Bromide ions

In a sulphate ion medium, ceric sulphate oxidises Br to Br2 according to the rate expression  

The dominant species of Ce(IV) existing under the reaction conditions is 00(804)3 and the activated complexes for the two paths must have compositions 0(804)2 Br and 00(804)261 . The latter path is subject to chloride-ion catalysis of the form = A q-1-A [OI ] which suggests an activated complex 0e(804)201Br2 . 8I0W oxidative breakdown of the complexes containing bromide gives Oe(III) and Br atoms or -BrJ. The latter go on to form molecular bromine however, their presence has been detected in this reaction from their ability to add to butadiene to form dibromooctadienes . 

A stopped-flow examination of the Oo(III) perchlorate oxidation produced kinetics  

The oxidation by Mn(Iir) in a perchlorate medium follows two kinetic paths depending on the bromide concentration, viz. 

Both reaction paths are acid-catalysed and are subject to retardation by specific ions probably by removal of free Br . The second-order dependence with respect to reductant has several precedents, e.g. Fe(iri) oxidation of 1 and Mn(III) oxidation of HN3. The acid catalysis results from suppression of the hydrolysis to MnOH which is ineffective in this oxidation. 

T0329 General Atomics, Supercritical Water Oxidation T0756 Supercritical Water Oxidation—General 

T0783 Terrapure Systems, L.L.C., Palladized Iron Remediation Technology T0817 T-Thermal Company, Submerged Quench Incineration 

T0022 Aero-Terra-Aqua Technologies Corporation, Aqua-Fix 

T0040 Andco Environmental Processes, Inc., Electrochemical Iron Generation 

T0042 Applied Environmental Services, Inc., Asphaltic Metals Stabilization 

---

The bromate-ferroin reaction has a quadratic autocatalytic sequence, but in this case the induction period is detennined primarily by the time required for the concentration of the hiliibitor bromide ion to fall to a critical low value tlirough the reactions... 

Bromide ion acts as an inliibitor through step (9) which competes for HBr02 with the rate detennining step for the autocatalytic process described previously, step (4) and step (5). Step (8) and Step (9) constitute a pseudo-first-order removal of Br with HBr02 maintained in a low steady-state concentration. Only once [Br ] < [Br ] = /fo[Br07]//r2 does step (3) become effective, initiating the autocatalytic growth and oxidation. 

The basie features of the oseillatory meehanism of the BZ reaetion are given by the Field-Koros-Noyes (FKN) model [14]- This involves three proeesses —A, B and C. Proeess A involves step (8) and step (9) from seetion A3,14.2.1. leading to removal of uiliibitor bromide ion. Proeess B involves step (3) and step (4) from Seetion A3.14.1.1 and gives the autoeatalytie oxidation of the eatalyst. This growth is limited partly by the disproportionation reaetion... 

In the laboratory, bromine is prepared by oxidation of bromide ion the oxidation is carried out by mixing solid potassium bromide with manganese(IV) oxide and distilling with concentrated sulphuric acid ... 

Some reactions require the bonds being broken or made in a reaction to be aligned with other parts ti- or free electrons) of a molecule. These requirements are called stereoelectronic effects. Figure 3-6f shows that the bromide ion has to open a bro-monium ion by an anti attack in order that the new bond is formed concomitantly with the breaking of one bond of the three-membered ring. 

The carbon atom m bromomethane can accept an electron pair if its covalent bond with bromine breaks with both electrons m that bond becoming an unshared pair of bromide ion Thus bromomethane acts as a Lewis acid m this reaction... 

The major difference between the two mechanisms is the second step The second step m the reaction of tert butyl alcohol with hydrogen chloride is the ummolecular dis sociation of tert butyloxonium ion to tert butyl cation and water Heptyloxonium ion however instead of dissociating to an unstable primary carbocation reacts differently It IS attacked by bromide ion which acts as a nucleophile We can represent the transition state for this step as... 

Bromide ion forms a bond to the primary carbon by pushing off a water molecule This step IS bimolecular because it involves both bromide and heptyloxonium ion Step 2 IS slower than the proton transfer m step 1 so it is rate determining Using Ingold s ter mmology we classify nucleophilic substitutions that have a bimolecular rate determining step by the mechanistic symbol Sn2... 

Step 2 IS the conversion of the bromonium ion to 1 2 dibromoethane by reaction with bromide ion (Br )... 

Unbranched primary alcohols and tertiary alcohols tend to react with hydrogen halides without rearrangement The alkyloxonmm ions from primary alcohols react rap idly with bromide ion for example m an Sn2 process Tertiary alcohols give tertiary alkyl halides because tertiary carbocations are stable and show little tendency to rearrange... 

The secondary carbon bears more of the positive charge than does the primary carbon and attack by the nucleophilic bromide ion is faster there Hence the major product is the secondary bromide... 

Deprotection by this method rests on the ease with which benzyl esters are cleaved by nucleophilic attack at the benzylic carbon m the presence of strong acids Bromide ion IS the nucleophile... 

Furan can be catalyticaHy oxidized in the vapor phase with oxygen-containing gases to maleic anhydride (93). Oxidation with bromine or in an electrochemical process using bromide ion gives 2,5-dimethoxy-2,5-dihydrofuran [332-77-4] (19) which is a cycHc acetal of maleic dialdehyde (94—96). 

The halogen displacement polymerization proceeds by a combination of the redistribution steps described for oxidative coupling polymerization and a sequence in which a phenoxide ion couples with a phenoxy radical (eq. 11) and then expels a bromide ion. The resultant phenoxy radical can couple with another phenoxide in a manner that is analogous to equation 11 or it can redistribute with other aryloxy radicals in a process analogous to equations 7 and 8. 

Electrochemical Process. Applying an electrical current to a brine solution containing propylene results in oxidation of propylene to propylene oxide. The chemistry is essentially the same as for the halohydrin process. AH of the chemistry takes place in one reactor. Most of the reported work uses sodium or potassium bromide as the electrolyte. Bromine, generated from bromide ions at the anode, reacts with propylene and water to form propylene bromohydrin. Hydroxide generated at the cathode then reacts with the bromohydrin to yield propylene oxide (217—219). The net reaction involves transfer of two electrons ... 

Silver Bromide. Silver bromide, AgBr, is formed by the addition of bromide ions to an aqueous solution of silver nitrate. The light yellow to green-yeUow precipitate is less soluble in ammonia than silver chloride, but it easily dissolves in the presence of other complexing agents, such as thiosulfate ions. 

At 25°C, pH 7.5, 1.5 ppm FAC, and 25 ppm cyanuric acid, the calculated HOCl concentration is only 0.01 ppm. Although the monochloroisocyanurate ion hydrolyzes to only a small extent, it serves as a reservoir of HOCl because of rapid hydrolysis. Indeed, this reaction is so fast that HClCy behaves like FAC in all wet methods of analysis. Furthermore, since HClCy absorbs uv only below 250 nm, which is filtered out of solar radiation by the earth s atmosphere, it is more resistant to decomposition than the photoactive C10 , which absorbs sunlight at 250—350 nm and represents the principal mode of chlorine loss in unstabilized pools (30). As Httie as 5 ppm of bromide ion prevents stabilization of FAC by cyanuric acid (23) (see also Cyanuric and ISOCYANURIC acids). 

---