Editing Fluorocarbon (section)

===Manufacture===
The development of the fluorocarbon industry coincided with [[World War II]].<ref name=McBee>{{cite journal
 |author=McBee ET
 |title=Fluorine Chemistry
 |journal=Ind. Eng. Chem.
 |volume=39 |issue=3 |pages=236–237 |date=March 1947 |doi=10.1021/ie50447a002}}</ref> Prior to that, fluorocarbons were prepared by reaction of fluorine with the hydrocarbon, i.e., direct fluorination. Because C-C bonds are readily cleaved by fluorine, direct fluorination mainly affords smaller perfluorocarbons, such as tetrafluoromethane, hexafluoroethane, and octafluoropropane.<ref name="Ullmann">{{Cite encyclopedia |title=Fluorine Compounds, Organic |encyclopedia=Ullmann's Encyclopedia of Industrial Chemistry |date=2000 |doi=10.1002/14356007.a11_349 |isbn=978-3-527-30385-4 |last2=Schwertfeger |first2=Werner |last3=Feiring |first3=Andrew |last4=Smart |first4=Bruce |last5=Behr |first5=Fred |last6=Vogel |first6=Herward |last7=McKusick |first7=Blaine |last1=Siegemund |first1=Günter}}</ref>

====Fowler process====
A major breakthrough that allowed the large scale manufacture of fluorocarbons was the [[Fowler process]]. In this process, [[cobalt trifluoride]] is used as the source of fluorine. Illustrative is the synthesis of [[perfluorohexane]]:
:{{chem2|C6H14 + 28 CoF3 -> C6F14 + 14 HF + 28 CoF2}}

The resulting cobalt difluoride is then regenerated, sometimes in a separate reactor:
:{{chem2|2 CoF2 + F2 -> 2 CoF3}}

Industrially, both steps are combined, for example in the manufacture of the Flutec range of fluorocarbons by F2 chemicals Ltd, using a vertical stirred bed reactor, with hydrocarbon introduced at the bottom, and fluorine introduced halfway up the reactor. The fluorocarbon vapor is recovered from the top.

====Electrochemical fluorination====
[[Electrochemical fluorination]] (ECF) (also known as the Simons' process) involves [[electrolysis]] of a substrate dissolved in [[hydrogen fluoride]]. As fluorine is itself manufactured by the electrolysis of hydrogen fluoride, ECF is a rather more direct route to fluorocarbons. The process proceeds at low voltage (5 – 6 V) so that free fluorine is not liberated. The choice of substrate is restricted as ideally it should be soluble in hydrogen fluoride. Ethers and tertiary amines are typically employed. To make perfluorohexane, trihexylamine is used, for example:

:{{chem2|N(C6H13)3 + 45 HF -> 3 C6F14 + NF3 + 42 H2}}

The perfluorinated amine will also be produced:
:{{chem2|N(C6H13)3 + 39 HF -> N(C6F13)3 + 39 H2}}