oscillatory behaviour was found to be more sensitive to the ratio of bromate and 4-aminophenol concentration than to their absolute concentrations. The reaction rates of 4-aminophenol with Ce(IV) and 4-aminophenol with ferritin were measured directly by spectroscopic methods in a sulfuric acid medium.展开更多
基金the Project of International Cooperation between China and Ukraine(No.043-05)National Natural Science Foundation and Key Lab of Polymer Materials of Gansu Province for their financial supports.
文摘A novel kinetic method for determination of trace amounts of cobalt ion was proposed and validated. The method is based on adding malic acid into classical Belousov-Zhabotinskii (B-Z) oscillating chemical system to form a double substrate one. The results showed that when the concentration of cobalt ion was in the range of 5.27× 10^-8 to 5.37 × 10^-12 mol L^-1, the change of the oscillating period was directly proportional to the negative logarithm of cobalt ion concentration. The sensitivity and precision of the developed method were quite satisfactory. The limit of detection was down to 5.20 × 10^-13 mol L^-1 which was a highest sensitivity found for determination of metal ions using oscillating chemical reaction so far. Some factors influencing the determination were also examined. The method has been successfully used to determine cobalt ion in vitamin B12 injection.
文摘The oscillation behavior of a two-dimension lattice-gas Brusselator model was investigated. We have adopted a coarse-grained kinetic Monte Carlo (CG-KMC) procedure, where m×m microscopic lattice sites are grouped together to form a CG cell, upon which CG processes take place with well-defined CG rates. Such a CG approach almost fails if the CG rates are obtained by a simple local mean field (s-LMF) approximation, due to the ignorance of correlation among adjcent cells resulting fl'om the trimolecular reaction in this nonlinear system. By proper incorporating such boundary effects, thus introduce the so-cMled b-LMF CG approach. Extensive numerical simulations demonstrate that the b-LMF method can reproduce the oscillation behavior of the system quite well, given that the diffusion constant is not too small. In addition, the deviation from the KMC results reaches a nearly zero minimum level at an intermediate cell size, which lies in between the effective diffusion length and the minimal size required to sustain a well-defined temporal oscillation.
文摘A novel oscillating chemical reaction using ninhydrin as a single organic substrate was represented in this paper. It distinguished from the classically catalyzed BZ oscillating chemical reaction due to there was no active methene (CH2=) and/or enol structure in the ninhydrin molecule, which served as single organic substrate. This suggested that the substrates used in catalyzed BZ reaction were not always the organic compounds containing active methene (CH2=) and/or enol structure and bromination process in this kind of catalyzed chemical oscillating reaction was not also necessary.
文摘The electrical oscillations across a liquid membrane in water/oil/water system was studied with octanol as oil phase by introducing two opposite charged surfactants in oil and aqueous phase, respectively. The sustained and rhythmic oscillation was observed. To a certain extent, the features of the oscillation (e.g. induction time, frequency, life time and orientation of the pulse pikes) strongly depend on the property of surfactant, dissolved in octanol. The mechanism may be explained by the formation and destruction of dual-ion surfactant membrane accompanying with emulsification at the interface and considering the coupling effect of diffusion and associated reaction in the vicinity of the interface.
基金sponsored by the Project of Youth Teachers Foundation of Education Ministry(3076),the Project of KJCXGC-01,NWNUNational Natural Science Foundation of China(29875018)
文摘A new chemical oscillating reaction system involving the manganese(II)-catalyzed reaction among potassium bromate, acetone and tyrosine in acidic medium was described in this paper. The apparent activation energy of the induction period (Ein) and that of oscillation period (Ep) were calculated, Ein=110.61KJ/mol, Ep=159.41KJ/mol. The optimum concentration of each reactant was investigated and a steady chemical oscillating system was obtained.
文摘A new Belousov-Zhabotinsky oscillator induced by Triton X-100 (a nonionic surfactant)with glucose as the organic substrate and Ce^(4+)as the catalyst has been reported in this paper.
基金Project supported by the National Natural Science Foundation of China and the State Key Laboratory of Coordination Chemistry in Nanjing University.
文摘In this paper we report a chemical oscillation catalyzed by [Ni(Me2[14]1,3-diene N4)]2+ (Me2[14]l,3-diene N4 denotes 2,3-dimethyl-l,4,8,ll-tetraazacyclotetradeca-1,3-diene) in BrO3--pyruvic acid-H2SO4 system.The domain of the existence of the oscillation was obtained.The effects of initial concentration of the components on the oscillation were studied.The features of the oscillations were described in detail.We also examined the effects of Ag+,Hg2+,CCl4,free radical inhibitors,etc.on the osillations.
基金Project supported by the National Natural Science Foundation of China.
文摘Based on a simple nonideal chemical reaction model, the closed system with reversible nonideal reactions and illumination is shown to be able to exhibit sustained oscillation. The essential points in the occurrence of such oscillations are the nonideality of reacting media, which gives rise to multiple chemical equilibria, and the energy flow through illumination and heat conduction, which gives rise to spontaneous transitions repeatedly between the multiple equilibrium states. During the oscillation, reacting media undergo only reversible chemical transformation and all irreversibilities are restricted to the coupling of the system to external world. This oscillation provides an example of the so-called endoreversible machine and a possible way to convert radiation energy of the light directly into mechanical energy.
基金supported by the Natural Science and Engineering Research Council (NSERC),Canada,the National Natural Science Foundation ofChina (21003010)the Doctoral Fund of the Ministry of Education of China (20101101120032)+1 种基金the China Postdoctoral Science Foundation(20100470558)the Excellent Young Scholars Research Fund of Beijing Institute of Technology (2009 Y1017)
文摘Temporal oscillations of the bromate-4-aminophenol system have been studied in the presence of four different catalysts: tris(1,10-phenanthroline)iron(Ⅱ) sulfate (ferroin), Ce(Ⅲ), Mn(Ⅱ), and Fe(Ⅱ). Transient temporal oscillations were observed in the four catalyzed systems when the reactions were conducted in a stirred batch reactor. The induction time was prolonged by the presence of ferroin, but it was shortened in the Ce(Ⅲ)- and Mn(Ⅱ)-catalyzed systems. On the other hand, the number of peaks was significantly decreased in the presence of ferroin. The development of oscillatory behaviour was found to be more sensitive to the ratio of bromate and 4-aminophenol concentration than to their absolute concentrations. The reaction rates of 4-aminophenol with Ce(IV) and 4-aminophenol with ferritin were measured directly by spectroscopic methods in a sulfuric acid medium.