Chlorine - History

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. Around 1630, chlorine was recognized as a gas by the Belgian chemist and physician Jan Baptist van Helmont.

Elemental chlorine was first prepared and studied in 1774 by Swedish chemist Carl Wilhelm Scheele, and, therefore, he is credited for its discovery. 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"). However, he failed to establish chlorine as an element, mistakenly thinking that it was the oxide obtained from the hydrochloric acid (see phlogiston theory). He named the new element within this oxide as muriaticum. Regardless of what he thought, Scheele did isolate chlorine by reacting MnO₂ (as the mineral pyrolusite) with HCl:

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 color, and the smell similar to aqua regia.

At the time, common chemical theory was: any acid is a compound that contains oxygen (still sounding in the German and Dutch names of oxygen: sauerstoff or zuurstof, both translating into English as acid stuff), 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.

In 1810, Sir Humphry Davy tried the same experiment again, and concluded that it is an element, and not a compound. He named this new element as chlorine, from the Greek word χλωρος (chlōros), meaning green-yellow. The name halogen, meaning "salt producer," was originally used for chlorine in 1811 by Johann Salomo Christoph Schweigger. However, this term was later used as a generic term to describe all the elements in the chlorine family (fluorine, bromine, iodine), after a suggestion by Jöns Jakob Berzelius in 1842. In 1823, Michael Faraday liquefied chlorine for the first time, and demonstrated that what was then known as "solid chlorine" had a structure of chlorine hydrate (Cl₂·H₂O).

Chlorine gas was first used by French chemist Claude Berthollet to bleach textiles in 1785. Modern bleaches resulted from further work by Berthollet, who first produced sodium hypochlorite in 1789 in his laboratory on the quay Javel in Paris, France, by passing chlorine gas through a solution of sodium carbonate. The resulting liquid, known as "Eau de Javel" ("Javel water"), was a weak solution of sodium hypochlorite. However, 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). 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. This is known as the chloralkali process, first introduced on an industrial scale in 1892, and now the source of essentially all modern elemental chlorine and sodium hydroxide production (a related low-temperature electrolysis reaction, the Hooker process, is now responsible for bleach and sodium hypochlorite production).

Elemental chlorine solutions dissolved in chemically basic water (sodium and calcium hypochlorite) was first used as anti-putrification agents and disinfectants in the 1820s, in France, long before the establishment of the germ theory of disease. This work is mainly due to Antoine-Germain Labarraque, who adapted Berthollet's "Javel water" bleach and other chlorine preparations for the purpose (see a more complete history, see below). Elemental chlorine has since served a continuous function in topical antisepsis (wound irrigation solutions and the like) as well as public sanitation (especially of swimming and drinking water).

In 1826, silver chloride was used to produce photographic images for the first time. Chloroform was first used as an anesthetic in 1847.

Polyvinyl chloride (PVC) was invented in 1912, initially without a purpose.

Chlorine gas was first introduced as a weapon on April 22, 1915, at Ypres by the German Army, and the results of this weapon were disastrous because gas masks had not been mass distributed and were tricky to get on quickly.