Chlorine is intermediate in reactivity between fluorine and bromine, and is one of the most reactive elements. Chlorine is a weaker oxidising agent than fluorine but a stronger one than bromine or iodine. This can be seen from the
standard electrode potentials of the X2/X− couples (F, +2.866 V; Cl, +1.395 V; Br, +1.087 V; I, +0.615 V;
At, approximately +0.3 V). However, this trend is not shown in the bond energies because fluorine is singular due to its small size, low polarisability, and inability to show
hypervalence. As another difference, chlorine has a significant chemistry in positive oxidation states while fluorine does not. Chlorination often leads to higher oxidation states than bromination or iodination but lower oxidation states than fluorination. Chlorine tends to react with compounds including M–M, M–H, or M–C bonds to form M–Cl bonds.
Hydrogen chloride The simplest chlorine compound is
hydrogen chloride, HCl, a major chemical in industry as well as in the laboratory, both as a gas and dissolved in water as
hydrochloric acid. It is often produced by burning hydrogen gas in chlorine gas, or as a byproduct of chlorinating
hydrocarbons. Another approach is to treat
sodium chloride with concentrated
sulfuric acid to produce hydrochloric acid, also known as the "salt-cake" process: At room temperature, hydrogen chloride is a colourless gas, like all the hydrogen halides apart from
hydrogen fluoride, since hydrogen cannot form strong
hydrogen bonds to the larger electronegative chlorine atom; however, weak hydrogen bonding is present in solid crystalline hydrogen chloride at low temperatures, similar to the hydrogen fluoride structure, before disorder begins to prevail as the temperature is raised. Unlike hydrogen fluoride, anhydrous liquid hydrogen chloride is difficult to work with as a solvent, because its boiling point is low, it has a small liquid range, its
dielectric constant is low and it does not dissociate appreciably into H2Cl+ and ions – the latter, in any case, are much less stable than the
bifluoride ions () due to the very weak hydrogen bonding between hydrogen and chlorine, though its salts with very large and weakly polarising cations such as
Cs+ and quaternary ammonium cation| (R =
Me,
Et,
Bun) may still be isolated. Anhydrous hydrogen chloride is a poor solvent, only able to dissolve small molecular compounds such as
nitrosyl chloride and
phenol, or salts with very low
lattice energies such as tetraalkylammonium halides. It readily protonates
nucleophiles containing lone-pairs or π bonds.
Solvolysis,
ligand replacement reactions, and oxidations are well-characterised in hydrogen chloride solution: :Ph3SnCl + HCl ⟶ Ph2SnCl2 + PhH (solvolysis) :Ph3COH + 3 HCl ⟶ + H3O+Cl− (solvolysis) : + BCl3 ⟶ + HCl (ligand replacement) :PCl3 + Cl2 + HCl ⟶ (oxidation)
Other binary chlorides , NiCl2(H2O)6 Nearly all elements in the periodic table form binary chlorides. The exceptions are decidedly in the minority and stem in each case from one of three causes: extreme inertness and reluctance to participate in chemical reactions (the
noble gases, with the exception of
xenon in the highly unstable
XeCl2 and XeCl4); extreme nuclear instability hampering chemical investigation before decay and transmutation (many of the heaviest elements beyond
bismuth); and having an electronegativity higher than chlorine's (
oxygen and
fluorine) so that the resultant binary compounds are formally not chlorides but rather oxides or fluorides of chlorine. Even though
nitrogen in NCl3 is bearing a negative charge, the compound is usually called
nitrogen trichloride. Chlorination of metals with Cl2 usually leads to a higher oxidation state than bromination with Br2 when multiple oxidation states are available, such as in
MoCl5 and
MoBr3. Chlorides can be made by reaction of an element or its oxide, hydroxide, or carbonate with hydrochloric acid, and then dehydrated by mildly high temperatures combined with either low pressure or anhydrous hydrogen chloride gas. These methods work best when the chloride product is stable to hydrolysis; otherwise, the possibilities include high-temperature oxidative chlorination of the element with chlorine or hydrogen chloride, high-temperature chlorination of a metal oxide or other halide by chlorine, a volatile metal chloride,
carbon tetrachloride, or an organic chloride. For instance,
zirconium dioxide reacts with chlorine at standard conditions to produce
zirconium tetrachloride, and
uranium trioxide reacts with
hexachloropropene when heated under
reflux to give
uranium tetrachloride. The second example also involves a reduction in
oxidation state, which can also be achieved by reducing a higher chloride using hydrogen or a metal as a reducing agent. This may also be achieved by thermal decomposition or disproportionation as follows: : ->[\ce{-78 ^\circ C}] This reaction is conducted in the oxidising solvent
arsenic pentafluoride. The trichloride anion, , has also been characterised; it is analogous to
triiodide.
Chlorine fluorides The three fluorides of chlorine form a subset of the
interhalogen compounds, all of which are
diamagnetic. Some cationic and anionic derivatives are known, such as , , , and Cl2F+. Some
pseudohalides of chlorine are also known, such as
cyanogen chloride (ClCN, linear), chlorine
cyanate (ClNCO), chlorine
thiocyanate (ClSCN, unlike its oxygen counterpart), and chlorine
azide (ClN3). It can act as a fluoride ion donor or acceptor (Lewis base or acid), although it does not dissociate appreciably into and ions.
Chlorine pentafluoride (ClF5) is made on a large scale by direct fluorination of chlorine with excess
fluorine gas at 350 °C and 250 atm, and on a small scale by reacting metal chlorides with fluorine gas at 100–300 °C. It melts at −103 °C and boils at −13.1 °C. It is a very strong fluorinating agent, although it is still not as effective as chlorine trifluoride. Only a few specific stoichiometric reactions have been characterised.
Arsenic pentafluoride and
antimony pentafluoride form ionic adducts of the form [ClF4]+[MF6]− (M = As, Sb) and water reacts vigorously as follows: :2 H2O + ClF5 ⟶ 4 HF + FClO2 The product,
chloryl fluoride, is one of the five known chlorine oxide fluorides. These range from the thermally unstable FClO to the chemically unreactive
perchloryl fluoride (FClO3), the other three being FClO2, F3ClO, and F3ClO2. All five behave similarly to the chlorine fluorides, both structurally and chemically, and may act as Lewis acids or bases by gaining or losing fluoride ions respectively or as very strong oxidising and fluorinating agents.
Chlorine oxides (ClO2) gas above a solution of hydrochloric acid and sodium chlorite in water, also containing dissolved chlorine dioxide , Cl2O7, the most stable of the chlorine oxides The
chlorine oxides are well-studied in spite of their instability (all of them are endothermic compounds). They are important because they are produced when
chlorofluorocarbons undergo photolysis in the upper atmosphere and cause the destruction of the ozone layer. None of them can be made from directly reacting the elements.
Dichlorine monoxide (Cl2O) is a brownish-yellow gas (red-brown when solid or liquid) which may be obtained by reacting chlorine gas with yellow
mercury(II) oxide. It is very soluble in water, in which it is in equilibrium with
hypochlorous acid (HOCl), of which it is the anhydride. It is thus an effective bleach and is mostly used to make
hypochlorites. It explodes on heating or sparking or in the presence of ammonia gas. Dichlorine hexoxide is a dark-red liquid that freezes to form a solid which turns yellow at −180 °C: it is usually made by reaction of chlorine dioxide with oxygen. Despite attempts to rationalise it as the dimer of ClO3, it reacts more as though it were chloryl perchlorate, [ClO2]+[ClO4]−, which has been confirmed to be the correct structure of the solid. It hydrolyses in water to give a mixture of chloric and perchloric acids: the analogous reaction with anhydrous
hydrogen fluoride does not proceed to completion. : + 5 Cl− + 6 H+ ⟶ 3 Cl2 + 3 H2O Perchlorates and perchloric acid (HOClO3) are the most stable oxo-compounds of chlorine, in keeping with the fact that chlorine compounds are most stable when the chlorine atom is in its lowest (−1) or highest (+7) possible oxidation states. Perchloric acid and aqueous perchlorates are vigorous and sometimes violent oxidising agents when heated, in stark contrast to their mostly inactive nature at room temperature due to the high activation energies for these reactions for kinetic reasons. Perchlorates are made by electrolytically oxidising sodium chlorate, and perchloric acid is made by reacting anhydrous
sodium perchlorate or
barium perchlorate with concentrated hydrochloric acid, filtering away the chloride precipitated and distilling the filtrate to concentrate it. Anhydrous perchloric acid is a colourless mobile liquid that is sensitive to shock that explodes on contact with most organic compounds, sets
hydrogen iodide and
thionyl chloride on fire and even oxidises silver and gold. Although it is a weak ligand, weaker than water, a few compounds involving coordinated are known. In addition, all the above chemical regularities are valid for "normal" or close to normal conditions, while at ultra-high pressures (for example, in the cores of large planets), chlorine can form a Na3Cl compound with sodium, which does not fit into traditional concepts of chemistry.
Organochlorine compounds Like the other carbon–halogen bonds, the C–Cl bond is a common functional group that forms part of core
organic chemistry. Formally, compounds with this functional group may be considered organic derivatives of the chloride anion. Due to the difference of electronegativity between chlorine (3.16) and carbon (2.55), the carbon in a C–Cl bond is electron-deficient and thus
electrophilic.
Chlorination modifies the physical properties of hydrocarbons in several ways: chlorocarbons are typically denser than
water due to the higher atomic weight of chlorine versus hydrogen, and aliphatic organochlorides are
alkylating agents because chloride is a
leaving group.
Alkanes and
aryl alkanes may be chlorinated under
free-radical conditions, with UV light. However, the extent of chlorination is difficult to control: the reaction is not
regioselective and often results in a mixture of various isomers with different degrees of chlorination, though this may be permissible if the products are easily separated. Aryl chlorides may be prepared by the
Friedel-Crafts halogenation, using chlorine and a
Lewis acid catalyst. Chlorinated organic compounds are found in nearly every class of biomolecules including
alkaloids,
terpenes,
amino acids,
flavonoids,
steroids, and
fatty acids. Organochlorides, including
dioxins, are produced in the high temperature environment of forest fires, and dioxins have been found in the preserved ashes of lightning-ignited fires that predate synthetic dioxins. In addition, a variety of simple chlorinated hydrocarbons including dichloromethane, chloroform, and
carbon tetrachloride have been isolated from marine algae. A majority of the
chloromethane in the environment is produced naturally by biological decomposition, forest fires, and volcanoes. Some types of organochlorides, though not all, have significant toxicity to plants or animals, including humans. Dioxins, produced when organic matter is burned in the presence of chlorine, and some
insecticides, such as
DDT, are
persistent organic pollutants which pose dangers when they are released into the environment. For example, DDT, which was widely used to control insects in the mid 20th century, also accumulates in food chains, and causes reproductive problems (e.g., eggshell thinning) in certain bird species. Due to the ready homolytic fission of the C–Cl bond to create chlorine radicals in the upper atmosphere,
chlorofluorocarbons have been discontinued due to the harm they do to the ozone layer. ==Occurrence==