TY - JOUR AU - Valent, Ivan AU - Pribus, Marek AU - Novak, Filip AU - Plankova, Sylvia AU - Blasko, Jaroslav AU - Kubinec, Robert AU - Almassy, Ambroz AU - Filo, Juraj AU - Sigmundova, Ivica AU - Sebechlebska, Tana AU - Lawson Bich, Thuy AU - Noszticzius, Zoltan TI - Unusual Chemistry in an Uncatalyzed Bromate-Aniline Oscillator: Ring-Contraction Oxidation of Aniline with Pulsative CO2 Production JF - JOURNAL OF PHYSICAL CHEMISTRY A J2 - J PHYS CHEM A VL - 123 PY - 2019 IS - 45 SP - 9669 EP - 9681 PG - 13 SN - 1089-5639 DO - 10.1021/acs.jpca.9b07766 UR - https://m2.mtmt.hu/api/publication/31056770 ID - 31056770 N1 - Department of Physical and Theoretical Chemistry, Faculty of Natural Sciences, Comenius University in Bratislava, Bratislava, 842 15, Slovakia Institute of Chemistry, Faculty of Natural Sciences, Comenius University in Bratislava, Bratislava, 842 15, Slovakia Department of Organic Chemistry, Faculty of Natural Sciences, Comenius University in Bratislava, Bratislava, 842 15, Slovakia Department of Physics, Faculty of Natural Sciences, Budapest University of Technology and Economics, Budapest, 1111, Hungary Bayer AG, Berlin, Germany Cited By :1 Export Date: 17 May 2021 CODEN: JPCAF Correspondence Address: Valent, I.; Department of Physical and Theoretical Chemistry, Slovakia; email: ivan.valent@uniba.sk Department of Physical and Theoretical Chemistry, Faculty of Natural Sciences, Comenius University in Bratislava, Bratislava, 842 15, Slovakia Institute of Chemistry, Faculty of Natural Sciences, Comenius University in Bratislava, Bratislava, 842 15, Slovakia Department of Organic Chemistry, Faculty of Natural Sciences, Comenius University in Bratislava, Bratislava, 842 15, Slovakia Department of Physics, Faculty of Natural Sciences, Budapest University of Technology and Economics, Budapest, 1111, Hungary Bayer AG, Berlin, Germany Cited By :1 Export Date: 9 June 2021 CODEN: JPCAF Correspondence Address: Valent, I.; Department of Physical and Theoretical Chemistry, Slovakia; email: ivan.valent@uniba.sk AB - The bromate-aniline oscillatory reaction was discovered 4 decades ago, but neither the detailed mechanism nor the key products or intermediates of the reaction were described. We report herein a detailed study of this reaction, which yielded new insights. We found that oscillatory oxidation of aniline by acidic bromate proceeds, to a significant extent, via a novel reaction pathway with the periodic release of carbon dioxide. Several products were isolated, and their structures, not described so far, were justified on the basis of MS and NMR. One of the main products of the reaction associated with the CO2 release route can be assigned to 2,2-dibromo-5-(phenylimino)cyclopent-3-en-1-one. A number of known compounds produced in the studied reaction, including unexpected brominated 1-phenylpyrroles and 1-phenylmaleimides, were identified by comparison with standards. A mechanism is suggested to explain the appearance of the detected compounds, based on coupling of the anilino radical with the produced 1,4-benzoquinone. We assume that the radical adduct reacts with bromine to form a cyclopropanone intermediate that undergoes a Favorskii-type rearrangement. Further oxidation and bromination steps including decarboxylation lead to the found brominated phenyliminocyclopentenones. The detected derivatives of 1-phenylpyrrole could be produced by a one-electron oxidation of a proposed intermediate 2-phenylamino-5-bromocyclopenta-1,3-dien-1-ol followed by beta-scission with the abstraction of carbon monoxide. Such a mechanism is known from the combustion chemistry of cyclopentadiene. The proposed mechanism of this reaction provides a framework for understanding the observed oscillatory kinetics. LA - English DB - MTMT ER - TY - JOUR AU - Muntean, Norbert AU - Lawson Bich, Thuy AU - Kály-Kullai, Kristóf AU - Gyökérné Wittmann, Mária AU - Noszticzius, Zoltán AU - Onel, L AU - Furrow, SD TI - Measurement of Hypoiodous Acid Concentration by a Novel Type Iodide Selective Electrode and a New Method To Prepare HOI. Monitoring HOI Levels in the Briggs-Rauscher Oscillatory Reaction JF - JOURNAL OF PHYSICAL CHEMISTRY A J2 - J PHYS CHEM A VL - 116 PY - 2012 IS - 25 SP - 6630 EP - 6642 PG - 13 SN - 1089-5639 DO - 10.1021/jp3015673 UR - https://m2.mtmt.hu/api/publication/2210869 ID - 2210869 N1 - Department of Physical Chemistry, Babes-Bolyai University, RO-400028 Cluj-Napoca, Romania Department of Physics, Budapest University of Technology and Economics, H-1521 Budapest, Hungary School of Chemistry, University of Leeds, Leeds LS2 9JT, United Kingdom Penn State Berks College, Pennsylvania State University, Reading, PA 19610, United States Cited By :8 Export Date: 17 May 2021 CODEN: JPCAF Correspondence Address: Wittmann, M.; Department of Physics, , H-1521 Budapest, Hungary; email: wittmann@eik.bme.hu AB - A new type of iodide selective electrode prepared by dipping a silver wire into molten silver iodide is reported. The electrode was calibrated for silver and iodide ions and the measured electromotive force for various Ag+ and I- concentrations was close to the theoretical within a few millivolts. Besides Ag+ and I- ions, however, the electrode also responds to hypoiodous acid. Thus, the electrode was calibrated for HOT as well, and for that purpose a new method of hypoiodous acid preparation was developed. To explain the close to Nemstian electrode response for HOI and also the effect of hydrogen ion and iodine concentration on that response, the corrosion potential theory suggested earlier by Noszticzius et al. was modified and developed further. Following oscillations in the Briggs-Rauscher reaction with the new electrode the potential crosses the "solubility limit potential" (SLP) of silver iodide. Potentials below SLP are controlled by the concentration of I-, but potentials above SLP are corrosion potentials determined by the concentration of HOI. Finally, the measured HOI oscillations are compared with calculated ones simulated by a model by Furrow et al. LA - English DB - MTMT ER - TY - JOUR AU - Roszol, László AU - Lawson Bich, Thuy AU - Koncz, Viktória Anna AU - Noszticzius, Zoltán AU - Gyökérné Wittmann, Mária AU - Sarkadi, Tamás AU - Koppa, Pál TI - Micropatterned Polyvinyl Butyral Membrane for Acid-Base Diodes JF - JOURNAL OF PHYSICAL CHEMISTRY B J2 - J PHYS CHEM B VL - 114 PY - 2010 IS - 43 SP - 13718 EP - 13725 PG - 8 SN - 1520-6106 DO - 10.1021/jp106773y UR - https://m2.mtmt.hu/api/publication/1401797 ID - 1401797 N1 - Department of Physics, Budapest University of Technology and Economics, 1521 Budapest, Hungary Department of Atomic Physics, Budapest University of Technology and Economics, 1521 Budapest, Hungary Cited By :12 Export Date: 17 May 2021 CODEN: JPCBF Correspondence Address: Wittmann, M.; Department of Physics, Budapest University of Technology and Economics, 1521 Budapest, Hungary; email: wittmann@eik.bme.hu Department of Physics, Budapest University of Technology and Economics, 1521 Budapest, Hungary Department of Atomic Physics, Budapest University of Technology and Economics, 1521 Budapest, Hungary Cited By :12 Export Date: 9 June 2021 CODEN: JPCBF Correspondence Address: Wittmann, M.; Department of Physics, Budapest University of Technology and Economics, 1521 Budapest, Hungary; email: wittmann@eik.bme.hu AB - Until now, polyvinyl alcohol (PVA) gel cylinders have been used in electrolyte diodes as a connecting element between the acidic and alkaline reservoirs. In this paper, a new connecting element is reported: a breath figure templated polyvinyl butyral (PVB) membrane prepared with dip-coating from a dichloromethane solution of the polymer in a humid atmosphere. The procedure gives a 1.5-2 mu m thick membrane with a hexagonal pattern, the average characteristic length of which is 1 mu m. After an acidic etching, it was found to be a good connecting element. The voltage-current characteristics and dynamic properties of PVA and PVB were measured and compared. The PVB membrane has a faster response to voltage changes than the PVA gel, but in both cases, there was a slow drift in the current that prevented it from reaching a steady state. Reproducible characteristics can be obtained, however, after the current reaches a well-defined quasi-steady state. LA - English DB - MTMT ER - TY - JOUR AU - Lawson Bich, Thuy AU - Fulop, J AU - Gyökérné Wittmann, Mária AU - Noszticzius, Zoltán AU - Muntean, Norbert AU - Szabó, Gabriella Stefánia AU - Onel, L TI - Iodomalonic Acid as an Anti-Inhibitor in the Resorcinol Inhibited Briggs-Rauscher Reaction JF - JOURNAL OF PHYSICAL CHEMISTRY A J2 - J PHYS CHEM A VL - 113 PY - 2009 IS - 51 SP - 14095 EP - 14098 PG - 4 SN - 1089-5639 DO - 10.1021/jp907364a UR - https://m2.mtmt.hu/api/publication/1315114 ID - 1315114 N1 - Center for Complex and Nonlinear Systems, Department of Physics, Budapest University of Technology and Economics, H-1521 Budapest, Hungary Department of Physical Chemistry, Babeş-Bolyai University, RO-400028 Cluj-Napoca, Romania Faculty of Chemistry, Al.I.Cuza University, RO-700506 Iaşi, Romania Cited By :19 Export Date: 17 May 2021 CODEN: JPCAF Correspondence Address: Wittmann, M.; Center for Complex and Nonlinear Systems, , H-1521 Budapest, Hungary; email: wittmann@eik.bme.hu AB - It was found that the inhibitory effect of resorcinol is less pronounced if it is added in a later stage of the Briggs-Rauscher reaction, which indicates that all accumulating intermediate-most probably iodomalonic acid-can suppress the inhibition. In fact, when iodomalonic acid was added to the reaction mixture, the inhibitory period was shortened considerably even at micromolar levels of the iodomalonic acid concentration. Moreover, iodomalonic acid call accelerate the rate of the reaction when applied in the same low concentrations, suggesting that it can be an autocatalytic intermediate of the Briggs-Rauscher reaction. LA - English DB - MTMT ER - TY - JOUR AU - Muntean, Norbert AU - Szabó, Gabriella Stefánia AU - Gyökérné Wittmann, Mária AU - Lawson Bich, Thuy AU - Fulop, J AU - Noszticzius, Zoltán AU - Onel, L TI - Reaction Routes Leading to CO2 and CO in the Briggs-Rauscher Oscillator: Analogies between the Oscillatory BR and BZ Reactions JF - JOURNAL OF PHYSICAL CHEMISTRY A J2 - J PHYS CHEM A VL - 113 PY - 2009 IS - 32 SP - 9102 EP - 9108 PG - 7 SN - 1089-5639 DO - 10.1021/jp905239w UR - https://m2.mtmt.hu/api/publication/1315115 ID - 1315115 N1 - Department of Physical Chemistry, Babes-Bolyai University, RO-400028 Cluj-Napoca, Romania Center for Complex and Nonlinear Systems, Department of Physics, Budapest University of Technology and Economics, H-1521 Budapest, Hungary Faculty of Chemistry, All.Cuza University, RO-700506 Iaşi, Romania Cited By :27 Export Date: 17 May 2021 CODEN: JPCAF Correspondence Address: Wittmann, M.; Center for Complex and Nonlinear Systems, , H-1521 Budapest, Hungary; email: wittmann@eik.bme.hu Department of Physical Chemistry, Babes-Bolyai University, RO-400028 Cluj-Napoca, Romania Center for Complex and Nonlinear Systems, Department of Physics, Budapest University of Technology and Economics, H-1521 Budapest, Hungary Faculty of Chemistry, All.Cuza University, RO-700506 Iaşi, Romania Cited By :27 Export Date: 9 June 2021 CODEN: JPCAF Correspondence Address: Wittmann, M.; Center for Complex and Nonlinear Systems, , H-1521 Budapest, Hungary; email: wittmann@eik.bme.hu AB - With Fenton-type experiments, it is shown that the intense CO2/CO evolution in the Briggs-Rauscher (BR) reaction is due to decarboxylation/decarbonylation of organic free radicals. The metal ion applied in the Fenton-type experiments was Fe2+ or Ti3+ or Mn2+ combined with H2O2 or S2O82- as a peroxide, whereas the organic substrate was malonic acid (MA) or a H mixture of MA and iodomalonic acid (IMA). Experiments with a complete BR system applying MA or the MA/IMA mixture indicate that practically all CO2 and CO comes from IMA. The decarboxylation/decarbonylation mechanisms of various iodomalonyl radicals can be analogous to that of the bromomalonyl radicals studied already in the Belousov-Zhabotinsky (BZ) reaction, It is found that an intense CO2/CO evolution requires the simultaneous presence of H2O2, IO3-, Mn2+, and IMA. It is suggested that the critical first step of this complex reaction takes place in the coordination sphere of Mn2+. That first step can initiate a chain reaction where organic and hydroperoxyl radicals are the chain carriers. A chain reaction was already found in a BZ oscillator as well. Therefore, the analogies between the BR and BZ oscillators are due to the fact that in both mechanisms, free radicals and, in most cases, also transition-metal complexes play an important role. LA - English DB - MTMT ER - TY - JOUR AU - Nagygyőry, S AU - Gyökérné Wittmann, Mária AU - Pintér, S AU - Visegrády, A AU - Dancsó, András AU - Lawson Bich, Thuy AU - Noszticzius, Zoltán AU - Hegedus, L AU - Forsterling, HD TI - Alternative reaction channels and carbene intermediates in the Ce4+ - malonic acid and Ce4+ - bromomalonic acid reactions. 1. CO2 measurements JF - JOURNAL OF PHYSICAL CHEMISTRY A J2 - J PHYS CHEM A VL - 103 PY - 1999 IS - 25 SP - 4885 EP - 4892 PG - 8 SN - 1089-5639 DO - 10.1021/jp990330+ UR - https://m2.mtmt.hu/api/publication/1122 ID - 1122 N1 - Ctr. for Complex/Nonlinear Syst., Department of Chemical Physics, Technical University of Budapest, H-1521 Budapest, Hungary Fachbereich Chemie, Philipps-Universität Marburg, D-35032 Marburg/Lahn, Germany Cited By :24 Export Date: 9 June 2021 CODEN: JPCAF Correspondence Address: Noszticzius, Z.; Ctr. for Complex/Nonlinear Syst., , H-1521 Budapest, Hungary; email: noszti@phy.bme.hu AB - The Ce4+-malonic/bromomalonic acid reactions play an important role in the oscillatory Belousov-Zhabotinsky reaction. In this work CO2 evolution from these reactions was studied with a sensitive acid quantitative method, by converting the CO2 to methane and measuring it with a flame ionization detector. It was found that the stoichiometries depend on the initial conditions in batch experiments or on the mixing rate of reagents in a semibatch reactor. These findings are explained by two main reaction channels: one for recombination and another for decarboxylation. Decarboxylation itself has two separate routes, one is dominant at low while the other at high Ce4+ concentrations. In the latter, formation of more than two CO2 molecules from one malonic/bromomalonic acid molecule was observed. Novel reaction schemes containing carbenes are proposed for these "high Ce4+" decarboxylation channels. To check the new mechanism, HPLC measurements are planned as a continuation of the research. LA - English DB - MTMT ER - TY - JOUR AU - Simon L., Péter AU - Lawson Bich, Thuy AU - Farkas, Henrik AU - Noszticzius, Zoltán TI - Application of the parametric representation method to construct bifurcation diagrams for highly non-linear chemical dynamical systems JF - JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS J2 - J CHEM SOC FARADAY T VL - 92 PY - 1996 SP - 2865 EP - 2871 PG - 7 SN - 0956-5000 DO - 10.1039/ft9969202865 UR - https://m2.mtmt.hu/api/publication/1131 ID - 1131 N1 - Cited By :2 Export Date: 9 June 2021 Correspondence Address: Simon, P.L.; Institute of Physics, , Budapest H-1521, Hungary AB - The parametric representation method has been shown to be a useful geometric tool to study tangent and Hopf bifurcations in chemical systems. As an example, we investigate the behaviour of a two-dimensional system of differential equations. This general model includes some known catalytic oxidation models as special cases. The general system can have one or three stationary solutions depending on the parameter values. The parametric representation method is applied to construct bifurcation diagrams for multistationarity and stability. LA - English DB - MTMT ER -