Halogen

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Group	17
Period
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The halogens or halogen elements are a series of nonmetal elements from Group 17 (old-style: VII or VIIA; Group 7 IUPAC Style) of the periodic table, comprising fluorine, F; chlorine, Cl; bromine, Br; iodine, I; and astatine, At. The undiscovered element 117, temporarily named ununseptium, may also be considered a halogen.

The group of halogens is the only group which contains elements in all three familiar states of matter at standard temperature and pressure.

Abundance

Owing to their high reactivity, the halogens are found in the environment only in compounds or as ions. Halide ions and oxoanions such as IO₃⁻ can be found in many minerals and in seawater. Halogenated organic compounds can also be found as natural products in living organisms. In their elemental forms, the halogens exist as diatomic molecules, but these only have a fleeting existence in nature and are much more common in the laboratory and in industry. At room temperature and pressure, fluorine and chlorine are gases, bromine is a liquid and iodine and astatine are solids; Group 17 is therefore the only periodic table group exhibiting all three states of matter at room temperature.

Etymology

The term halogen originates from 18th century scientific French nomenclature based on adaptations of Greek roots: hals (sea) or halas (salt), and gen- (to generate) — referring to elements which produce a salt in union with a metal.

Properties

The halogens show a number of trends when moving down the group - for instance, decreasing electronegativity and reactivity, increasing melting and boiling point.

Halogen	Standard Atomic Weight (u)	Melting Point (K)	Boiling Point (K)	Electronegativity (Pauling)
Fluorine	18.998	53.53	85.03	3.98
Chlorine	35.453	171.6	239.11	3.16
Bromine	79.904	265.8	332.0	2.96
Iodine	126.904	386.85	457.4	2.66
Astatine	(210)	575	610 ?	2.2
Ununseptium	(291)*	*	*	*

* Ununseptium has not yet been discovered; values are either unknown if no value appears, or are estimates based on other similar chemicals.

Diatomic halogen molecules

halogen	molecule	structure	model	d(X−X) / pm (gas phase)	d(X−X) / pm (solid phase)
fluorine	F2	File:Difluorine-2D-dimensions.png	File:Fluorine-3D-vdW.png	143	149
chlorine	Cl2	File:Dichlorine-2D-dimensions.png	File:Chlorine-3D-vdW.png	199	198
bromine	Br2	File:Dibromine-2D-dimensions.png	File:Bromine-3D-vdW.png	228	227
iodine	I2	File:Diiodine-2D-dimensions.png	File:Iodine-3D-vdW.png	266	272

Chemistry

Reactivity

Halogens are highly reactive, and as such can be harmful or lethal to biological organisms in sufficient quantities. This high reactivity is due to their atoms being one electron short of a full outer shell of eight electrons. They can gain this electron by reacting with atoms of other elements. Fluorine is the most reactive element in existence, attacking such inert materials as glass, and forming compounds with the heavier noble gases. It is a corrosive and highly toxic gas. The reactivity of fluorine is such that, if used or stored in laboratory glassware, it can react with glass in the presence of small amounts of water to form SiF₄. Thus fluorine must be handled with substances such as Teflon, extremely dry glass, or metals such as copper or steel which form a protective layer of fluoride on their surface.

Both chlorine and bromine are used as disinfectants for drinking water, swimming pools, fresh wounds, dishes, and surfaces. They kill bacteria and other potentially harmful microorganisms through a process known as sterilization. Their reactivity is also put to use in bleaching. Sodium hypochlorite, which is produced from chlorine, is the active ingredient of most fabric bleaches and chlorine-derived bleaches are used in the production of some paper products.

Hydrogen halides

The halogens all form binary compounds with hydrogen, the hydrogen halides, HX (HF, HCl, HBr, HI), a series of particularly strong acids. When in aqueous solution, the hydrogen halides are known as hydrohalic acids. HAt, or "hydrastatic acid", should also qualify, but it is not typically included in discussions of hydrohalic acid due to astatine's extreme instability toward alpha decay.

Interhalogen compounds

Main article: Interhalogen

The halogens react with each other to form interhalogen compounds. Diatomic interhalogen compounds (e.g. BrF, ICl, ClF) bear resemblance to the pure halogens in some respects. The properties and behaviour of a diatomic interhalogen compound tend to be intermediate between those of its parent halogens. Some properties, however, are found in neither parent halogen − Cl₂ and I₂ are soluble in CCl₄ but ICl is not, since it is a polar molecule due to the relatively large electronegativity difference between I and Cl.

Organohalogen compounds

Many synthetic organic compounds such as plastic polymers, and a few natural ones, contain halogen atoms; these are known as halogenated compounds or organic halides. Chlorine is by far the most abundant of the halogens, and the only one needed in relatively large amounts (as chloride ions) by humans. For example, chloride ions play a key role in brain function by mediating the action of the inhibitory transmitter GABA and are also used by the body to produce stomach acid. Iodine is needed in trace amounts for the production of thyroid hormones such as thyroxine. On the other hand, neither fluorine nor bromine are believed to be essential for humans, although small amounts of fluoride can make tooth enamel resistant to decay.

Drug discovery

In drug discovery, the incorporation of halogen atoms into a lead drug candidate results in analogues that are more lipophilic and less water soluble. Consequently, halogen atoms are used to improve penetration through lipid membranes. However, there is an undesirable tendency for halogenated drugs to accumulate in lipid tissue.

The chemical reactivity of halogen atoms depends on both their point of attachment to the lead and the nature of the halogen. Aromatic halogen groups are far less reactive than aliphatic halogen groups, which can exhibit considerable chemical reactivity. For aliphatic carbon-halogen bonds the C-F bond is the strongest and usually less chemically reactive than aliphatic C-H bonds. The other aliphatic-halogen bonds are weaker, their reactivity increasing down the periodic table. They are usually more chemically reactive than aliphatic C-H bonds. Consequently, the most popular halogen substitutions are the less reactive aromatic fluorine and chlorine groups.

See also

• Pseudohalogen
• Halogen bond

References

1. N. N. Greenwood, A. Earnshaw, Chemistry of the Elements, 2nd ed., Butterworth-Heinemann, Oxford, UK, 1997.
2. G. Thomas, Medicinal Chemistry an Introduction, John Wiley & Sons, West Sussex, UK, 2000.

Explanation of above periodic table slice:

bgcolor="Template:Element color/Halogens" | Halogens	Atomic numbers in Template:Element color/Gas are gases	Atomic numbers in Template:Element color/Liquid are liquids	Atomic numbers in Template:Element color/Solid are solids
style="border:Template:Element frame/Primordial;" | Solid borders indicate primordial elements (older than the Earth)	style="border:Template:Element frame/Natural radio;" | Dashed borders indicate radioactive natural elements	style="border:Template:Element frame/Synthetic;" | Dotted borders indicate radioactive synthetic elements	style="border:Template:Element frame/Undiscovered;" | No borders indicates undiscovered elements

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