Chlorofluorocarbons, ozone

NRDC). A private environmental advisory group, founded in 1970, whose function is to point out serious environmental hazards and to oversee the enforcement of regulations pertaining to them. It was influential in postponement of the breeder reactor and in recognition of the chlorofluorocarbon-ozone problem. It operates primarily through the courts. Its main office is at 40 West 20th Street, New York, NY 10011 Website http //www.nrdc.org. 

The Chlorofluorocarbon-Ozone Question.— For information on atmospheric chloro-fluorocarbons(CFCl3 and CF2CI2 derived from aerosol dispensers) and the possibility that they damage the Earth s ozone shield via stratospheric photo-dissociation ... 

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. 

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). 

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. 

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. 

Trichloroethylene is being evaluated by the industry as a precursor in the production of hydrochlorofluorocarbons (HCEC), the replacement products for the chlorofluorocarbons impHcated in the depletion of the stratospheric ozone. At this time it is too early to project any estimates or probabihties for potential volume changes as a result of this opportunity (23). 

A leader in the refrigerants industry, we manufacture and supply customers with economical chlorofluorocarbon (CFC) replacements and non-ozone depleting hydrofluorocarbon (HFC) refrigerants for automotive, home, commercial and transportation uses. In the Americas and Asia, you can find these products under the Genetron name and in Europe and the Middle East under Honeywell Refrigerants. 

The other global environmental problem, stratospheric ozone depletion, was less controversial and more imminent. The U.S. Senate Committee Report supporting the Clean Air Act Amendments of 1990 states, Destruction of the ozone layer is caused primarily by the release into the atmosphere of chlorofluorocarbons (CFCs) and similar manufactured substances—persistent chemicals that rise into the stratosphere where they catalyze the destruction of stratospheric ozone. A decrease in stratospheric ozone will allow more ultraviolet (UV) radiation to reach Earth, resulting in increased rates of disease in humans, including increased incidence of skin cancer, cataracts, and, potentially, suppression of the immune system. Increased UV radiation has also been shown to damage crops and marine resources."... 

The Montreal Protocol of July 1987 resulted in an international treaty in which the industrialized nations agreed to halt the production of most ozone-destroying chlorofluorocarbons by the year 2000. This deadline was hastily changed to 1996, in February 1992, after a U.S. National Aeronautics and Space Administration (NASA) satellite and high-altitude sampling aircraft found levels of chlorine monoxide over North America that were 5i % greater than that measured over Antarctica. 

An important effect of air pollution on the atmosphere is change in spectral transmission. The spectral regions of greatest concern are the ultraviolet and the visible. Changes in ultraviolet radiation have demonstrable adverse effects e.g., a decrease in the stratospheric ozone layer permits harmful UV radiation to penetrate to the surface of the earth. Excessive exposure to UV radiation results in increases in skin cancer and cataracts. The worldwide effort to reduce the release of stratospheric ozone-depleting chemicals such as chlorofluorocarbons is directed toward reducing this increased risk of skin cancer and cataracts for future generations. 

As you know, most countries are phasing out certain refrigerants to lessen damage to the ozone layer. The chemicals being phased out are chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs). Replacements are hydrofluorocarbons (HFCs) and certain blends. The DuPont web site (www.dupont.com) gives the handy Table I of recommended replacement refrigerants for various applications. 

Another area of potential interest is in refrigerator liners. The move away from the ozone-layer-damaging chlorofluorocarbons (CFCs) to HCFCs in the USA and pentane/cyclopentane blends in Europe has not been without problems. These newer materials have an adverse effect on ABS whereas the nitrile resin appears satisfactory, if more expensive. 

The hazard identification step is perhaps the most important, because any hazard not identified will not be considered in the decision process. For example, the impact of chlorofluorocarbons on atmospheric ozone was unknown for much of the period of their use, and this potential hazard was not considered until recent years. 

During the 1980s, it became recognized that chlorofluorocarbons (CFCs), widely used as aerosol propellants, are damaging the ozone layer, and aerosol manufacturers were asked to use other propellants. Some... 

The question of the fate of chlorofluorocarbons upon their release into the atmosphere IS of great interest at present because of the potential damage to the earth s protective ozone layer caused by the reaction of ozone with photochemically generated chlorine atoms... 

Unfortunately, the thermodynamically favored reactions of trichlo-rolluoromethane (CFC-11) and dichlorodifluoromethane (CFC-12) with water do not proceed to a significant degree below 300 C and at least 200 atm (1 atm = 101.325 kPa) or greater [42] (equation 44) Even at 4000 atm randoimzation rather than complete hydrolysis occurs, leaving another chlorofluorocarbon, chlorotri-fluoromethane (CFC-13), which is also potentially harmful to the earth s ozone layer... 

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