Bromine

2008/9 Schools Wikipedia Selection. Related subjects: Chemical elements

35 selenium ← bromine → krypton Cl ↑ Br ↓ I Periodic Table - Extended Periodic Table
General
Name, Symbol, Number	bromine, Br, 35
Chemical series	halogens
Group, Period, Block	17, 4, p
Appearance	gas/liquid: red-brown solid: metallic luster
Standard atomic weight	79.904 (1)  g·mol−1
Electron configuration	[Ar] 4s2 3d10 4p5
Electrons per shell	2, 8, 18, 7
Physical properties
Phase	liquid
Density (near r.t.)	(Br2, liquid) 3.1028  g·cm−3
Melting point	265.8  K (-7.2 ° C, 19 ° F)
Boiling point	332.0  K (58.8 ° C, 137.8 ° F)
Critical point	588 K, 10.34 MPa
Heat of fusion	(Br2) 10.571   kJ·mol−1
Heat of vaporization	(Br2) 29.96   kJ·mol−1
Specific heat capacity	(25 °C) (Br2) 75.69  J·mol−1·K−1
Vapor pressure P(Pa) 1 10 100 1 k 10 k 100 k at T(K) 185 201 220 244 276 332
Atomic properties
Crystal structure	orthorhombic
Oxidation states	5, 4, 3, 1, -1 (strongly acidic oxide)
Electronegativity	2.96 (Pauling scale)
Ionization energies ( more)	1st:  1139.9   kJ·mol−1
	2nd:  2103  kJ·mol−1
	3rd:  3470  kJ·mol−1
Atomic radius	115   pm
Atomic radius (calc.)	94  pm
Covalent radius	114  pm
Van der Waals radius	185 pm
Miscellaneous
Magnetic ordering	nonmagnetic
Electrical resistivity	(20 °C) 7.8×1010  Ω·m
Thermal conductivity	(300 K) 0.122  W·m−1·K−1
Speed of sound	(20 °C) ? 206 m/s
CAS registry number	7726-95-6
Selected isotopes
Main article: Isotopes of bromine iso NA half-life DM DE ( MeV) DP 79Br 50.69% 79Br is stable with 44 neutrons 81Br 49.31% 81Br is stable with 46 neutrons
References

Bromine (pronounced /ˈbroʊmiːn/, /ˈbroʊmaɪn/, /ˈbroʊmɪn/, Greek: βρῶμος, brómos, meaning "stench (of he-goats)" ), is a chemical element with the symbol Br and atomic number 35. A halogen element, bromine is a red volatile liquid at standard room temperature that is intermediate in reactivity between chlorine and iodine. Bromine vapours are corrosive and toxic. Approximately 730,000,000 kg was produced in 1993. The main applications for bromine are in fire retardants and fine chemicals.

History

Bromine was discovered independently by two chemists Antoine Balard and Carl Jacob Löwig in 1825 and 1826.

Balard found bromide salts in the ash of sea weed from the salt marshes of Montpellier in 1826. The seaweed was used to produce iodine, but also contained bromine.

Carl Jacob Löwig working at the laboratory of Leopold Gmelin produced elemental bromine by reacting mineral salts, which contained bromides, with chlorine gas. The publication of the results was delayed and Balard published his results first.

Bromine was not produced in quantity until 1860. The French chemist and physicist Joseph-Louis Gay-Lussac suggested the name bromine due to the characteristic smell of the vapors. Some also suggest that it may have been discovered by Bernard Courtois, the man who discovered iodine.

Isotopes

Bromine has 2 stable isotopes: Br-79 (50.69%) and Br-81 (49.31%). At least another 23 isotopes are known to exist. Many of the bromine isotopes are fission products. Several of the heavier bromine isotopes from fission are delayed neutron emitters. All of the radioactive bromine isotopes are relatively short lived. The longest half life is the neutron deficient Br-77 at 2.376 days. The longest half life on the neutron rich side is Br-82 at 1.471 days. A number of the bromine isotopes exhibit metastable isomers. Stable Br-79 exhibits a radioactive isomer, with a half life of 4.86 seconds. It decays by isomeric transition to the stable ground state.

Notable characteristics

Bromine is the only liquid nonmetallic element at room temperature and one of only six elements on the periodic table that are liquid at or close to room temperature. The pure chemical element has the physical form of a diatomic molecule, Br₂. It is a dense, mobile, reddish-brown liquid, that evaporates easily at standard temperature and pressures to give a red vapor (its colour resembles nitrogen dioxide) that has a strong disagreeable odour resembling that of chlorine. Bromine is a halogen, and is less reactive than chlorine and more reactive than iodine. Bromine is slightly soluble in water, and highly soluble in carbon disulfide, aliphatic alcohols (such as methanol), and acetic acid. It bonds easily with many elements and has a strong bleaching action.

Certain bromine-related compounds have been evaluated to have an ozone depletion potential or bioaccumulate in living organisms. As a result many industrial bromine compounds are no longer manufactured, are being restricted, or scheduled for phasing out.

Bromine is a powerful oxidizing agent. It reacts vigorously with metals, especially in the presence of water, as well as most organic compounds, especially upon illumination.

Bromine has no known role in human health. Organobromine compounds do occur naturally, a famous example being Tyrian purple. Most organobromine compounds in nature arise via the action of vanadium bromoperoxidase.

Occurrence and production

World bromine production trend

The diatomic element Br₂ does not occur naturally. Instead, bromine exists exclusively as bromide salts in diffuse amounts in crustal rock. Due to leaching, bromide salts have accumulated in sea water (85 ppm), but at a lower concentration than chloride. Bromine may be economically recovered from bromide-rich brine wells and from the Dead Sea waters (up to 50000 ppm).

Approximately 500,000 metric tons (worth around US$350 million) of bromine are produced per year (2001) worldwide with the United States and Israel being the primary producers. Bromine production has increased sixfold since the 1960s. The largest bromine reserve in the United States is located in Columbia and Union County, Arkansas, U.S. Israel's bromine reserves are contained in the waters of the Dead Sea. The bromide-rich brines are treated with chlorine gas, flushing through with air. In this treatment, bromide anions are oxidized to bromine by the chlorine gas.

2 Br⁻ + Cl₂ → 2 Cl⁻ + Br₂

Because of its commercial availability and long shelf-life, bromine is not typically prepared. Small amounts of bromine can however be generated through the reaction of solid sodium bromide with concentrated sulfuric acid (H₂SO₄). The first stage is formation of hydrogen bromide (HBr), which is a gas, but under the reaction conditions some of the HBr is oxidized further by the sulfuric acid to form bromine (Br₂) and sulfur dioxide (SO₂).

NaBr (s) + H₂SO₄ (aq) → HBr (aq) + NaHSO₄ (aq)

2 HBr (aq) + H₂SO₄ (aq) → Br₂ (g) + SO₂ (g) + 2 H₂O (l)

Similar alternatives, such as the use of dilute hydrochloric acid with sodium hypochlorite, are also available. The most important thing is that the anion of the acid (in the above examples, sulfate and chloride, respectively) be more electronegative than bromine, allowing the substitution reaction to occur.

Compounds

Organic chemistry

Organic compounds are brominated by either addition or substitution reactions. Bromine undergoes electrophilic addition to the double-bonds of alkenes, via a cyclic bromonium intermediate. In non-aqueous solvents such as carbon disulfide, this affords the di-bromo product. For example, reaction with ethylene will produce 1,2-dibromoethane. Bromine also undergoes electrophilic addition to phenols and anilines. When used as bromine water, the corresponding bromohydrin is formed instead. So reliable is the reactivity or bromine that bromine water is employed as a reagent to test for the presence alkenes, phenols, and anilines. Like the other halogens, bromine participates in free radical reactions. For example hydrocarbons are brominated upon treatment with bromine in the presence of light.

Bromine, sometimes with a catalytic amount of phosphorus, easily brominates carboxylic acids at the α-position. This method, the Hell-Volhard-Zelinsky reaction, is the basis of the commercial route to bromoacetic acid.

N-Bromosuccinimide is commonly used as a substitute for elemental bromine, being easier to handle, and reacting more mildly and thus more selectively.

Organic bromides are often preferable relative to the less reactive chlorides and more expensive iodide-containing reagent]]s. Thus, Grignard and organolithium compound are most often generated from the corresponding bromides.

Inorganic chemistry

Bromine is an oxidizer, and it will oxidize iodide ions to iodine, being itself reduced to bromide:

Br₂ + 2 I⁻ → 2 Br⁻ + I₂

Bromine will also oxidize metals and metaloids to the corresponding bromides. Anhydrous bromine is less reactive toward many metals than hydrated bromine, however. Dry bromine reacts vigorously with aluminium, titanium, mercury as well as alkaline earths and alkali metals.

Applications

A wide variety of organobromine compounds are used in industry. Some are prepared from bromine and others are prepared from hydrogen bromide, which is obtained by burning hydrogen in bromine.

Illustrative of the addition reaction is the preparation of 1,2-Dibromoethane, the organobromine compound produced in the largest amounts:

C₂H₄ + Br₂ → CH₂BrCH₂Br

Ethylene bromide is an additive in gasolines containing lead anti- engine knocking agents. It scavenges lead by forming volatile lead bromide, which is exhausted from the engine. This application has declined since the 1970s due to environmental regulations. Ethylene bromide is also used as a fumigant, but again this application is declining.

Brominated flame retardants represent a commodity of growing importance. Specific compound used produced for this purpose include tetrabromobisphenol A, decabromodiphenyl ether, and vinyl bromide.

The bromides of calcium, sodium, and zinc account for a sizable part of the bromine market. These salts form dense solutions in water that are used as drilling fluids.

Miscellaneous uses:

• Several dyes, agrichemicals, and pharmaceuticals are organobromine compounds. 1-Bromo-3-chloropropane, 1-bromoethylbenzene, and 1-bromoalkanes are prepared by the antimarkovnikov addition of HBr to alkenes. Ethidium bromide, EtBr, is used as a DNA stain in gel electrophoresis.
• Bromine is also used in for the production of brominated vegetable oil, which is used as an emulsifier in many citrus-flavored soft drinks.
• High refractive index compounds
• Water purification compounds, Disinfectants
• Potassium bromide is used in some photographic developers to inhibit the formation of fog (undesired reduction of silver).

Safety

Elemental bromine is toxic and causes burns. As an oxidizing agent, it is incompatible with most organic and inorganic compounds. Care needs to taken when transporting bromine, it is commonly carried in steel tanks lined with lead, supported by strong metal frames.

When certain ionic compounds containing Bromine are mixed with Potassium permanganate (KMnO₄), they will form a pale brown cloud of Bromine gas. This gas smells like bleach and is very irritating to the mucus membranes. This form of Bromine will appear to diffuse slowly, but it will suddenly disappear. Upon exposure, one should move to fresh air immediately. If symptoms arise, medical attention is needed.