Bromous acid

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Bromous acid
Bromige saeure.png
Space-filling model of the bromous acid molecule
Bromous acid molecule ball.png
Names
IUPAC names
hydroxy-λ3-bromanone
hydroxidooxidobromine
bromous acid
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
Properties
HBrO2
Molar mass 112.911 g/mol
Related compounds
Other anions
Hydrobromic acid; hypobromous acid; bromic acid; perbromic acid
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Infobox references

Bromous acid is the inorganic compound with the formula of HBrO2. It is an unstable compound, although salts of its conjugate base - bromites - have been isolated. In acidic solution, bromites decompose to bromine.[1]

Discovery[edit]

In 1905, Richards A. H. proved the existence of bromous acid through a series of experiments involving silver nitrate (AgNO3) and bromine.[2] The reaction of excess cold aqueous to form hypobromous acid (HBrO), silver bromide (AgBr) and nitric acid (HNO3):

Br2 + AgNO3 + H2O → HBrO + AgBr + HNO3

Richards discovered that the effect of adding excess liquid bromide in a concentrated silver nitrate (AgNO3) resulted in a different reaction mechanism. From numbers of equivalent portions of acid-bromine formed from the previous reaction, the ratio between oxygen and bromine was calculated, with the exact value of O: Br (0.149975: 0.3745), suggesting the acid compound contains two oxygen atom to one bromine atom. Thus, the chemical structure of the acid compound was deducted as HBrO2.[2]

According to Richards, hypobromous acid (HBrO) arises by the reaction of bromine and silver nitrate solution:[2]

Br2 + AgNO3 + H2O → HBrO + AgBr + HNO3
2AgNO3 + HBrO + Br2 + H2O → HBrO2 + 2 AgBr

Isomerism[edit]

The molecule HBrO2 has a bent structure with ∠(H−O−Br) angles of 106.1o. HOBrO also adopts a non-planar conformation with one isomer structure (2a) adopts a with dihedral angle ∠(H−O−Br− O) of 74.2°. Moreover, the planar structures of two other isomers (2b - cis and 2c - trans) are transition state for fast enantiomerization.[3]

Another study identified three isomers: HOOBr, HOBrO, and HBr(O)O.[4]

Synthesis[edit]

A oxidation reaction between hypobromous acid (HBrO) and hypochlorous acid (HClO) can be used to produce bromous acid (HBrO2) and hydrochloric acid (HCl).[5]

HBrO + HClO → HBrO2 + HCl

A redox reaction of hypobromous acid (HBrO) can form bromous acid (HBrO2) as its product:[5]

HBrO + H2O + e → HBrO2

The disproportion reaction of two equivalents hypobromous acid (HBrO) results in the formation of both bromous acid (HBrO2) and bromic acid (HBr):[5]

2 HBrO → HBrO2 + HBr

A rearrangement reaction, which results from the syn-proportion of bromic acid (HBrO3) and hydrobromic acid (HBr) gives bromous acid (HBrO2):[5]

2 HBrO3 + HBr → 3 HBrO2

Sodium bromate[edit]

The salts NaBrO2·3H2O and Ba(BrO2)2·H2O have been crystallized. Upon treatment of these aqueous solutions with salts of Pb2+, Hg2+, and Ag+, the corresponding heavy metal bromites precipitate as solids.[1]

Belousov-Zaboutinsky Reaction[edit]

Bromous acid is a product of the Belousov-Zaboutinsky reaction resulting from the combination of potassium bromate, cerium(IV) sulfate, propanedioic acid and citric acid in dilute sulfuric acid. Bromous acid is an intermediate stage of the reaction between bromate ion (BrO
3
) and bromine (Br):[6][7]

  • BrO
    3
    + 2Br → HBrO2 + HBrO

Other relevant reactions in such oscillating reactions are:

  • HBrO2 + BrO
    3
    + H+ → 2BrO2. + H2O
  • 2HBrO2 → BrO
    3
    + HOBr + H+

Bromites reduce permanganates to manganates (VI):[1]

  • 2MnO
    4
    + BrO
    2
    + OH → 2MnO2−
    4
    + BrO
    3
    + H2O

pKa measurement[edit]

The acid dissociation constant of bromous acid, Ka = , was determined using different methods.

The value of pKa for bromous acid was estimated in a research studying the decomposition of bromites. The research measured the rate of bromite decomposition as a function of hydrogen and bromite ion concentrations. The experimental data of the log of the initial velocity were plotted against pH. Using this method, the estimated pKa value for bromous acid was 6.25.[8]

Using another method, the value of pKa for bromous acid was measured based on the initial velocity of the reaction between sodium bromites and potassium iodine in pH range 2.9-8, at 25oC and ionic strength of 0.06M. The first order dependence of the initial velocity of this disproportional reaction on [H+] in the pH range of 4.5-8. The value of acid dissociation constant measured by this method is Ka= (3.7 ± 0.9) x 10−4 (M) and pKa= 3.43 ± 0.05.[9]

References[edit]

  1. ^ a b c Egon Wiberg, Arnold Frederick Holleman (2001) Inorganic Chemistry, Elsevier ISBN 0-12-352651-5
  2. ^ a b c "Journal of the Society of Chemical Industry. v.25 1906.". HathiTrust. Retrieved 2017-04-28. 
  3. ^ Glaser, Rainer; Jost, Mary (2012-08-16). "Disproportionation of bromous acid HOBrO by direct O-transfer and via anhydrides O(BrO)2 and BrO-BrO2. An ab initio study of the mechanism of a key step of the Belousov-Zhabotinsky oscillating reaction". The Journal of Physical Chemistry A. 116 (32): 8352–8365. ISSN 1520-5215. PMID 22871057. doi:10.1021/jp301329g. 
  4. ^ Souza, Gabriel L. C. de; Brown, Alex (2016-07-01). "The ground and excited states of HBrO2 [HOOBr, HOBrO, and HBr(O)O] and HBrO3 (HOOOBr and HOOBrO) isomers". Theoretical Chemistry Accounts. 135 (7): 178. ISSN 1432-881X. doi:10.1007/s00214-016-1931-8. 
  5. ^ a b c d C., Ropp, R. (2013-01-01). Encyclopedia of the alkaline earth compounds. Elsevier. ISBN 9780444595508. OCLC 964753424. 
  6. ^ Vassalini, Irene; Alessandri, Ivano. "Spatial and Temporal Control of Information Storage in Cellulose by Chemically Activated Oscillations". ACS Applied Materials & Interfaces. 7 (51): 28708–28713. doi:10.1021/acsami.5b11857. 
  7. ^ Field, Richard J.; Koros, Endre; Noyes, Richard M. (1972-12-01). "Oscillations in chemical systems. II. Thorough analysis of temporal oscillation in the bromate-cerium-malonic acid system". Journal of the American Chemical Society. 94 (25): 8649–8664. ISSN 0002-7863. doi:10.1021/ja00780a001. 
  8. ^ Massagli, A. "Kinetic investigation of the decomposition of bromite - ScienceDirect". Inorganica Chimica Acta. 4: 593–596. doi:10.1016/S0020-1693(00)93357-7. Retrieved 2017-04-27. 
  9. ^ Faria, R. B.; Epstein, Irving R.; Kustin, Kenneth (1994-01-01). "Kinetics of Disproportionation and pKa of Bromous Acid". The Journal of Physical Chemistry. 98 (4): 1363–1367. ISSN 0022-3654. doi:10.1021/j100055a051.