Formation and Stability of Hypobromous Acid in Perchloric Acid Solutions of Bromine and Bromate Ions

Betts, R. H.; Mackenzie, Agnes N.

doi:10.1139/v51-075

Cited by 15 publications

(15 citation statements)

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“…-0.80 -- N e~v experimental evidence presented in cletail in a succeeding paper (2) indicates that Item (6) above is, in all likelihoocl, responsible for t h e anomalous behavior of this exchange reaction. Briefly, tliese experiments show that bromine a n d brornate .are thermodynamicall!.…”

Section: Canadian J O U R N a L Of C'hemistrp 1'ol 29mentioning

confidence: 93%

“…Points (2) and (3) abdve may be thus escludecl Irom further consideration. EFfects related to transient catalysis by trace impurities would be expected to be ~ionreproducible, whereas no u n d~~e scatter ol results was observed in duplicate experiments.…”

Section: Canadian J O U R N a L Of C'hemistrp 1'ol 29mentioning

confidence: 99%

“…In a succeecling paper (2), further chemical investigations are clescribecl dealing mainly with the role ol 115-pobromous acid in this system.…”

Section: Introductionmentioning

confidence: 99%

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Isotopic Exchange Reactions in the System Bromine – Bromate – Hypobromous Acid

Betts¹,

Mackenzie²

1951

Can. J. Chem.

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Radiotracer studies ivith BrS' show that bromine and bromate ion i l l perchloric acid solution 1111dergo isotopic eschange a t a measurable rate. 'The ki~leticli of the process suggest that secouclary chen~ical reactions occur, leading LC) thc iormation of signihcant co~~ccntrations of hypohrornous acid i l l the systc~n. The isotopic exchange betiveen h > , p o b r o n~o~~s acid and bromine is complete ivithin the ti~iie required to separate these slx.c:ics.

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Section: Canadian J O U R N a L Of C'hemistrp 1'ol 29mentioning

confidence: 93%

Section: Canadian J O U R N a L Of C'hemistrp 1'ol 29mentioning

confidence: 99%

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Isotopic Exchange Reactions in the System Bromine – Bromate – Hypobromous Acid

Betts¹,

Mackenzie²

1951

Can. J. Chem.

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“…Curve 2 (dashed line): NaBrC>2, purified by adding silver nitrate to the alkaline solution and removing the AgBrprecipitate by ultracentrifugation. Curve 2 (triangles: HOBr absorption spectrum [10]. Curve 3 (dash-dotted line): difference of curves 1 and 2.…”

Section: Methodsmentioning

confidence: 99%

“…Curve 3 (dash-dotted line): difference of curves 1 and 2. Curve 3 (circles): Br2-absorption spectrum [10,11] [12].…”

Section: Methodsmentioning

confidence: 99%

Formation of BrO₂ in the Belousov-Zhabotinsky-System — Investigation of the HBrO₂ /BrO₃ ^–-Reaction

Försterling

Lamberz

Schreiber

1980

Zeitschrift Für Naturforschung A

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The reaction between HBr02 and bromate was studied in sulfuric acid solution. From the spectral dependence of the absorbance in the region from 400 to 600 nm it is concluded that Br02 is an intermediate of the reaction. From the maximum concentration of Br02 the equilibrium constant of the BrOa/B^O-i-equilibrium is evaluated; furthermore, a value for the ratio of the rate constants for the HBr02/Br03~-reaction and the disproportionation reaction of HBr02 is given.The autocatalytic formation of Ce 4+ is one of the essential reactions in the Belousov-Zhabotinskysystem [1,2] In preceding experiments [4,5, 6] we have been able to detect Br02 formed in this reaction. The kinetics experimentally observed was found to be in qualitative agreement with the FKN-reaction scheme. In a quantitative respect, however, the experimental results disagreed with theory; as an example, the Br02-concentrations experimentally obtained were 1/10 of the calculated values only. In order to overcome this discrepany, reaction (R2) was investigated in more detail. Experimental ProcedureSince HBr02 is not stable in acid solution, we have studied reaction (R2) by injecting NaBr02 (solved in 0.1 m NaOH) into aim solution of NaBr(>3 in 1 m sulfuric acid assuming that the reactionis much faster than all other reactions under consideration. Care was taken to use reagents of high purity. 1 m H2SO4 was prepared by dilution of conc. H2S04 (p.a. Merck) in bidistilled water. NaBrÜ3 (p.a. Fluka) was twice recrystallized from hot water. The absorption spectrum of solutions of NaBrC>3 in 1 m H2S04 changed significantly in the course of purification (Fig. 1); this fact is mainly due to the elimination of Br~-and BrO~-impurities. We were not able to reduce the residual 480 nm-absorption band by further recrystallization. NaBr02 was prepared by a modified procedure [7] basing on the synthesis described by Breiss [8]. The product was three times recrystallized from 0.1 m NaOH; the absorption spectrum given in Fig. 2 was found to be in excellent agreement with the spectra reported in [8,9]. The residual Br~-impurity of this product was estimated using the following procedure: alkaline solutions of NaBr02 (initial concentration 2.81 • 10~4 m) were injected into 1 m sulfuric acid and the absorption spectra of the reaction products were taken (Figure 3). In the case of curve 1, NaBr02 was used without further purification; in the case of curve 2, the alkaline solution of NaBr02 had been purified from Br~ by adding silver nitrate and removing the AgBr-precipitate by ultracentrifugation. The difference spectrum of curves 1 and 2 was found to agree with the spectrum of Br2 (curve 3). From the absorbance A =0.018 at X = 400 nm the Br2-concentration 1.1 • 10 -5 m was calculated (fiBr2 = 172 1 • mole-1 • cm-1 ).Assuming the reaction path 3 Br-+ HBr02 + 3 H+ -» 2 Br2 + 2 H20 the concentration of the Br~-impurity was estimat-0340-4811 I 80 / 1200-1354 $ 01.00/0. -Please order a reprint rather than making your own copy.

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The oxidation of cerous ions by bromate ions comparison of experimental data with computer calculations

Barkin

Bixon

Noyes

et al. 1977

Int J of Chemical Kinetics

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The oxidation of cerous ions by bromate ions in sulfuric acid medium was followed spectrophotometrically under various experimental conditions. The results were compared to the calculated predictions on the basis of a mechanism suggested by R. M. Noyes and collaborators.The computations were done by solving the complete set of the kinetic differential equations. The results of the computations show that the proposed mechanism explains adequately most of our and previous experimental data. In particular, the mechanism predicts the main features of the reaction, namely, the induction and the fast and slow reaction periods which occur during the oxidation.

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Formation and Stability of Hypobromous Acid in Perchloric Acid Solutions of Bromine and Bromate Ions

Cited by 15 publications

References 1 publication

Isotopic Exchange Reactions in the System Bromine – Bromate – Hypobromous Acid

Isotopic Exchange Reactions in the System Bromine – Bromate – Hypobromous Acid

Formation of BrO₂ in the Belousov-Zhabotinsky-System — Investigation of the HBrO₂ /BrO₃ ^–-Reaction

The oxidation of cerous ions by bromate ions comparison of experimental data with computer calculations

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Formation and Stability of Hypobromous Acid in Perchloric Acid Solutions of Bromine and Bromate Ions

Cited by 15 publications

References 1 publication

Isotopic Exchange Reactions in the System Bromine – Bromate – Hypobromous Acid

Isotopic Exchange Reactions in the System Bromine – Bromate – Hypobromous Acid

Formation of BrO2 in the Belousov-Zhabotinsky-System — Investigation of the HBrO2 /BrO3 –-Reaction

The oxidation of cerous ions by bromate ions comparison of experimental data with computer calculations

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Formation of BrO₂ in the Belousov-Zhabotinsky-System — Investigation of the HBrO₂ /BrO₃ ^–-Reaction