Chlorination bromination compared

This corresponds to a decreased nucleophilicity of the complexed anions. The energetic effort depends on the bromine content in the sphere of ligands. The higher the bromine content, compared to the chlorine content, the easier an halide ion can be splitted from the dimeric anion. 

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. 

The marketing of bromine/chlorine products is based primarily on comparing the oxidizing and disinfecting properties of the various granules and tablets both with directly competing products and other technologies. 

When evaluating isotope peak intensities, the first step is to compare the intensity of the (P + 2) peak to the relative abundances of the heavy isotopes of bromine, chlorine, sulfur, and silicon. If there is a fairly close fit (with one or more... 

Figure 16.1 shows Vs(r) and the sites of the a-hole Vs,max for SeBrCl, obtained with the Wave Function Analysis-Surface Analysis Suite [45]. The selenium has two cr-hole Vs,max the one on the extension of the Cl-Se bond is stronger, due to the greater electronegativity of chlorine compared to bromine. The bromine Vs nax is more positive than that of the chlorine, which is also in keeping with the trends summarized in Sect. 16.1. 

The heats of formation of Tt-complexes are small thus, — A//2soc for complexes of benzene and mesitylene with iodine in carbon tetrachloride are 5-5 and i2-o kj mol , respectively. Although substituent effects which increase the rates of electrophilic substitutions also increase the stabilities of the 7r-complexes, these effects are very much weaker in the latter circumstances than in the former the heats of formation just quoted should be compared with the relative rates of chlorination and bromination of benzene and mesitylene (i 3 o6 x 10 and i a-Sq x 10 , respectively, in acetic acid at 25 °C). 

Suggested formulations for various polymers using hexabromocyclododecane (HBCD), a brominated aHphatic a chlorinated paraffin, ie, a chlorinated aHphatic and decabromodiphenyl oxide, a brominated aromatic, are shown in Tables 2—4. These suggested formulations may not be strictiy comparable because of differences in the nature of the base resins. However, the suggestions are specific to a given UL-94 rating. 

Health and Safety Factors and Regulations. Iodine is much safer to handle at ordinary temperatures than the other halogens because iodine is a soHd and its vapor pressure is only 1 kPa (7.5 mm Hg) at 25°C, compared to 28.7 kPa (215 mm Hg) for bromine and 700 kPa (6.91 atm) for chlorine. When handling properly packed containers, usual work clothes are sufficient. In the handling of soHd, unpacked iodine, mbber gloves, mbber apron, and safety goggles are recommended. Respirators or masks are also recommended. 

In swimming pools disinfected by bromine, bromamide and bromimide can form. These compounds have about half the disinfecting power of HOBr giving bromine an advantage compared to chlorine. Chloramide and cblorimide have 80 to 100 times less disinfecting power than HOCl. Bromides. 

Several patents describe solvent-free bulk-phase halogenation (67—69). Dry soHd butyl mbber is fed into a specially designed extmder reactor and contacted with chlorine or bromine vapor. The by-product HCl or HBr ate vented directly without a separate neutralization step. Halogenated butyl mbbers produced are essentially comparable in composition and properties to commercial products made by the solution process. 

The present method offers several advantages over earlier methods. The use of carbon tetrachloride instead of diethyl ether as solvent avoids the intrusion of certain radical-chain reactions with solvent which are observed with bromine and to a lesser degree with chlorine. In addition, the potassium bromide has a reduced solubility in carbon tetrachloride compared to diethyl ether, thus providing additional driving force for the reaction and ease of purification of product. The selection of bro-... 

The stereochemistry of both chlorination and bromination of several cyclic and acyclic dienes has been determined. The results show that bromination is often stereo-specifically anti for the 1,2-addition process, whereas syn addition is preferred for 1,4-addition. Comparable results for chlorination show much less stereospeciftcity. It appears that chlorination proceeds primarily through ion-pair intermediates, whereas in bromina-hon a stereospecific anfi-l,2-addition may compete with a process involving a carbocation mtermediate. The latter can presumably give syn or anti product. 

Important differences are seen when the reactions of the other halogens are compared to bromination. In the case of chlorination, although the same chain mechanism is operative as for bromination, there is a key difference in the greatly diminished selectivity of the chlorination. For example, the pri sec selectivity in 2,3-dimethylbutane for chlorination is 1 3.6 in typical solvents. Because of the greater reactivity of the chlorine atom, abstractions of primary, secondary, and tertiary hydrogens are all exothermic. As a result of this exothermicity, the stability of the product radical has less influence on the activation energy. In terms of Hammond s postulate (Section 4.4.2), the transition state would be expected to be more reactant-like. As an example of the low selectivity, ethylbenzene is chlorinated at both the methyl and the methylene positions, despite the much greater stability of the benzyl radical ... 

Bromine chloride s reactivity with metals is not as great as that of bromine however, it is comparable to chlorine. Dry BrCl is typically two orders of magnitude less reactive with metals than dry bromine. Most BrCI is less corrosive than bromine. Like chlorine, BrCl is stored and shipped in steel containers. Also, Kynar and Viton plastics and Teflon are preferred over polyvinyl chloride (PVC) when BrCl is in the liquid or vapor states. 

The enhanced selectivity of alkane bromination over chlorination can be explained by turning once again to the Hammond postulate. In comparing the abstractions of an alkane hydrogen by Cl- and Br- radicals, reaction with Br- is less exergonic. As a result, the transition state for bromination resembles the alkyl radical more closely than does the transition state for chlorination, and the stability of that radical is therefore more important for bromination than for chlorination. 

Compare the reaction enthalpies for the halogenation of ethene by chlorine, bromine, and iodine. What trend, if any, exists in these numbers Use bond enthalpies to estimate the enthalpies of reaction. 

Photochemical degradation of brominated dibenzodioxins and fiirans has been studied. Decay of these compounds under environmental conditions is much faster compared to the chlorine analogues due to the higher values for the quantum yields of the bromine compounds. 

Since chlorine is always in more than a hundred-fold excess compared to bromine the reaction is occurring by pseudo monomolecular kinetics. The reaction occurs via nucleophilic aromatic substitution by an addition-elimination mechanism, the so-called SjsfAr mechanism (ref. 24). 

This reaction has been also described for low chlorinated dibenzodioxins. Assuming an identical MS response factor for monoBrDD and monobromohydroxy-biphenyl ether (monoBrDPE) a quantification study shows that monoBrDPE is much more stable towards photolysis compared to monoBrDD, because it accumulates in the mixture of the reaction products. For the dibrominated dibenzodioxins the same reaction (ether fission) is observed but to a minor extent. With triBrDD and higher brominated BrDD no diaryl-ether products are observed at all. 

Lower chemical reactivity with non-target molecules is useful for another performance-related reason. Microorganisms prefer the protection and luxuriant environment in biofilms (the adherent microbial communities that cause detrimental surface-fouling effects in water cooling systems). Most (>99%) of the viable microorganisms in industrial systems are found in biofilms, not floating around freely in the bulk recirculating water. Compared to unstabilized chlorine or bromine, STABREX more effectively removes and disinfects biofilms as shown in Table 6. 

The new stabilized bromine antimicrobial is an excellent antimicrobial having been proven superior in field and laboratory experiments compared to chlorine, stabilized chlorine, and equal to or better than solid hypobromite antimicrobials. The product is effective for the control of microbial biofilms and highly diverse microbial communities, including those that harbor Legionella. 

Disinfection by-products (e.g., adsorbable organic halides such as trihalomethanes) are more than 50% decreased compared to equivalent chlorine treatments in standardized AOX test with STABREX3. In practice, disinfection by-products are decreased even further in STABREX applications because less oxidant is required to control the microbial fouling process compared to bromine or chlorine applications. 

STABREX is easier and simpler to use compared to any other oxidant available for industrial water treatment. The product is pumped directly from returnable transporters (PortaFeed Systems)17 with standard chemical feed equipment. Previously, the only practical ways to apply bromine were to oxidize bromide solutions on-site with chlorine in dual liquid feed systems, or with one of the solid organically-stabilized bromine products applied from sidestream erosion feeders. The former is cumbersome and complex, and the latter is prone to dusting and difficult to control. Other oxidants require complex handling and feed of toxic volatile gases, unstable liquids, multiple-component products, or reactive solids. Simplicity in use results in reduced risk to workers and to the environment. 

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