Chlorofluorocarbon*

The necessity of phasing out production and use of CFCs is explained in Sections 8.3 and 12.1. The lesson to be learned is that inert does not necessarily mean harmless no product or by-product of industry can be released into the environment without careful consideration of the consequences. The questions that remain are how can existing stocks of these very inert fluids be destroyed/ and what can take their place as refrigerants and solvents  

This reaction is easily controlled, uses an inexpensive reagent, and gives benign products that are easily disposable. The method also shows promise as a means of converting inert saturated fluorocarbons into more reactive fluoroalkenes or fluoroarenes for use in syntheses. 

Fluorocarbons containing hydrogen but no chlorine (HFCs) pose no 

Nonfluorine CFC substitutes have been considered, but few are fully satisfactory. For example, we could go back 50 years to the use of anhydrous ammonia as a refrigerant, but NH3 is as toxic now as it ever was. Cyclopentane could be used as a foam-blowing agent, but it is less effective than HCFC-141b and besides would contribute to the volatile organic compound load in the troposphere, which is the root cause of ozone pollution (Section 8.3.2). On the other hand, supercritical CO2 is emerging as an alternative to CFCs in various steps in the preparation of fluorocarbon polymers (Section 8.1.3). 

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Aerosol sprays consist of a material dissolved or suspended in a liquid which when pressure is released volatilizes to produce a fine spray. The spray carries the active material. Used in hair lacquers, paints, etc. the propellant should be inert and non-inflammable. Chlorofluorocarbons have been used extensively but are now being replaced. 

Many condensable vapours have been used as refrigerants, but the main ones are the chlorofluorocarbons (Freons ), ammonia and carbon dioxide. 

One of the chief uses of chloromethane is as a starting material from which sili cone polymers are made Dichloromethane is widely used as a paint stripper Trichloromethane was once used as an inhalation anesthetic but its toxicity caused it to be replaced by safer materials many years ago Tetrachloromethane is the starting mate rial for the preparation of several chlorofluorocarbons (CFCs) at one time widely used as refrigerant gases Most of the world s industrialized nations have agreed to phase out all uses of CFCs because these compounds have been implicated m atmospheric processes that degrade the Earth s ozone layer... 

It is the use of LIDAR devices as tools for spectroscopic measurements on the various gases present in the atmosphere which concerns us here. These include ozone, carbon dioxide, the CFCs (chlorofluorocarbons, such as CFC-11, trichlorofluoromethane, and CFC-12, dichlorodifluoromethane, used as refrigerants) and all those molecules regarded as atmospheric pollutants. 

Cm.OROCARBONSANDCm.OROHYDROCARBONS - CARBONTETRACm ORIDE] (Vol5) CFCs. See Chlorofluorocarbons... 

Chlorofluorocarbons (CFCs). Prior to 1978 most aerosol products contained chlorofluorocarbon propeUants. Since that time, the use of chlorinated fluorocarbons for aerosols has been seriously curtailed. These compounds have been impHcated in the depeletion of the ozone (qv) layer and are considered to be greenhouse gases (see Airpollution Atmospheric modeling). 

Table 2. Physical Properties of Chlorofluorocarbon and Hydrocarbon Propellants...

Production of hydrogen fluoride from reaction of Cap2 with sulfuric acid is the largest user of fluorspar and accounts for approximately 60—65% of total U.S. consumption. The principal uses of hydrogen fluoride are ia the manufacture of aluminum fluoride and synthetic cryoHte for the Hall aluminum process and fluoropolymers and chlorofluorocarbons that are used as refrigerants, solvents, aerosols (qv), and ia plastics. Because of the concern that chlorofluorocarbons cause upper atmosphere ozone depletion, these compounds are being replaced by hydrochlorofluorocarbons and hydrofluorocarbons. 

North American HF production capacity has declined since the early 1980s and several smaller producers, such as Harshaw and Essex, have closed plants. Production is expected to continue to decline in the short term because of chlorofluorocarbon (CPC) cutbacks, but is expected to rebound later in the 1990s as replacement hydrochlorofluorocarbons are introduced to the marketplace. 

It appears that the ultimate replacements for the high volume chlorofluorocarbon products are to be more highly fluorinated organic chemicals, thus requiring significantly higher volumes of HF in thek manufacture. 

Properties. The physical properties of aHphatic fluorine compounds containing chlorine are similar to those of the PECs or HECs (3,5). They usually have high densities and low boiling points, viscosities, and surface tensions. The irregularity in the boiling points of the fluorinated methanes, however, does not appear in the chlorofluorocarbons. Their boiling points consistently increase with the number of chlorines present. The properties of some CECs and HCECs are shown in Tables 3 and 4. 

Table 3. Physical Properties of Aliphatic Chlorofluorocarbons (CFCs) ...

The chlorofluorocarbons react with molten alkah metals and CCI2F2 reacts vigorously with molten aluminum, but with most metals they do not react below 200°C. An exception is the dechlorination of chlorofluorocarbons with two or more carbon atoms in the presence of Zn, Mg, or A1 in polar solvents. A commercial synthesis of chlorotriduoroethylene [79-38-9] employs this reaction ... 

Most chlorofluorocarbons are hydrolytically stable, CCI2F2 being considerably more stable than either CCl F or CHCI2F. Chlorofluoromethanes and ethanes disproportionate in the presence of aluminum chloride. For example, CCl F and CCI2F2 give CCIF and CCl CHCIF2 disproportionates to CHF and CHCl. The carbon—chlorine bond in most chlorofluorocarbons can be homolyticaHy cleaved under photolytic conditions (185—225 nm) to give chlorine radicals. This photochemical decomposition is the basis of the prediction that chlorofluorocarbons that reach the upper atmosphere deplete the earth s ozone shield. 

M. Yamabe, "HCEC-225s as CEC-113 Substitutes" in Symposium on Progress on the Depelopment and Use of Chlorofluorocarbon (CEC) Altematipes, 200th ACS national Meeting, Abstract No. 22, Washington, D.C., Aug. 28, 1990. 

CFG = chlorofluorocarbon HCFC = hydrochlorofluorocarbon see Fluorine compounds,organic-aliphatic. 

The patent Hterature indicates that the AUiedSignal process uses lower boiling solvents such as chlorofluorocarbons as the cooling/extraction baths (16), whereas the processes of Stamicarbon indicate the use of decalin solvent followed by cooling and slow removal of the decalin in successively hotter chambers while stretching (17). 

Synthetic oils have been classified by ASTM into synthetic hydrocarbons, organic esters, others, and blends. Synthetic oils may contain the following compounds diaLkylben2enes, poly(a-olefins) polyisobutylene, cycloaUphatics, dibasic acid esters, polyol esters, phosphate esters, siUcate esters, polyglycols, polyphenyl ethers, siUcones, chlorofluorocarbon polymers, and perfluoroalkyl polyethers. 

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