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.
Potassium bromide and sodium bromide were used as anticonvulsants and sedatives in the late 19th and early 20th centuries, until it was gradually superseded by chloral hydrate and then the barbiturates.
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 decay by isomeric transition to the stable ground state.
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 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.
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 556,000 metric tons (worth around US$2.5 billion) of bromine are produced per year (2007) worldwide with the United States, China, 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. China's bromine reserves are located in the Shandong Province and 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.
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).
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.
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 reagents. Thus, Grignard and organolithium compound are most often generated from the corresponding bromides.
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.
Illustrative of the addition reaction is the preparation of 1,2-Dibromoethane, the organobromine compound produced in the largest amounts:
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.
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.
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. Upon exposure, one should move to fresh air immediately. If symptoms arise, medical attention is needed.