Fluorine Compounds - History

History

The word "fluorine" derives from the Latin stem of the main source mineral, fluorite, which was first mentioned in 1529 by Georgius Agricola, who described it as a flux—an additive that helps melt ores and slags during smelting. Fluorite stones were called schone flusse in the German of the time. Agricola, writing in Latin but describing 16th century industry, invented several hundred new Latin terms. For the schone flusse stones, he used the Latin noun fluores, "fluxes", because they made metal ores flow when in a fire. After Agricola, the name for the mineral evolved to fluorspar (still commonly used) and then to fluorite.

Some sources claim that the first production of hydrofluoric acid was by Heinrich Schwanhard, a German glass cutter, in 1670. A peer-reviewed study of Schwanhard's writings, though, showed no specific mention of fluorite and only discussion of an extremely strong acid. It was hypothesized that this was probably nitric acid or aqua regia, both capable of etching soft glass. Andreas Sigismund Marggraf made the first recorded preparation of "fluoric acid" (hydrofluoric acid in modern nomenclature) in 1764 when he heated fluorite with sulfuric acid in glass, which was greatly corroded by the product. In 1771, Swedish chemist Carl Wilhelm Scheele repeated this reaction. In 1810, French physicist André-Marie Ampère suggested that the acid was a compound of hydrogen with an unknown element, analogous to chlorine. Fluorite was then shown to be mostly composed of calcium fluoride.

Sir Humphry Davy originally suggested the name fluorine, taking the root from the name of "fluoric acid" and the -ine suffix, similarly to other halogens. This name, with modifications, came to most European languages. (Greek, Russian, and several other languages use the name ftor or derivatives, which was suggested by Ampère and comes from the Greek φθόριος (phthorios), meaning "destructive".) The new Latin name (fluorum) gave the element its current symbol, F, although the symbol Fl is seen in early papers. The symbol Fl is now used for the super-heavy element flerovium.

Owing to its extreme reactivity, elemental fluorine was not isolated until many years after the characterization of fluorite. Progress in isolating elemental fluorine was slow because its electrolytical preparation was hard to perform and because the gas reacted with most materials. The generation of elemental fluorine proved to be exceptionally dangerous, killing or blinding several early experimenters. Jean Dussaud referred to these men as "fluorine martyrs", a term still used.

Edmond Frémy thought that passing electric current through pure hydrofluoric acid might work. Previously, hydrogen fluoride was only available in a water solution. Frémy therefore devised a method for producing dry hydrogen fluoride by acidifying potassium bifluoride (KHF₂). Unfortunately, pure hydrogen fluoride did not pass an electric current.

French chemist Henri Moissan, formerly one of Frémy's students, continued the search. After trying many different approaches, he built on Frémy's earlier attempt by combining potassium bifluoride and hydrogen fluoride. The resultant solution conducted electricity. Moissan also constructed especially corrosion-resistant equipment: containers crafted from a mixture of platinum and iridium (more chemically resistant than pure platinum) with fluorite stoppers. After 74 years of effort by many chemists, on 26 June 1886, Moissan reported the isolation of elemental fluorine. Moissan's report to the French Academy of making fluorine showed appreciation for the feat:

One can indeed make various hypotheses on the nature of the liberated gas; the simplest would be that we are in the presence of fluorine

Moissan later devised a less expensive apparatus for making fluorine: copper equipment coated with copper fluoride. In 1906, two months before his death, Moissan received the Nobel Prize in chemistry for his fluorine isolation as well as the invention of the electric arc furnace.

During the 1930s and 1940s, the DuPont company commercialized organofluorine compounds at large scales. Following trials of chlorofluorcarbons as refrigerants by researchers at General Motors, DuPont developed large-scale production of Freon-12. DuPont and GM formed a joint venture in 1930 to market the new product; in 1949 DuPont took over the business. Freon proved to be a marketplace hit, rapidly replacing earlier, more toxic, refrigerants and growing the overall market for kitchen refrigerators.

In 1938, polytetrafluoroethylene (DuPont brand name Teflon) was discovered by accident by a recently-hired DuPont PhD, Roy J. Plunkett. While working with tetrafluoroethylene gas, he noticed missing weight. Scraping down his container, he found white flakes of a polymer new to the world. Tests showed the substance was resistant to corrosion from most substances and had better high temperature stability than any other plastic. By early 1941, a crash program was making commercial quantities.

Large-scale productions of elemental fluorine began during World War II. Germany used high-temperature electrolysis to produce tons of chlorine trifluoride, a compound planned to be used as an incendiary. The Manhattan project in the United States produced even more fluorine for use in uranium separation. Gaseous uranium hexafluoride was used to separate uranium-235, an important nuclear explosive, from the heavier uranium-238 in centrifuges and diffusion plants. Because uranium hexafluoride releases small quantities of corrosive fluorine, the separation plants were built with special materials. All pipes were coated with nickel; joints and flexible parts were fabricated from Teflon.

In 1958, a DuPont research manager in the Teflon business, Bill Gore, left the company because of its unwillingess to develop Teflon as wire-coating insulation. Gore's son Robert found a method for solving the wire-coating problem and the company W. L. Gore and Associates was born. In 1969, Robert Gore developed an expanded PTFE membrane which led to the large Gore-tex business in breathable rainwear. The company developed many other uses of PTFE.

In the 1970s and 1980s, concerns developed over the role chlorofluorocarbons play in damaging the ozone layer. By 1996, almost all nations had banned chlorofluorocarbon refrigerants and commercial production ceased. Fluorine continued to play a role in refrigeration though: hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs) were developed as replacement refrigerants.