Bromine ratios

Aromatic bromine compounds can be formed and transformed during various thermal processes, like aromatic chlorine compounds (ref. 22). Brominated dibenzodioxins and -furans and mixed brominated/chlorinated compounds have been detected in trace levels in the fly ash of a municipal waste incinerator (ref. 23).Chlorine is generally abundant compared to the bromine of typical municipal waste the chlorine vs. bromine ratio is in the range of 250 1. 

Results For the St. Louis data, the target transformation analysis results for the fine fraction without July Uth and 5th are given in table 6. The presence of a motor vehicle source, a sulfur source, a soil or flyash source, a titanium source, and a zinc source are indicated. The sulfur, titanium and zinc factors were determined from the simple initial test vectors for those elements. The concentration of sulfur was not related to any other elements and represents a secondary sulfate aerosol resulting from the conversion of primary sulfur oxide emissions. Titanium was found to be associated with sulfur, calcium, iron, and barium. Rheingrover ( jt) identified the source of titanium as a paint-pigment factory located to the south of station 112. The zinc factor, associated with the elements chlorine, potassium, iron and lead, is attributed to refuse incinerator emissions. This factor could also represent particles from zinc and/or lead smelters, though a high chlorine concentration is usually associated with particles from refuse incinerators ( ). The sulfur concentration in the refined sulfate factor is consistent with that of ammonium sulfate. The calculated lead concentration in the motor vehicle factor of ten percent and a lead to bromine ratio of about 0.28 are typical of values reported in the literature (25). The concentration of lead in... 

For some industrial cooling water applications, where process contamination is often an inherent problem, a high chlorine/low bromine ratio product may be preferable. This type of problem can happen, for example, where repeated hot/cold cycles are part of the process and some valve leakage and interchange of water between circuits may occur. Thus, the (lower cost) chlorine component is employed in satisfying the contaminant halogen demand and the bromine component (perhaps with some degree of Br recycle) subsequently acts as a biocide. 

Nitrogen tribromide (NBrs) is reported as a red, oily, volatile liquid with offensive odor [6, 8]. From later work it appears, however, that nitrogen tribromide is a solid substance of a deep red color with nitrogen to bromine ratio 1 3 [40]. This extremely temperature-sensitive substance explodes even at —100 °C in Nujol-pentane suspension (1 2.7) with the slightest mechanical disturbance [40]. 

Isotopic clusters are especially apparent when atoms such as bromine and chlorine are present m an organic compound The natural ratios of isotopes m these elements are... 

Treatment of 2 4 6 tn tert butylphenol with bromine in cold acetic acid gives the compound CigH29BrO in quantitative yield The infrared spectrum of this compound contains absorptions at 1630 and 1655 cm Its H NMR spectrum shows only three peaks (all singlets) at 8 1 2 13 and 6 9 in the ratio 9 18 2 What is a reasonable structure for the compound" ... 

For other elements that occur with major relative abundances of more than one isotope in the natural state, the isotope pattern becomes much more complex. For example, with chlorine and bromine, the presence of these elements is clearly apparent from the isotopes Cl and for chlorine and Br and Br for bromine. Figure 47.2a shows the molecular ion region for the compound chlorodecane. Now, there are new situations in that C, C, C1, and Cl isotopes all have probabilities of occurring together. Thus, there are molecular ion peaks for + Cl, C + Cl, + Cl, and so on. Even so, the isotopic ratio of 3 1 for Cl to Cl is very clear... 

Partial mass spectra showing the isotope patterns in the molecular ion regions for ions containing carbon and (a) only one chlorine atom, (b) only one bromine atom, and (c) one chlorine and one bromine atom. The isotope patterns are quite different from each other. Note how the halogen isotope ratios appear very clearly as 3 1 for chlorine in (a), 1 1 for bromine in (b), and 3 4 1 for chlorine and bromine in (c). If the numbers of halogens were not known, the pattern could be used in a reverse sense to decide their number. 

Bromine Trifluoride. Bromine trifluoride is produced commercially by the reaction of fluorine with bromine ia a continuous gas-phase process where the ratio of fluorine to bromine is maintained close to 3 1. It is also produced ia a Hquid-phase batch reaction where fluorine is added to Hquid bromine at a temperature below the boiling poiat of bromine trifluoride. 

Health and Safety Factors. Fluorocarbons containing bromine or iodine are more toxic than the corresponding chloro compounds. When the ratio of the fluorine to other halogens is high, the toxicity can be quite low, especially for bromofluorocarbons. Perfluoro-l-bromooctane [423-55-2] has an LD q of greater than 64 mL/kg when adininistered into the gastrointestinal tract, and has Htde effect when instilled into the lungs (49). Other examples are included in Table 7. 

Similar reactions occur with ammonia and HOBr (19—25), but since HOBr is a stronger electrophile than HOCl, formation rates are faster. Because of rapid bromine transfer between bromamines, equihbrium concentrations of the respective bromamines are obtained quickly. Mon ohrom amine predominates at basic pH at high N Br ratios. Below pH 8.5, NHBr2 and NBr predominate. Tribromamine formation is favored at lower pH and higher Br N ratios. The bromamines are less stable than chloramines but are better disinfectants. 

Halobutyls. Chloro- and bromobutyls are commercially the most important butyl mbber derivatives. The halogenation reaction is carried out in hydrocarbon solution using elemental chlorine or bromine (equimolar ratio with enchained isoprene). The halogenation is fast, and proceeds mainly by an ionic mechanism. The stmctures that may form include the following ... 

Halogenated Butyl Rubber. The halogenation is carried out in hydrocarbon solution using elemental chlorine or bromine in a 1 1 molar ratio with enchained isoprene. The reactions ate fast chlorination is faster. Both chlorinated and brominated butyl mbbers can be produced in the same plant in blocked operation. However, there are some differences in equipment and reaction conditions. A longer reaction time is requited for hromination. Separate faciUties are needed to store and meter individual halogens to the reactor. Additional faciUties are requited because of the complexity of stabilising brominated butyl mbber. 

Hydroxyquinoline forms the complex with Cu(II) in ratio 1 1 at pH 5-7. The composition of the complex is changed on 1 2 at pH>7. 8-Hydroxy-quinoline accepts bromine therefore its excess has been removed with NaOH solution. The complex was extracted with chloroform. It was shown that double extraction was enough to extract the complex. The detection limit is 5x10 M during 10c and at current generation IxlO A. 

A somewhat different approach to the production of thermoplastic polyolefin rubbers has been adopted by Allied Chemical with their ET polymers. With these materials butyl rubber is grafted on to polyethylene chains using a phenolic material such as brominated hydroxymethyl phenol. The initial grades of these polymers, which were introduced commercially towards the end of the 1970s, had polyethylene butyl rubber ratios of 50 50 and 75 25. Both low-density and high-density polyethylene-based varieties were produced. 

Because the product composition is kinetically controlled, the isomer ratio will be governed by the relative magnitudes of AG, AGI, and AG, the energies of activation for the ortho, meta, and para transition states, respectively. In Fig. 4.7 a qualitative comparison of these AG values is made. At the transition state, a positive charge is present on the benzene ring, primarily at positions 2, 4, and 6 in relation to the entering bromine. 

Interpretation of tiie ratio of capture of competing nucleophiles has led to the estimate that bromonium ions have lifetimes on the order of 10 s in methanol. This lifetime is about 100 times longer than fliat for secondary caibocations. There is also direct evidence for the existence of bromonium ions. The bromonium ion related to propene can be observed by NMR spectroscopy when l-bromo-2-fluoropropane is subjected to superacid conditions. The terminal bromine adopts a bridging position in the resulting cation. 

The bromination of 3-aroyloxycyclohexanes gives rise to a mixture of stereoisomeric and positionally isomeric addition products. The product composition for Ar = phenyl is shown. Account for the formation of each of the products and describe the factors which will affect the product ratio. 

Bromination of the enolate anion from the reaction of 3j -acetoxypregna-5,16-dien-20-one (1) with methylmagnesium bromide in the presence of cuprous chloride affords (after treatment with sodium iodide to dehalo-genate any 5,6-dibromide) a mixture of 17a-bromo- and 17)5-bromo-16a-methyl compounds (11) and (12) in a ratio 9 1. The 17a-iodides can be obtained in an analogous reaction. 

In radical reactions not involving bromine or chlorine on the substrate, rearrangements are much rarer One example is the fluorination of di-tert butyl ketone which produces perfluormated / rt-buty isobutyl ketone [J5] Although isolated yields are poor only the rearranged ketone could be isolated This is perhaps only the second example of a 1,2-acyl shift Low fluorine substrate ratios show that this rearrangement occurs after monofluorination... 

With Freon 112 or 113 as a solvent, fluonnation of pnmary butyl halides with bromine trifluonde can give mixtures of primary and secondary fluorides When 1,4 dibromobutane is the substrate, 93% l-bromo-4-fluorobutane and 1% 1-bro-mo-3-fluorobutane is obtained, with 1,4 dichlorobutane, the product contains 65% l-chloro-3-fluorobutane and 35% 1-chloro 4 fluorobutane When 4-bromo- or 4-chlorobutyl trifluoroacetate is used, the ratio of 4-fluorobutyl tnfluoroacetate to 3 fluorobutyl trifluoroacetate is 1 4 The effect of solvent is measured in another set of experiments When the reaction of bromine trifluonde and l,3-dichloro-2-fluoropropane in either Freon 113 or hydrogen fluoride is allowed to proceed to 40% conversion, the product mixture has the composition shown m Table 1 [/O] When 1 chloro 2,3-dibromopropane is combined with one-third of a mole of bromine trifluonde, both 1 bromo 3 chloro-2-fluoropropane and l-chloro-2,3-di-fluoropropane are formed [//] (equation 10)... 

Bromine is substantially less abundant in crustal rocks than either fluorine or chlorine at 2.5 ppm it is forty-sixth in order of abundance being similar to Hf 2.8, Cs 2.6, U 2.3, Eu 2.1 and Sn 2.1 ppm. Like chlorine, the largest natural source of bromine is the oceans, which contain 6.5 x 10 %, i.e. 65 ppm or 65mg/l. The mass ratio Cl Br is 300 1 in the oceans, corresponding to an atomic ratio... 

Calculate the mass ratio of a bromine atom to an atom of (a) neon (b) calcium (c) helium... 

With bromine monochloride at 0°C in a variety of solvents, 1 was converted into addition products, the product distribution being a function of solvent. A change in halogenating agent also altered the product ratio. (Scheme 4) Nucleophilic displacement reactions between these products and silver fluoride was found to cause preferential bromine substitution (83G149). 

Brief reaction of 3-aminodibenzofuran with chlorine in carbon tetrachloride at room temperature gave the 4-chloro product. After 5 min, a 1 0.4 ratio of 3-amino-4-chloro and 3-amino-1,2,4-trichloro derivatives had formed. Subsequent diazotization and reaction with Cu(I)37 Cl gave products with a labeled chlorine in the 3-position (90SC2501). 2-Methoxydibenzofuran was brominated to give the 3-bromo (33%) and a little of the 1-bromo derivative [39JA1365 84AHC(35)2],... 

Treatment with NCS in carbon tetrachloride converted the parent into the 2,3-dichloro derivative. The 2,3-dibromo compound was made similarly with NBS (74BSF2239), or with bromine in chloroform in the presence of sodium acetate (72CHE13). Monobromination is possible, but generally mixtures form with 2- and 3-bromo products in ratios of the order of 1 3 (72CHE13). It was possible to prepare 3-bromobenzo[h]sele-nophene by reaction of the 2,3-dibromo derivative with butyl lithium followed by hydrolysis. Four moles of bromine gave the 2,3,6-tribromo derivative from benzo[h]selenophene (74BSF2239). 

---