Chlorine is a chemical element; it has 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 alchemists, which commonly involved the heating of chloride salts like ammonium chloride (sal ammoniac) and sodium chloride (table salt), producing various chemical substances containing chlorine such as hydrogen chloride, mercury(II) chloride (corrosive sublimate), and . However, the nature of free chlorine gas as a separate substance was only recognised around 1630 by Jan Baptist van Helmont. Carl Wilhelm Scheele wrote a description of chlorine gas in 1774, supposing it to be an oxide of a new element. In 1809, chemists suggested that the gas might be a pure element, and this was confirmed by Sir Humphry Davy in 1810, who named it after the Ancient Greek (, "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 20th most abundant element in Earth's crust. These crystal deposits are nevertheless dwarfed by the huge reserves of chloride in seawater.
Elemental chlorine is commercially produced from brine by electrolysis, predominantly in the chloralkali process. The high oxidising potential of elemental chlorine led to the development of commercial bleaches and disinfectants, and a reagent for many processes in the chemical industry. Chlorine is used in the manufacture of a wide range of consumer products, about two-thirds of them organic chemicals such as polyvinyl chloride (PVC), many intermediates for the production of plastics, and other end products which do not contain the element. As a common disinfectant, elemental chlorine and chlorine-generating compounds are used more directly in swimming pools to keep them sanitary. Elemental chlorine at high concentration is extremely dangerous, and poisonous to most living organisms. As a chemical warfare agent, chlorine was first used in World War I as a 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. See Lunca in Vânători-Neamț, Romania.
Early discoveries Around 900, the authors of the Arabic writings attributed to Jabir ibn Hayyan (Latin: Geber) and the Persian physician and alchemist Abu Bakr al-Razi ( 865–925, Latin: Rhazes) were experimenting with sal ammoniac (ammonium chloride), which when it was distilled together with vitriol (hydrated sulfates of various metals) produced hydrogen chloride. vol. II, pp. 41–42; pp. 141–42. 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.. 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).. 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. p. 1002. 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. From "Complexionum atque mistionum elementalium figmentum." (Formation of combinations and of mixtures of elements), §37, p. 105: "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 : "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 : "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."
Isolation
The element was first studied in detail in 1774 by Swedish chemist Carl Wilhelm Scheele, and he is credited with the discovery. In section 6 on pp. 93–94 of his paper , Scheele described how chlorine was produced when a mixture of hydrochloric acid and manganese dioxide (Brunsten) was heated: "6) (a) På 1/2 uns fint rifven Brunsten slogs 1 uns ren Spiritus salis. ... samt lukten fo̊rsvunnen." ( 6) (a) On one half ounce of finely ground Braunstein [pyrolusite] was poured one ounce of pure spiritus salis [spirit of salt, hydrogen chloride]. After this mixture had been standing in the cold for one hour, the acid had assumed a dark brown colour. One part of this solution was poured into a glass, which was placed over the fire. The solution gave off an odour like warm aqua regia and after one quarter's hour duration, it was as clear and colourless as water, and the smell had disappeared.) For an English translation of the relevant passages of this article, see: The Early History of Chlorine : Papers by Carl Wilhelm Scheele (1774), C. L. Berthollet (1785), Guyton de Morveau (1787), J. L. Gay-Lussac and L. J. Thenard (1809) (Edinburgh, Scotland: Alembic Club, 1912), pp. 5–10. Scheele produced chlorine by reacting (as the mineral pyrolusite) with HCl:
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. 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"). He failed to establish chlorine as an element.
Common chemical theory at that time held that an acid is a compound that contains oxygen (the element's name is from the Greek roots ("acid") and ("producer", literally 'begetter')Lavoisier renamed "vital air" to in 1777 from the Greek roots (; "acid", literally 'sharp', from the taste of acids) and (; "producer", literally 'begetter') because he mistakenly believed that oxygen was a constituent of all acids. , so a number of chemists, including Claude Berthollet, suggested that Scheele's dephlogisticated muriatic acid air must be a combination of oxygen and the yet undiscovered element, muriaticum.
In 1809, Joseph Louis Gay-Lussac and Louis-Jacques Thénard tried to decompose dephlogisticated muriatic acid air by reacting it with charcoal to release the free element muriaticum (and carbon dioxide). 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. See: § De la nature et des propriétés de l'acide muriatique et de l'acide muriatique oxigéné (On the nature and properties of muriatic acid and of oxidised muriatic acid), pp. 339–58. From pp. 357–58: "Le gaz muriatique oxigéné n'est pas, en effect, décomposé ... comme un corps composé." ("In fact, oxygenated muriatic acid is not decomposed by charcoal, and it might be supposed, from this fact and those that are communicated in this Memoir, that this gas is a simple body. The phenomena that it presents can be explained well enough on this hypothesis; we shall not seek to defend it, however, as it appears to us that they are still better explained by regarding oxygenated muriatic acid as a compound body.") For a full English translation of this section, see: Joseph Louis Gay-Lussac and Louis Jacques Thénard, "On the nature and the properties of muriatic acid and of oxygenated muriatic acid" (Lemoyne College, Syracuse, New York)