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1.
Onel L Bourceanu G Wittmann M Noszticzius Z 《The journal of physical chemistry. A》2005,109(45):10314-10322
The uncatalyzed reactions of bromomalonic acid (BrMA) with acidic bromate and with hypobromous acid were studied in 1 M sulfuric acid, a usual medium for the oscillatory Belousov-Zhabotinsky (BZ) reaction, by following the rate of the carbon dioxide evolution associated with these reactions. In addition, the decarboxylation rate of dibromomalonic acid (Br2MA) was also measured to determine the first-order rate constant of its decomposition (4.65 x 10(-5) s(-1) in 1 M H2SO4). The dependence of that rate constant on the hydrogen ion concentration suggests a carbocation formation. A slow oligomerization of BrMA observed in sulfuric acid solutions is also rationalized as a carbocationic process. The initial rate of the BrMA-BrO3- reaction is a bilinear function of the BrMA and BrO3- concentrations with a second-order rate constant of 3.8 x 10(-4) M(-1) s(-1). When a great excess of BrO3- is applied, then BrMA is oxidized mostly to CO2. A reaction scheme compatible with the experimental finding is also given. On the other hand, when less BrO3- and more organic substrate - BrMA or malonic acid (MA)--is applied, then addition reactions of various carbocations with the enol form of the organic substrates should be taken into account in later stages of the reaction. It was discovered that HOBr, which brominates BrMA to Br2MA when BrMA is in excess, can also oxidize BrMA when HOBr is in excess. As Br2MA does not react with HOBr, it is assumed that the acyl hypobromite, formed in the first step of the HOBr and BrMA reaction, can react with an additional HOBr to give oxidation products. It was found that the initial rate of the reaction can be described by the following experimental rate law: k(BHOB)[BrMA]0[HOBr]0(2), where k(BHOB) = 5 M(-2) s(-1). A reaction scheme for the oxidation of BrMA by HOBr is given for conditions where HOBr is in excess. Model calculations illustrate qualitatively that the suggested reaction schemes are able to mimic the experiments. (More quantitative simulations are prevented by kinetic data missing for the various carbocation intermediates.) Finally, the effects of these newly observed reactions on oscillatory BZ systems are discussed briefly. 相似文献
2.
S. M. Blagojević S. R. Anić Ž. D. Čupić N. D. Pejić Lj. Z. Kolar-Anić 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2009,83(9):1496-1501
The kinetic investigations of the malonic acid decomposition (8.00 × 10−3 mol dm−3 ≤ [CH2(COOH)2]0 ≤ 4.30 × 10−2 mol dm−3) in the Belousov-Zhabotinsky (BZ) system in the presence of bromate, bromide, sulfuric acid and cerium sulfate, were performed
in the isothermal closed well stirred reactor at different temperatures (25.0°C ≤ T ≤ 45.0°C). The formal kinetics of the overall BZ reaction, and particularly kinetics in characteristic periods of BZ reaction,
based on the analyses of the bromide oscillograms, was accomplished. The evolution as well as the rate constants and the apparent
activation energies of the reactions, which exist in the preoscillatory and oscillatory periods, are also successfully calculated
by numerical simulations. Simulations are based on the model including the Br2O species.
The article is published in the original. 相似文献
3.
Onel L Wittmann M Pelle K Noszticzius Z Sciascia L 《The journal of physical chemistry. A》2007,111(32):7805-7812
CO and CO2 evolution was measured in a cerium and in a ferroin-catalyzed Belousov-Zhabotinsky (BZ) reaction. These gases were stripped from the reaction mixture by a N2 carrier gas, mixed with H2, converted to methane on a Ni catalyst, and then measured by a flame ionization detector (FID). CO could be detected separately by absorbing CO2 on a soda lime column. In separate experiments it was proven that CO is produced in a reaction of BrO2* radicals with bromomalonic acid (BrMA). To this end BrO2(.-) radicals were generated in two different ways: (i) in the reaction HBrO2 + HBrO3 <--> 2 BrO2(.-) + H2O and (ii) by reducing HBrO3 to BrO2(.-) by Fe(2+). It was found that (.-)OH radicals--produced by Fenton's reagent--can also generate CO from BrMA. We propose that CO can be formed when an inorganic radical (like BrO2(.-) or (.-)OH) reacts with the enol form of BrMA producing an acyl radical which decarbonylates in the next step. Malonic acid (MA)-BrMA mixtures were prepared by a new method modifying Zaikin and Zhabotinsky's original recipe to minimize the production of dibromomalonic acid (Br2MA). 相似文献
4.
Several substrates have been employed in different oscillatory systems. A serious limitation is the low solubility in water. This has been overcome by employing aqueous-organic mixed media in the iodate-system as well as the uncatalyzed and catalyzed [Ce(III) or Ferroin] systems. The present paper deals with the study of fifteen new substrates in the bromate-Mn(II) oscillatory system employing aqueous-organic mixed media.
. . , - , (Ce(III) ), . -Mn(II) - .相似文献
5.
Prakashanand Caumul 《Tetrahedron letters》2005,46(47):8125-8127
The Baylis-Hillman reaction has been successfully performed under aqueous acidic conditions at pH 1, using a range of substrates and tertiary amines as catalysts. 相似文献
6.
The kinetics of the isotope exchange reactions of RCH(COOH)2 (RH, D, Me, Et, Bu, and Ph) in D2O solution were studied by using 1H NMR spectroscopy. It was observed that the rate of isotope exchange reaction was inhibited by the presence of 1 M of DNO3, DCl, DBr or D2SO4 and catalyzed by the presence of 4 M of D2SO4. No inhibition effect was observed in the case of D3PO4. The effect of inorganic acids follows the order of D3PO4>D2SO4 ≫ (DNO3, DCl, DBr). The conjugated base (RCH(COOD)(COO−)) of RCH(COOD)2 plays an important role in the isotope exchange reaction. The presence of deuterium ion suppresses the generation of RCH(COOD)(COO−) ion from RCH(COOD)2 and inhibits the rate of isotope exchange. In general, the order of reactivity of RCH(COOH)2 toward isotope exchange with deuterium atom is RPh>(H, Br)>Me>(Et, Bu). © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 455–461, 1999 相似文献
7.
Horst-Dieter F?rsterling Szilvia Murányi Zoltán Noszticzius 《Reaction Kinetics and Catalysis Letters》1990,42(2):217-226
A new theory of the Belousov-Zhabotinsky (BZ) reaction, the Radicalator model, is presented. This model is based on a negative feedback loop involving a fast reaction between malonyl and bromine dioxide radicals. Experimental evidence for the validity of the model is given for BZ systems in 3 M and 1 M sulfuric acid solution. 相似文献
8.
Lal V Khalizov AF Lin Y Galvan MD Connell BT Zhang R 《The journal of physical chemistry. A》2012,116(24):6078-6090
Epoxides have recently been identified as important intermediates in the gas phase oxidation of hydrocarbons, and their hydrolysis products have been observed in ambient aerosols. To evaluate the role of epoxides in the formation of secondary organic aerosols (SOA), the kinetics and mechanism of heterogeneous reactions of two model epoxides, isoprene oxide and α-pinene oxide, with sulfuric acid, ammonium bisulfate, and ammonium sulfate have been investigated using complementary experimental techniques. Kinetic experiments using a fast flow reactor coupled to an ion drift-chemical ionization mass spectrometer (ID-CIMS) show a fast irreversible loss of the epoxides with the uptake coefficients (γ) of (1.7 ± 0.1) × 10(-2) and (4.6 ± 0.3) × 10(-2) for isoprene oxide and α-pinene oxide, respectively, for 90 wt % H(2)SO(4) and at room temperature. Experiments using attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR) reveal that diols are the major products in ammonium bisulfate and dilute H(2)SO(4) (<25 wt %) solutions for both epoxides. In concentrated H(2)SO(4) (>65 wt %), acetals are formed from isoprene oxide, whereas organosulfates are produced from α-pinene oxide. The reaction of the epoxides with ammonium sulfate is slow and no products are observed. The epoxide reactions using bulk samples and Nuclear Magnetic Resonance (NMR) spectroscopy reveal the presence of diols as the major products for isoprene oxide, accompanied by aldehyde formation. For α-pinene oxide, organosulfate formation is observed with a yield increasing with the acidity. Large yields of organosulfates in all NMR experiments with α-pinene oxide are attributed to the kinetic isotope effect (KIE) from the use of deuterated sulfuric acid and water. Our results suggest that acid-catalyzed hydrolysis of epoxides results in the formation of a wide range of products, and some of the products have low volatility and contribute to SOA growth under ambient conditions prevailing in the urban atmosphere. 相似文献
9.
A. S. Kovalenko L. P. Tikhonova F. S. Moshkovich 《Reaction Kinetics and Catalysis Letters》1990,42(2):383-388
The concentration dependences of autowave parameters have been established for the Belousov-Zhabotinsky reactions involving Fe(phen)
3
2+
and Fe(dipy)
3
2+
as catalysts and malonic or -ketoglutaric acid as a reductant. Plots of autowave parameters against reactant concentration and solution viscosity in such systems containing agar-agar and SiO2 gel are given. 相似文献
10.
11.
Orte A Talavera EM Maçanita AL Orte JC Alvarez-Pez JM 《The journal of physical chemistry. A》2005,109(39):8705-8718
2',7'-Difluorofluorescein (Oregon Green 488, OG488) is a novel fluorescein dye derivative which presents important advantages for improving the fluorimetric applications in the biomedical and biochemical sciences. In aqueous solution it displays four prototropic forms, namely cation (C), neutral (N), monoanion (M), and dianion (D). In previous works, we found (J. Phys. Chem. A 2005, 109, 734-747, 2840-2846) that OG488 undergoes excited-state proton transfer reactions, which may affect the results from applications using this dye. We established that the excited-state proton transfer (ESPT) reactions between neutral, monoanionic, and dianionic forms of OG488 are promoted by acetate buffer, and we characterized the ground and excited species involved. We also solved the kinetics of the prototropic reactions using global compartmental analysis. In the present paper, we extend our study on the ESPT reactions of OG488 to acidic media, in which only the three prototropic species cation, neutral, and monoanion coexist. We have solved the kinetics of the three-state ESPT reaction by means of global three-compartmental analysis of a fluorescence decay surface in moderately acidic media (pH between 1.1 and 3.0), recovering the kinetic and spectral parameters of this three-state system. This system is one of the most complex solved to date, due to the strong overlap of the absorption and emission spectra of the neutral and monoanionic forms of OG488. We also found that the cation behaves as "super" photoacid, showing a very high deprotonation rate constant (1.04 x 10(11) s(-1)) and an enhanced acidity. Therefore, we also carried out experiments at very high perchloric acid concentrations, dealing with some other effects which become noteworthy at these [H(+)]. The presence of xanthylium cation quenching due to "free" water molecules, and the reduction in the amount of water clusters acting as proton acceptors, are processes which alter notably the time course of the excited-species in this high [H(+)] range. 相似文献
12.
Curti C Battistini L Zanardi F Rassu G Zambrano V Pinna L Casiraghi G 《The Journal of organic chemistry》2010,75(24):8681-8684
The first uncatalyzed, diastereoselective vinylogous Mukaiyama aldol reaction is reported, between pyrrole/furan-based dienoxy silanes and aromatic aldehydes on salty water/methanol medium, at almost human body temperature, under ultrasonic irradiation. With pyrrole dienes the reaction is anti-selective, while that of furan dienes is syn-selective. The dual role of water as both reaction medium and promoter is highlighted. 相似文献
13.
A. V. Chernysheva V. M. Chernyshev P. V. Korolenko V. A. Taranushich 《Russian Journal of Applied Chemistry》2008,81(10):1813-1817
Thermodynamic and kinetic features of the reaction of aminoguanidine with malonic acid in aqueous solutions at pH 0.5–1.3 to give mono-and diguanylhydrazides of malonic acid were examined, and the reaction mechanism was suggested. 相似文献
14.
Hegedüs L Försterling HD Onel L Wittmann M Noszticzius Z 《The journal of physical chemistry. A》2006,110(47):12839-12844
In the present mechanistic schemes of the ferroin-catalyzed oscillatory Belousov-Zhabotinsky (BZ) reaction the oxidation of the organic substrates (bromomalonic or malonic acid) by ferriin (the oxidized form of the catalyst) plays an important role. As the organic products of these reactions were not yet identified experimentally, they were studied here by an HPLC technique. It was found that the main organic oxidation product of bromomalonic acid is bromo-ethene-tricarboxylic acid (BrEETRA), the same compound that is formed when bromomalonic acid is oxidized by Ce4+ (another catalyst of the BZ reaction). Formation of BrEETRA is explained here by a new mechanism that is more realistic than the one suggested earlier. To find any oxidation product of malonic acid in the ferriin-malonic acid reaction was not successful, however. Neither ethane-tetracarboxylic acid (ETA) nor malonyl malonate (MAMA), the usual products of the Ce4+- malonic acid reaction, nor any other organic acid, not even CO2, was found as a product of the reaction. We propose that malonic acid is not oxidized in the ferriin-malonic acid reaction, and it plays only the role of a complex forming catalyst in a process where Fe3+ oxidizes mostly its phenantroline ligand. 相似文献
15.
Nakata S Matsushita M Sato T Suematsu NJ Kitahata H Amemiya T Mori Y 《The journal of physical chemistry. A》2011,115(26):7406-7412
The excitation of the photosensitive Belousov-Zhabotinsky (BZ) reaction induced by light stimulation was systematically investigated. A stepwise increase in the light intensity induced the excitation, whereas a stepwise decrease did not induce the excitation. The threshold values for the excitation were found to be a function of the initial and final light intensities, time variation in light intensity, and the concentration of NaBrO(3). The experimental results were qualitatively reproduced by a theoretical calculation based on a three-variable Oregonator model modified for the photosensitive BZ reaction. These results suggest that although the steady light irradiation is known to inhibit oscillation and chemical waves in the BZ system under almost all conditions, the stepwise increase in the light irradiation leads to the rapid production of an activator, resulting in the photoexcitation. 相似文献
16.
Sustained oscillations in the potential of Pt redox and bromide selective electrodes are observed in homogeneous systems containing bromate, metal—ion catalyst, aqueous sulfuric acid, and saccharides.
Pt , , - , .相似文献
17.
Noise can stabilize a metastable state in such a way that the system remains in this state for a longer time than in the absence of noise. When this phenomenon is observed in chaos, it is called "noise-induced order." We have experimentally detected noise-induced order in the Belousov-Zhabotinsky reaction. That is, when noise is added to the chaos with the flow rate near the period-three oscillation, a decrease of the maximum Lyapunov exponent and a convergence of the Fourier spectrum are observed. Moreover, the analysis on the one-dimensional return map reveals that noise-induced order is caused by the convergence of the chaotic trajectory into the laminar region. 相似文献
18.
P. K. R. Nair A. Mittal S. V. Kadamne K. Srinivasulu 《Reaction Kinetics and Catalysis Letters》1982,19(1-2):201-205
Oscillatory behavior in the uncatalyzed aqueous acidic bromate oxidation of 3,4-dimethoxybenzaldehyde (veratraldehyde) is reported. The generally used H2SO4 can be substituted by HNO3, HClO4, CCl3 COOH and H3PO4 in this system. The length of the induction period is found to be dependent on the initial concentrations of the reagents and this effect is more prominent in the case of acidity. The precipitate accumulated in the reaction during oscillations has been identified. A plausible mechanism is also suggested. Experiments with allyl alcohol, a bromine scavenger, suggest that elemental bromine formed in the reaction has a role in the mechanism together with or besides bromide inons.
3,4- () . H2SO4 HNO3, HClO4, CCl3 COOH H3PO4 . . , , . . , , , , , .相似文献
19.
Under Minisci reaction conditions, nucleophilic carbon free radicals readily substitute ferrocene (as the ferricinium ion) and protonated acetophenone, the latter reaction being highly positionally specific. 相似文献
20.
Self-oscillation for the microgel particles ( approximately 200 nm in diameter) was studied by changing initial substrate concentrations (i.e., malonic acid, sodium bromate, and nitric acid) of the Belousov-Zhabotinsky (BZ) reaction that is used for chemical energy for the self-oscillation. The cross-linked microgels are composed of N-isopropylacrylamide and ruthenium tris(2,2'-bipyridine), Ru(bpy) 3, which is a catalyst for the BZ reaction. Comparing with the homogeneous, stirred solution of the bulk solution for the BZ reaction, swelling/deswelling oscillation of the microgels showed longer induction period, different dependence of initial substrate concentrations on oscillation period, and different oscillation rhythm. The change in oscillation for the microgels can be understood by considering the microgel network effect. 相似文献