Chlorine

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Chlorine, 17Cl
A glass container filled with chlorine gas
Chlorine
Pronunciation/ˈklɔːrn, -n/ (KLOR-een, -⁠eyen)
Appearancepale yellow-green gas
Standard atomic weight Ar°(Cl)
Chlorine in the periodic table
Hydrogen Helium
Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon
Sodium Magnesium Aluminium Silicon Phosphorus Sulfur Chlorine Argon
Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
Caesium Barium Lanthanum Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury (element) Thallium Lead Bismuth Polonium Astatine Radon
Francium Radium Actinium Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium Copernicium Nihonium Flerovium Moscovium Livermorium Tennessine Oganesson
F

Cl

Br
sulfurchlorineargon
kJ/mol
Heat of vaporisation(Cl2) 20.41 kJ/mol
Molar heat capacity(Cl2)
33.949 J/(mol·K)
Vapour pressure
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 128 139 153 170 197 239
Atomic properties
Discovery and first isolation
Carl Wilhelm Scheele (1774)
Recognized as an element byHumphry Davy (1808)
Isotopes of chlorine
Main isotopes[8] Decay
abun­dance half-life (t1/2) mode pro­duct
35Cl 76%
stable
36Cl trace 3.01×105 y
β
36Ar
ε
36S
37Cl 24% stable
 Category: Chlorine
| references

Chlorine is a

symbol Cl and atomic number 17. The second-lightest of the halogens, it appears between fluorine and bromine in the periodic table and its properties are mostly intermediate between them. Chlorine is a yellow-green gas at room temperature. It is an extremely reactive element and a strong oxidising agent: among the elements, it has the highest electron affinity and the third-highest electronegativity on the revised Pauling scale, behind only oxygen
and fluorine.

Chlorine played an important role in the experiments conducted by medieval

Ancient Greek
χλωρός (khlōrós, "pale green") because of its colour.

Because of its great reactivity, all chlorine in the Earth's crust is in the form of ionic chloride compounds, which includes table salt. It is the second-most abundant halogen (after fluorine) and twenty-first most abundant chemical element in Earth's crust. These crustal deposits are nevertheless dwarfed by the huge reserves of chloride in seawater.

Elemental chlorine is commercially produced from

poison gas
weapon.

In the form of chloride

ions, chlorine is necessary to all known species of life. Other types of chlorine compounds are rare in living organisms, and artificially produced chlorinated organics range from inert to toxic. In the upper atmosphere, chlorine-containing organic molecules such as chlorofluorocarbons have been implicated in ozone depletion. Small quantities of elemental chlorine are generated by oxidation of chloride ions in neutrophils as part of an immune system
response against bacteria.

History

The most common compound of chlorine, sodium chloride, has been known since ancient times; archaeologists have found evidence that

rock salt was used as early as 3000 BC and brine as early as 6000 BC.[9]

Early discoveries

Around 900, the authors of the Arabic writings attributed to

sulfates of various metals) produced hydrogen chloride.[10] However, it appears that in these early experiments with chloride salts, the gaseous products were discarded, and hydrogen chloride may have been produced many times before it was discovered that it can be put to chemical use.[11] One of the first such uses was the synthesis of mercury(II) chloride (corrosive sublimate), whose production from the heating of mercury either with alum and ammonium chloride or with vitriol and sodium chloride was first described in the De aluminibus et salibus ("On Alums and Salts", an eleventh- or twelfth century Arabic text falsely attributed to Abu Bakr al-Razi and translated into Latin in the second half of the twelfth century by Gerard of Cremona, 1144–1187).[12] Another important development was the discovery by pseudo-Geber (in the De inventione veritatis, "On the Discovery of Truth", after c. 1300) that by adding ammonium chloride to nitric acid, a strong solvent capable of dissolving gold (i.e., aqua regia) could be produced.[13] Although aqua regia is an unstable mixture that continually gives off fumes containing free chlorine gas, this chlorine gas appears to have been ignored until c. 1630, when its nature as a separate gaseous substance was recognised by the Brabantian chemist and physician Jan Baptist van Helmont.[14][en 1]

Carl Wilhelm Scheele, discoverer of chlorine

Isolation

The element was first studied in detail in 1774 by Swedish chemist Carl Wilhelm Scheele, and he is credited with the discovery.[15][16] Scheele produced chlorine by reacting MnO2 (as the mineral pyrolusite) with HCl:[14]

4 HCl + MnO2 → MnCl2 + 2 H2O + Cl2

Scheele observed several of the properties of chlorine: the bleaching effect on

litmus, the deadly effect on insects, the yellow-green colour, and the smell similar to aqua regia.[17] He called it "dephlogisticated muriatic acid air" since it is a gas (then called "airs") and it came from hydrochloric acid (then known as "muriatic acid").[16] He failed to establish chlorine as an element.[16]

Common chemical theory at that time held that an acid is a compound that contains oxygen (remnants of this survive in the German and Dutch names of

Claude Berthollet, suggested that Scheele's dephlogisticated muriatic acid air must be a combination of oxygen and the yet undiscovered element, muriaticum.[18][19]

In 1809,

Louis-Jacques Thénard tried to decompose dephlogisticated muriatic acid air by reacting it with charcoal to release the free element muriaticum (and carbon dioxide).[16] They did not succeed and published a report in which they considered the possibility that dephlogisticated muriatic acid air is an element, but were not convinced.[20]

In 1810,

Jöns Jakob Berzelius in 1826.[23][24] In 1823, Michael Faraday liquefied chlorine for the first time,[25][26][27] and demonstrated that what was then known as "solid chlorine" had a structure of chlorine hydrate (Cl2·H2O).[14]

Later uses

Chlorine gas was first used by French chemist

Javel water"), was a weak solution of sodium hypochlorite. This process was not very efficient, and alternative production methods were sought. Scottish chemist and industrialist Charles Tennant first produced a solution of calcium hypochlorite ("chlorinated lime"), then solid calcium hypochlorite (bleaching powder).[28] These compounds produced low levels of elemental chlorine and could be more efficiently transported than sodium hypochlorite, which remained as dilute solutions because when purified to eliminate water, it became a dangerously powerful and unstable oxidizer. Near the end of the nineteenth century, E. S. Smith patented a method of sodium hypochlorite production involving electrolysis of brine to produce sodium hydroxide and chlorine gas, which then mixed to form sodium hypochlorite.[30] This is known as the chloralkali process, first introduced on an industrial scale in 1892, and now the source of most elemental chlorine and sodium hydroxide.[31] In 1884 Chemischen Fabrik Griesheim of Germany developed another chloralkali process which entered commercial production in 1888.[32]

Elemental chlorine solutions dissolved in

Antoine-Germain Labarraque, who adapted Berthollet's "Javel water" bleach and other chlorine preparations.[33] Elemental chlorine has since served a continuous function in topical antisepsis (wound irrigation solutions and the like) and public sanitation, particularly in swimming and drinking water.[17]

Chlorine gas was first used as a weapon on April 22, 1915, at the

gas masks were difficult to deploy and had not been broadly distributed.[36][37]

Properties

Chlorine, liquefied under a pressure of 7.4 bar at room temperature, displayed in a quartz ampule embedded in acrylic glass
Solid chlorine at −150 °C

Chlorine is the second

ionisation energy, electron affinity, enthalpy of dissociation of the X2 molecule (X = Cl, Br, I), ionic radius, and X–X bond length. (Fluorine is anomalous due to its small size.)[38]

All four stable halogens experience intermolecular

highest occupied antibonding πg molecular orbital and the lowest vacant antibonding σu molecular orbital.[39] The colour fades at low temperatures, so that solid chlorine at −195 °C is almost colourless.[38]

Like solid bromine and iodine, solid chlorine crystallises in the orthorhombic crystal system, in a layered lattice of Cl2 molecules. The Cl–Cl distance is 198 pm (close to the gaseous Cl–Cl distance of 199 pm) and the Cl···Cl distance between molecules is 332 pm within a layer and 382 pm between layers (compare the van der Waals radius of chlorine, 180 pm). This structure means that chlorine is a very poor conductor of electricity, and indeed its conductivity is so low as to be practically unmeasurable.[38]

Isotopes

Chlorine has two stable isotopes, 35Cl and 37Cl. These are its only two natural isotopes occurring in quantity, with 35Cl making up 76% of natural chlorine and 37Cl making up the remaining 24%. Both are synthesised in stars in the

primordially. Of these, the most commonly used in the laboratory are 36Cl (t1/2 = 3.0×105 y) and 38Cl (t1/2 = 37.2 min), which may be produced from the neutron activation of natural chlorine.[38]

The most stable chlorine radioisotope is 36Cl. The primary decay mode of isotopes lighter than 35Cl is

thermal neutron activation of 35Cl and spallation of 39K and 40Ca. In the subsurface environment, muon capture by 40Ca becomes more important as a way to generate 36Cl.[42][43]

Chemistry and compounds

Halogen bond energies (kJ/mol)[39]
X XX HX BX3 AlX3 CX4
F 159 574 645 582 456
Cl 243 428 444 427 327
Br 193 363 368 360 272
I 151 294 272 285 239

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

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.[39]

Given that E°(1/2O2/H2O) = +1.229 V, which is less than +1.395 V, it would be expected that chlorine should be able to oxidise water to oxygen and hydrochloric acid. However, the kinetics of this reaction are unfavorable, and there is also a bubble overpotential effect to consider, so that electrolysis of aqueous chloride solutions evolves chlorine gas and not oxygen gas, a fact that is very useful for the industrial production of chlorine.[44]

Hydrogen chloride

Structure of solid deuterium chloride, with D···Cl hydrogen bonds

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:[45]

NaCl + H2SO4 150 °C NaHSO4 + HCl
NaCl + NaHSO4 540–600 °C Na2SO4 + HCl

In the laboratory, hydrogen chloride gas may be made by drying the acid with concentrated sulfuric acid. Deuterium chloride, DCl, may be produced by reacting benzoyl chloride with heavy water (D2O).[45]

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.[45] Hydrochloric acid is a strong acid (pKa = −7) because the hydrogen bonds to chlorine are too weak to inhibit dissociation. The HCl/H2O system has many hydrates HCl·nH2O for n = 1, 2, 3, 4, and 6. Beyond a 1:1 mixture of HCl and H2O, the system separates completely into two separate liquid phases. Hydrochloric acid forms an azeotrope with boiling point 108.58 °C at 20.22 g HCl per 100 g solution; thus hydrochloric acid cannot be concentrated beyond this point by distillation.[46]

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 HCl
2
ions – the latter, in any case, are much less stable than the bifluoride ions (HF
2
) 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 NR+
4
(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 electrophiles containing lone-pairs or π bonds. Solvolysis, ligand replacement reactions, and oxidations are well-characterised in hydrogen chloride solution:[47]

Ph3SnCl + HCl ⟶ Ph2SnCl2 + PhH (solvolysis)
Ph3COH + 3 HCl ⟶ Ph
3
C+
HCl
2
+ H3O+Cl (solvolysis)
Me
4
N+
HCl
2
+ BCl3Me
4
N+
BCl
4
+ HCl (ligand replacement)
PCl3 + Cl2 + HCl ⟶ PCl+
4
HCl
2
(oxidation)

Other binary chlorides

Hydrated nickel(II) chloride, 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.[48] 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

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:[48]

EuCl3 + 1/2 H2 ⟶ EuCl2 + HCl
ReCl5 at "bp" ReCl3 + Cl2
AuCl3 160 °C AuCl + Cl2

Most metal chlorides with the metal in low oxidation states (+1 to +3) are ionic. Nonmetals tend to form covalent molecular chlorides, as do metals in high oxidation states from +3 and above. Both ionic and covalent chlorides are known for metals in oxidation state +3 (e.g. scandium chloride is mostly ionic, but aluminium chloride is not). Silver chloride is very insoluble in water and is thus often used as a qualitative test for chlorine.[48]

Polychlorine compounds

Although dichlorine is a strong oxidising agent with a high first ionisation energy, it may be oxidised under extreme conditions to form the [Cl2]+ cation. This is very unstable and has only been characterised by its electronic band spectrum when produced in a low-pressure discharge tube. The yellow [Cl3]+ cation is more stable and may be produced as follows:[49]

Cl2 + ClF + AsF5 −78 °C [Cl3]+[AsF6]

This reaction is conducted in the oxidising solvent arsenic pentafluoride. The trichloride anion, [Cl3], has also been characterised; it is analogous to triiodide.[50]

Chlorine fluorides

The three fluorides of chlorine form a subset of the

diamagnetic.[50] Some cationic and anionic derivatives are known, such as ClF
2
, ClF
4
, ClF+
2
, and Cl2F+.[51] 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).[50]

Chlorine monofluoride (ClF) is extremely thermally stable, and is sold commercially in 500-gram steel lecture bottles. It is a colourless gas that melts at −155.6 °C and boils at −100.1 °C. It may be produced by the reaction of its elements at 225 °C, though it must then be separated and purified from chlorine trifluoride and its reactants. Its properties are mostly intermediate between those of chlorine and fluorine. It will react with many metals and nonmetals from room temperature and above, fluorinating them and liberating chlorine. It will also act as a chlorofluorinating agent, adding chlorine and fluorine across a multiple bond or by oxidation: for example, it will attack carbon monoxide to form carbonyl chlorofluoride, COFCl. It will react analogously with hexafluoroacetone, (CF3)2CO, with a potassium fluoride catalyst to produce heptafluoroisopropyl hypochlorite, (CF3)2CFOCl; with nitriles RCN to produce RCF2NCl2; and with the sulfur oxides SO2 and SO3 to produce ClSO2F and ClOSO2F respectively. It will also react exothermically with compounds containing –OH and –NH groups, such as water:[50]

H2O + 2 ClF ⟶ 2 HF + Cl2O

Chlorine trifluoride (ClF3) is a volatile colourless molecular liquid which melts at −76.3 °C and boils at 11.8  °C. It may be formed by directly fluorinating gaseous chlorine or chlorine monofluoride at 200–300 °C. One of the most reactive chemical compounds known, the list of elements it sets on fire is diverse, containing hydrogen, potassium, phosphorus, arsenic, antimony, sulfur, selenium, tellurium, bromine, iodine, and powdered molybdenum, tungsten, rhodium, iridium, and iron. It will also ignite water, along with many substances which in ordinary circumstances would be considered chemically inert such as asbestos, concrete, glass, and sand. When heated, it will even corrode noble metals as palladium, platinum, and gold, and even the noble gases xenon and radon do not escape fluorination. An impermeable fluoride layer is formed by sodium, magnesium, aluminium, zinc, tin, and silver, which may be removed by heating. Nickel, copper, and steel containers are usually used due to their great resistance to attack by chlorine trifluoride, stemming from the formation of an unreactive layer of metal fluoride. Its reaction with hydrazine to form hydrogen fluoride, nitrogen, and chlorine gases was used in experimental rocket engine, but has problems largely stemming from its extreme hypergolicity resulting in ignition without any measurable delay. Today, it is mostly used in nuclear fuel processing, to oxidise uranium to uranium hexafluoride for its enriching and to separate it from plutonium, as well as in the semiconductor industry, where it is used to clean chemical vapor deposition chambers.[52] It can act as a fluoride ion donor or acceptor (Lewis base or acid), although it does not dissociate appreciably into ClF+
2
and ClF
4
ions.[53]

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:[54]

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.[55]

Chlorine oxides

Yellow chlorine dioxide (ClO2) gas above a solution of hydrochloric acid and sodium chlorite in water, also containing dissolved chlorine dioxide
Structure of dichlorine heptoxide, 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.[56]

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.[56]

Chlorine dioxide (ClO2) was the first chlorine oxide to be discovered in 1811 by Humphry Davy. It is a yellow paramagnetic gas (deep-red as a solid or liquid), as expected from its having an odd number of electrons: it is stable towards dimerisation due to the delocalisation of the unpaired electron. It explodes above −40 °C as a liquid and under pressure as a gas and therefore must be made at low concentrations for wood-pulp bleaching and water treatment. It is usually prepared by reducing a chlorate as follows:[56]

ClO
3
+ Cl + 2 H+ ⟶ ClO2 + 1/2 Cl2 + H2O

Its production is thus intimately linked to the redox reactions of the chlorine oxoacids. It is a strong oxidising agent, reacting with

potassium borohydride. It dissolves exothermically in water to form dark-green solutions that very slowly decompose in the dark. Crystalline clathrate hydrates ClO2·nH2O (n ≈ 6–10) separate out at low temperatures. However, in the presence of light, these solutions rapidly photodecompose to form a mixture of chloric and hydrochloric acids. Photolysis of individual ClO2 molecules result in the radicals ClO and ClOO, while at room temperature mostly chlorine, oxygen, and some ClO3 and Cl2O6 are produced. Cl2O3 is also produced when photolysing the solid at −78 °C: it is a dark brown solid that explodes below 0 °C. The ClO radical leads to the depletion of atmospheric ozone and is thus environmentally important as follows:[56]

Cl• + O3 ⟶ ClO• + O2
ClO• + O• ⟶ Cl• + O2

Chlorine perchlorate (ClOClO3) is a pale yellow liquid that is less stable than ClO2 and decomposes at room temperature to form chlorine, oxygen, and dichlorine hexoxide (Cl2O6).[56] Chlorine perchlorate may also be considered a chlorine derivative of perchloric acid (HOClO3), similar to the thermally unstable chlorine derivatives of other oxoacids: examples include chlorine nitrate (ClONO2, vigorously reactive and explosive), and chlorine fluorosulfate (ClOSO2F, more stable but still moisture-sensitive and highly reactive).[57] 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.[56]

Dichlorine heptoxide (Cl2O7) is the anhydride of perchloric acid (HClO4) and can readily be obtained from it by dehydrating it with phosphoric acid at −10 °C and then distilling the product at −35 °C and 1 mmHg. It is a shock-sensitive, colourless oily liquid. It is the least reactive of the chlorine oxides, being the only one to not set organic materials on fire at room temperature. It may be dissolved in water to regenerate perchloric acid or in aqueous alkalis to regenerate perchlorates. However, it thermally decomposes explosively by breaking one of the central Cl–O bonds, producing the radicals ClO3 and ClO4 which immediately decompose to the elements through intermediate oxides.[56]

Chlorine oxoacids and oxyanions

Standard reduction potentials for aqueous Cl species[44]
E°(couple) a(H+) = 1
(acid)
E°(couple) a(OH) = 1
(base)
Cl2/Cl +1.358 Cl2/Cl +1.358
HOCl/Cl +1.484 ClO/Cl +0.890
ClO
3
/Cl
+1.459
HOCl/Cl2 +1.630 ClO/Cl2 +0.421
HClO2/Cl2 +1.659
ClO
3
/Cl2
+1.468
ClO
4
/Cl2
+1.277
HClO2/HOCl +1.701 ClO
2
/ClO
+0.681
ClO
3
/ClO
+0.488
ClO
3
/HClO2
+1.181 ClO
3
/ClO
2
+0.295
ClO
4
/ClO
3
+1.201 ClO
4
/ClO
3
+0.374

Chlorine forms four oxoacids: hypochlorous acid (HOCl), chlorous acid (HOClO), chloric acid (HOClO2), and perchloric acid (HOClO3). As can be seen from the redox potentials given in the adjacent table, chlorine is much more stable towards disproportionation in acidic solutions than in alkaline solutions:[44]

Cl2 + H2O ⇌ HOCl + H+ + Cl Kac = 4.2 × 10−4 mol2 l−2
Cl2 + 2 OH ⇌ OCl + H2O + Cl Kalk = 7.5 × 1015 mol−1 l

The hypochlorite ions also disproportionate further to produce chloride and chlorate (3 ClO ⇌ 2 Cl + ClO
3
) but this reaction is quite slow at temperatures below 70 °C in spite of the very favourable equilibrium constant of 1027. The chlorate ions may themselves disproportionate to form chloride and perchlorate (4 ClO
3
⇌ Cl + 3 ClO
4
) but this is still very slow even at 100 °C despite the very favourable equilibrium constant of 1020. The rates of reaction for the chlorine oxyanions increases as the oxidation state of chlorine decreases. The strengths of the chlorine oxyacids increase very quickly as the oxidation state of chlorine increases due to the increasing delocalisation of charge over more and more oxygen atoms in their conjugate bases.[44]

Most of the chlorine oxoacids may be produced by exploiting these disproportionation reactions. Hypochlorous acid (HOCl) is highly reactive and quite unstable; its salts are mostly used for their bleaching and sterilising abilities. They are very strong oxidising agents, transferring an oxygen atom to most inorganic species. Chlorous acid (HOClO) is even more unstable and cannot be isolated or concentrated without decomposition: it is known from the decomposition of aqueous chlorine dioxide. However, sodium chlorite is a stable salt and is useful for bleaching and stripping textiles, as an oxidising agent, and as a source of chlorine dioxide. Chloric acid (HOClO2) is a strong acid that is quite stable in cold water up to 30% concentration, but on warming gives chlorine and chlorine dioxide. Evaporation under reduced pressure allows it to be concentrated further to about 40%, but then it decomposes to perchloric acid, chlorine, oxygen, water, and chlorine dioxide. Its most important salt is sodium chlorate, mostly used to make chlorine dioxide to bleach paper pulp. The decomposition of chlorate to chloride and oxygen is a common way to produce oxygen in the laboratory on a small scale. Chloride and chlorate may comproportionate to form chlorine as follows:[58]

ClO
3
+ 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 ClO
4
are known.[58] The Table below presents typical oxidation states for chlorine element as given in the secondary schools or colleges. Anyhow in university chemistry courses it should be pointed out that there are more complex chemical compounds, the structure of which can only be explained using modern quantum chemical methods, for example, cluster technetium chloride [(CH3)4N]3[Tc6Cl14], in which 6 of the 14 chlorine atoms are formally divalent, and oxidation states are fractional [1].[59] 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 exhibit an oxidation state of -3, forming a Na3Cl compound with sodium, which does not fit into traditional concepts of chemistry.[60]

Chlorine oxidation state −1 +1 +3 +5 +7
Name chloride hypochlorite chlorite chlorate perchlorate
Formula Cl ClO ClO
2
ClO
3
ClO
4
Structure The chloride ion The hypochlorite ion The chlorite ion The chlorate ion The perchlorate ion

Organochlorine compounds

Suggested mechanism for the chlorination of a carboxylic acid by phosphorus pentachloride to form an acyl chloride

Like the other carbon–halogen bonds, the C–Cl bond is a common functional group that forms part of core

alkylating agents because chloride is a leaving group.[61]

Lewis acid catalyst.[61] The haloform reaction, using chlorine and sodium hydroxide, is also able to generate alkyl halides from methyl ketones, and related compounds. Chlorine adds to the multiple bonds on alkenes and alkynes as well, giving di- or tetrachloro compounds. However, due to the expense and reactivity of chlorine, organochlorine compounds are more commonly produced by using hydrogen chloride, or with chlorinating agents such as phosphorus pentachloride (PCl5) or thionyl chloride (SOCl2). The last is very convenient in the laboratory because all side products are gaseous and do not have to be distilled out.[61]

Many organochlorine compounds have been isolated from natural sources ranging from bacteria to humans.[62][63] Chlorinated organic compounds are found in nearly every class of biomolecules including alkaloids, terpenes, amino acids, flavonoids, steroids, and fatty acids.[62][64] 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.[65] In addition, a variety of simple chlorinated hydrocarbons including dichloromethane, chloroform, and carbon tetrachloride have been isolated from marine algae.[66] A majority of the chloromethane in the environment is produced naturally by biological decomposition, forest fires, and volcanoes.[67]

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.[68] Due to the ready homolytic fission of the C–Cl bond to create chlorine radicals in the upper atmosphere, chlorofluorocarbons have been phased out due to the harm they do to the ozone layer.[56]

Occurrence and production

Liquid chlorine analysis

Chlorine is too reactive to occur as the free element in nature but is very abundant in the form of its chloride salts. It is the twenty-first most abundant element in Earth's crust and makes up 126 

parts per million of it, through the large deposits of chloride minerals, especially sodium chloride, that have been evaporated from water bodies. All of these pale in comparison to the reserves of chloride ions in seawater: smaller amounts at higher concentrations occur in some inland seas and underground brine wells, such as the Great Salt Lake in Utah and the Dead Sea in Israel.[69]

Small batches of chlorine gas are prepared in the laboratory by combining hydrochloric acid and manganese dioxide, but the need rarely arises due to its ready availability. In industry, elemental chlorine is usually produced by the electrolysis of sodium chloride dissolved in water. This method, the chloralkali process industrialized in 1892, now provides most industrial chlorine gas.[31] Along with chlorine, the method yields hydrogen gas and sodium hydroxide, which is the most valuable product. The process proceeds according to the following chemical equation:[70]

2 NaCl + 2 H2O → Cl2 + H2 + 2 NaOH

The electrolysis of chloride solutions all proceed according to the following equations:

Cathode: 2 H2O + 2 e → H2 + 2 OH
Anode: 2 Cl → Cl2 + 2 e

In diaphragm cell electrolysis, an

caustic alkali is produced and the brine is partially depleted. Diaphragm methods produce dilute and slightly impure alkali, but they are not burdened with the problem of mercury disposal and they are more energy efficient.[31]

Membrane cell electrolysis employs permeable membrane as an ion exchanger. Saturated sodium (or potassium) chloride solution is passed through the anode compartment, leaving at a lower concentration. This method also produces very pure sodium (or potassium) hydroxide but has the disadvantage of requiring very pure brine at high concentrations.[72]

Membrane cell process for chloralkali production

In the

organochlorine compounds
is recovered as chlorine. The process relies on oxidation using oxygen:

4 HCl + O2 → 2 Cl2 + 2 H2O

The reaction requires a catalyst. As introduced by Deacon, early catalysts were based on copper. Commercial processes, such as the Mitsui MT-Chlorine Process, have switched to chromium and ruthenium-based catalysts.[73] The chlorine produced is available in cylinders from sizes ranging from 450 g to 70 kg, as well as drums (865 kg), tank wagons (15 tonnes on roads; 27–90 tonnes by rail), and barges (600–1200 tonnes).[74]

Applications

Sodium chloride is the most common chlorine compound, and is the main source of chlorine for the demand by the chemical industry. About 15000 chlorine-containing compounds are commercially traded, including such diverse compounds as chlorinated

aluminium trichloride for catalysis, the chlorides of magnesium, titanium, zirconium, and hafnium which are the precursors for producing the pure form of those elements.[17]

Quantitatively, of all elemental chlorine produced, about 63% is used in the manufacture of organic compounds, and 18% in the manufacture of inorganic chlorine compounds.

perchloroethylene, allyl chloride, epichlorohydrin, chlorobenzene, dichlorobenzenes, and trichlorobenzenes. The major inorganic compounds include HCl, Cl2O, HOCl, NaClO3, chlorinated isocyanurates, AlCl3, SiCl4, SnCl4, PCl3, PCl5, POCl3, AsCl3, SbCl3, SbCl5, BiCl3, and ZnCl2.[74]

Sanitation, disinfection, and antisepsis

Combating putrefaction

In France (as elsewhere),

Eau de Javel") not only destroyed the smell of putrefaction of animal tissue decomposition, but also actually retarded the decomposition.[78][33]

Labarraque's research resulted in the use of chlorides and hypochlorites of lime (

exhumations,[80] embalming, outbreaks of epidemic disease, fever, and blackleg in cattle.[77]

Disinfection

Labarraque's chlorinated lime and soda solutions have been advocated since 1828 to prevent infection (called "contagious infection", presumed to be transmitted by "

miasmas"), and to treat putrefaction of existing wounds, including septic wounds.[81] In his 1828 work, Labarraque recommended that doctors breathe chlorine, wash their hands in chlorinated lime, and even sprinkle chlorinated lime about the patients' beds in cases of "contagious infection". In 1828, the contagion of infections was well known, even though the agency of the microbe
was not discovered until more than half a century later.

During the

Paris cholera outbreak of 1832, large quantities of so-called chloride of lime were used to disinfect the capital. This was not simply modern calcium chloride, but chlorine gas dissolved in lime-water (dilute calcium hydroxide) to form calcium hypochlorite (chlorinated lime). Labarraque's discovery helped to remove the terrible stench of decay from hospitals and dissecting rooms, and by doing so, effectively deodorised the Latin Quarter of Paris.[82] These "putrid miasmas" were thought by many to cause the spread of "contagion" and "infection" – both words used before the germ theory of infection. Chloride of lime was used for destroying odors and "putrid matter". One source claims chloride of lime was used by Dr. John Snow to disinfect water from the cholera-contaminated well that was feeding the Broad Street pump in 1854 London,[83] though three other reputable sources that describe that famous cholera epidemic do not mention the incident.[84][85][86] One reference makes it clear that chloride of lime was used to disinfect the offal and filth in the streets surrounding the Broad Street pump – a common practice in mid-nineteenth century England.[84]
: 296 

Semmelweis and experiments with antisepsis

Ignaz Semmelweis

Perhaps the most famous application of Labarraque's chlorine and

childbed fever ("puerperal fever") in the maternity wards of Vienna General Hospital in Austria in 1847.[87]

Much later, during World War I in 1916, a standardized and diluted modification of Labarraque's solution containing hypochlorite (0.5%) and boric acid as an acidic stabilizer was developed by Henry Drysdale Dakin (who gave full credit to Labarraque's prior work in this area). Called Dakin's solution, the method of wound irrigation with chlorinated solutions allowed antiseptic treatment of a wide variety of open wounds, long before the modern antibiotic era. A modified version of this solution continues to be employed in wound irrigation in modern times, where it remains effective against bacteria that are resistant to multiple antibiotics (see Century Pharmaceuticals).[88]

Public sanitation

Liquid pool chlorine

The first continuous application of chlorination to drinking U.S. water was installed in

US Department of Treasury called for all drinking water to be disinfected with chlorine. Chlorine is presently an important chemical for water purification (such as in water treatment plants), in disinfectants, and in bleach. Even small water supplies are now routinely chlorinated.[90]

Chlorine is usually used (in the form of hypochlorous acid) to kill bacteria and other microbes in drinking water supplies and public swimming pools. In most private swimming pools, chlorine itself is not used, but rather sodium hypochlorite, formed from chlorine and sodium hydroxide, or solid tablets of chlorinated isocyanurates. The drawback of using chlorine in swimming pools is that the chlorine reacts with the amino acids in proteins in human hair and skin. Contrary to popular belief, the distinctive "chlorine aroma" associated with swimming pools is not the result of elemental chlorine itself, but of chloramine, a chemical compound produced by the reaction of free dissolved chlorine with amines in organic substances including those in urine and sweat.[91] As a disinfectant in water, chlorine is more than three times as effective against Escherichia coli as bromine, and more than six times as effective as iodine.[92] Increasingly, monochloramine itself is being directly added to drinking water for purposes of disinfection, a process known as chloramination.[93]

It is often impractical to store and use poisonous chlorine gas for water treatment, so alternative methods of adding chlorine are used. These include

trichloro-s-triazinetrione, sometimes referred to as "trichlor". These compounds are stable while solid and may be used in powdered, granular, or tablet form. When added in small amounts to pool water or industrial water systems, the chlorine atoms hydrolyze from the rest of the molecule, forming hypochlorous acid (HOCl), which acts as a general biocide, killing germs, microorganisms, algae, and so on.[94][95]

Use as a weapon

World War I

Chlorine gas, also known as bertholite, was first

Kaiser Wilhelm Institute in Berlin, in collaboration with the German chemical conglomerate IG Farben, which developed methods for discharging chlorine gas against an entrenched enemy.[98] After its first use, both sides in the conflict used chlorine as a chemical weapon, but it was soon replaced by the more deadly phosgene and mustard gas.[99]

Middle east

Chlorine gas was also used during the

truck bombs with mortar shells and chlorine tanks. The attacks killed two people from the explosives and sickened more than 350. Most of the deaths were caused by the force of the explosions rather than the effects of chlorine since the toxic gas is readily dispersed and diluted in the atmosphere by the blast. In some bombings, over a hundred civilians were hospitalized due to breathing difficulties. The Iraqi authorities tightened security for elemental chlorine, which is essential for providing safe drinking water to the population.[100][101]

On 23 October 2014, it was reported that the

Islamic State of Iraq and the Levant had used chlorine gas in the town of Duluiyah, Iraq.[102] Laboratory analysis of clothing and soil samples confirmed the use of chlorine gas against Kurdish Peshmerga Forces in a vehicle-borne improvised explosive device attack on 23 January 2015 at the Highway 47 Kiske Junction near Mosul.[103]

Another country in the middle east, Syria, has used chlorine as a chemical weapon[104] delivered from barrel bombs and rockets.[105][106] In 2016, the OPCW-UN Joint Investigative Mechanism concluded that the Syrian government used chlorine as a chemical weapon in three separate attacks.[107] Later investigations from the OPCW's Investigation and Identification Team concluded that the Syrian Air Force was responsible for chlorine attacks in 2017 and 2018.[108]

Biological role

The

electrolyte disturbances. Hypochloremia (having too little chloride) rarely occurs in the absence of other abnormalities. It is sometimes associated with hypoventilation.[110] It can be associated with chronic respiratory acidosis.[111] Hyperchloremia (having too much chloride) usually does not produce symptoms. When symptoms do occur, they tend to resemble those of hypernatremia (having too much sodium). Reduction in blood chloride leads to cerebral dehydration; symptoms are most often caused by rapid rehydration which results in cerebral edema. Hyperchloremia can affect oxygen transport.[112]

Hazards

Chlorine
Hazards
GHS labelling:[113]
GHS03: Oxidizing GHS06: Toxic GHS09: Environmental hazard
Danger
H270, H315, H319, H330, H335, H400
P220, P233, P244, P261, P304, P312, P340, P403, P410
NFPA 704 (fire diamond)

Chlorine is a toxic gas that attacks the respiratory system, eyes, and skin.[115] Because it is denser than air, it tends to accumulate at the bottom of poorly ventilated spaces. Chlorine gas is a strong oxidizer, which may react with flammable materials.[116][117]

Chlorine is detectable with measuring devices in concentrations as low as 0.2 parts per million (ppm), and by smell at 3 ppm. Coughing and vomiting may occur at 30 ppm and lung damage at 60 ppm. About 1000 ppm can be fatal after a few deep breaths of the gas.

IDLH (immediately dangerous to life and health) concentration is 10 ppm.[118] Breathing lower concentrations can aggravate the respiratory system and exposure to the gas can irritate the eyes.[119] When chlorine is inhaled at concentrations greater than 30 ppm, it reacts with water within the lungs, producing hydrochloric acid (HCl) and hypochlorous acid
(HOCl).

When used at specified levels for water disinfection, the reaction of chlorine with water is not a major concern for human health. Other materials present in the water may generate

disinfection by-products that are associated with negative effects on human health.[120][121]

In the United States, the Occupational Safety and Health Administration (OSHA) has set the permissible exposure limit for elemental chlorine at 1 ppm, or 3 mg/m3. The National Institute for Occupational Safety and Health has designated a recommended exposure limit of 0.5 ppm over 15 minutes.[118]

In the home, accidents occur when hypochlorite bleach solutions come into contact with certain acidic drain-cleaners to produce chlorine gas.[122] Hypochlorite bleach (a popular laundry additive) combined with ammonia (another popular laundry additive) produces chloramines, another toxic group of chemicals.[123]

Chlorine-induced cracking in structural materials

Chlorine is widely used for purifying water, especially potable water supplies and water used in swimming pools. Several catastrophic collapses of swimming pool ceilings have occurred from chlorine-induced

acetal resin and polybutene. Both materials were used in hot and cold water domestic plumbing, and stress corrosion cracking caused widespread failures in the US in the 1980s and 1990s.[125]

injection molding
defect in the joint and slowly grew until the part failed. The fracture surface shows iron and calcium salts that were deposited in the leaking joint from the water supply before failure and are the indirect result of the chlorine attack.

Chlorine-iron fire

The element iron can combine with chlorine at high temperatures in a strong exothermic reaction, creating a chlorine-iron fire.[126][127] Chlorine-iron fires are a risk in chemical process plants, where much of the pipework that carries chlorine gas is made of steel.[126][127]

See also

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Explanatory notes

  1. ^ van Helmont, Joannis Baptistae (1682). Opera omnia [All Works] (in Latin). Frankfurt-am-Main, (Germany): Johann Just Erythropel. From "Complexionum atque mistionum elementalium figmentum." (Formation of combinations and of mixtures of elements), §37, p. 105: Archived 2023-12-30 at the Wayback Machine "Accipe salis petrae, vitrioli, & alumnis partes aequas: exsiccato singula, & connexis simul, distilla aquam. Quae nil aliud est, quam merum sal volatile. Hujus accipe uncias quatuor, salis armeniaci unciam junge, in forti vitro, alembico, per caementum (ex cera, colophonia, & vitri pulverre) calidissime affusum, firmato; mox, etiam in frigore, Gas excitatur, & vas, utut forte, dissilit cum fragore." (Take equal parts of saltpeter [i.e., sodium nitrate], vitriol [i.e., concentrated sulfuric acid], and alum: dry each and combine simultaneously; distill off the water [i.e., liquid]. That [distillate] is nothing else than pure volatile salt [i.e., spirit of nitre, nitric acid]. Take four ounces of this [viz, nitric acid], add one ounce of Armenian salt [i.e., ammonium chloride], [place it] in a strong glass alembic sealed by cement ([made] from wax, rosin, and powdered glass) [that has been] poured very hot; soon, even in the cold, gas is stimulated, and the vessel, however strong, bursts into fragments.) From "De Flatibus" (On gases), p. 408 Archived 2023-12-30 at the Wayback Machine: "Sal armeniacus enim, & aqua chrysulca, quae singula per se distillari, possunt, & pati calorem: sin autem jungantur, & intepescant, non possunt non, quin statim in Gas sylvestre, sive incoercibilem flatum transmutentur." (Truly Armenian salt [i.e., ammonium chloride] and nitric acid, each of which can be distilled by itself, and submitted to heat; but if, on the other hand, they be combined and become warm, they cannot but be changed immediately into carbon dioxide [note: van Helmont's identification of the gas is mistaken] or an incondensable gas.)
    See also:
    • Helmont, Johannes (Joan) Baptista Van, Encyclopedia.Com Archived 2021-12-18 at the Wayback Machine: "Others were chlorine gas from the reaction of nitric acid and sal ammoniac; … "
    • Wisniak, Jaime (2009) "Carl Wilhelm Scheele," Revista CENIC Ciencias Químicas, 40 (3): 165–73; see p. 168: "Early in the seventeenth century Johannes Baptiste van Helmont (1579–1644) mentioned that when sal marin (sodium chloride) or sal ammoniacus and aqua chrysulca (nitric acid) were mixed together, a flatus incoercible (non-condensable gas) was evolved."

General bibliography

External links