Halocarbon systems

Halocarbon systems are almost invariably controlled by mechanical or electronic thermostatic expansion valves, requiring a superheat signal to operate the control. The superheating of the suction gas into the compressor will cause it to expand, resulting in a lower mass flow for a given swept volume. Reduction of the superheat setting of the expansion valve will therefore result in better use of the compressor. The limit will be reached when there is insufficient signal to work the expansion valve. 

Propellants. The propellant, said to be the heart of an aerosol system, maintains a suitable pressure within the container and expels the product once the valve is opened. Propellants may be either a Hquefied halocarbon, hydrocarbon, or halocarbon—hydrocarbon blend, or a compressed gas such as carbon dioxide (qv), nitrogen (qv), or nitrous oxide. 

Several types of fluids are used as refrigerants in mechanical compression systems ammonia, halocarbon compounds, hydrocarbons, carbon dioxide, sulfur dioxide, and cryogenic fluids. A wide temperature range therefore is afforded. These fluids boil and condense isotherm ally. The optimum temperature or pressure at which each can be used can be deterrnined from the economics of the system. The optimum refrigerant can be deterrnined only... 

At least two catalytic processes have been used to purify halogenated streams. Both utilize fluidized beds of probably noimoble metal catalyst particles. One has been estimated to oxidize >9000 t/yr of chlorinated wastes from a vinyl chloride monomer plant (45). Several companies have commercialized catalysts which are reported to resist deactivation from a wider range of halogens. These newer catalysts may allow the required operating temperatures to be reduced, and stiU convert over 95% of the halocarbon, such as trichlorethylene, from an exhaust stream. Conversions of C-1 chlorocarbons utilizing an Englehardt HDC catalyst are shown in Figure 8. For this system, as the number of chlorine atoms increases, the temperatures required for destmction decreases. 

Operated in this manner, the shell-and-tube type is a flooded evaporator (see Figure 7.3) and has oil drainage pots if using ammonia, or a mixture bleed system if the refrigerant is one of the halocarbons. The speed of the liquid within the tubes should be about 1 m/ s or more, to promote internal turbulence for good heat transfer. End cover baffles will constrain the flow to a number of passes, as with the shell-and-tube condenser. (See Section 6.4.)... 

Refrigeration system pipes are sized to offer a lowresistance to flow, since this reflects directly on compression ratio, commensurate with economy of pipe cost and minimum flow velocities to ensure oil return with the halocarbons. 

Other radical reactions not covered in this chapter are mentioned in the chapters that follow. These include additions to systems other than carbon-carbon double bonds [e.g. additions to aromatic systems (Section 3.4.2.2.1) and strained ring systems (Section 4.4.2)], transfer of heteroatoms [eg. chain transfer to disulfides (Section 6.2.2.2) and halocarbons (Section 6.2.2.4)] or groups of atoms [eg. in RAFT polymerization (Section 9.5.3)], and radical-radical reactions involving heteroatom-centered radicals or metal complexes [e g. in inhibition (Sections 3.5.2 and 5.3), NMP (Section 9.3.6) and ATRP (Section 9.4)]. 

Salmon AG, Nash JA, Walkin CM, et al. 1985. Dechlorination of halocarbons by microsomes and vesicular reconstituted cytochrome P-450 systems under reductive conditions. Br J Ind Med 42 305-311. 

This chapter, therefore, ends the monograph with a potpourri of reactions all of which occur without a change in oxidation state. In many cases, the reaction is one of nucleophilic attack at an electrophilic C-atom. The result is often hydrolytic bond cleavage (e.g., in carbohydrate conjugates, disubstitut-ed methylene and methine groups, imines, oximes, isocyanates, and nitriles, and various ring systems) or a nucleophilic substitution (e.g., hydrolytic de-halogenation of halocarbons and chloroplatin derivatives, and cyclization reactions). The formation of multiple bonds by dehydration is a special case to be discussed separately. 

Chlorinated organic compounds (dioxins, other halocarbons) Combustion of municipal wastes, paper processing, cleaning solvents Toxic effects including birth defects, reproductive failure, cancer, and systemic poisoning. 

In the case of iridium, complex [IrH2(PPh3)2(acetone)2] BF4 (11) was the first to carry out catalytically the dehydrogenation of cycloalkanes [13, 14]. However, it was later realized that the halocarbons used as solvents reacted with 11 to produce the stable species [HL2lr(p-Cl)2(. i-X)IrL2H]BF4 (X = Cl (14) or H (15)) [16] (Scheme 13.8), and that elimination of the solvent by running the reactions in neat alkane not only improved yields but also permitted the activation of other previously unreactive cycloalkanes, such as methyl- and ethyl-cyclopentane. However, it was also noted that the system in some cases was not catalytic, due mainly to decomposition of the catalyst at the temperatures employed [16]. 

EPA. 1982e. Purgeable halocarbons Test method - method 601. Cincinnati, OH U.S. Environmental Protection Agency, Environmental Monitoring Systems Laboratory. 

Like many volatile halocarbons and other hydrocarbons, inhalation exposure to carbon tetrachloride leads to rapid depression of the central nervous system. Because of its narcotic properties, carbon tetrachloride was used briefly as an anesthetic in humans, but its use was discontinued because it was less efficacious and more toxic than other anesthetics available (Hardin 1954 Stevens and Forster 1953). Depending on exposure levels, common signs of central nervous system effects include headache, giddiness, weakness, lethargy, and stupor (Cohen 1957 Stevens and Forster 1953 Stewart and Witts 1944). Effects on vision (restricted peripheral vision, amblyopia) have been observed in some cases (e.g., Johnstone 1948 Smyth et al. 1936 Wrtschafter 1933), but not in others (e.g., Stewart and Wtts 1944). In several fatal cases, microscopic examination of brain tissue taken at autopsy revealed focal areas of fatty degeneration and necrosis, usually associated with congestion of cerebral blood vessels (Ashe and Sailer 1942 Cohen 1957 Stevens and Forster 1953). 

Figure 1 is a sketch of a complete apparatus for the preparation of tetrachloro-diborane(4). Boron chlorides are very corrosive and attack many elastomers and vacuum greases, so only Teflon, Viton, and halocarbon greases should be used for seals and lubrication in the vacuum system. 

Recent investigations in the field of plasma etching have almost universally found that surfaces subjected to ion bombardment (e.g., the target surface in Fig. 1) react (i.e., etch) much more rapidly than those which are held near plasma potential. Examples of this type have been reported by Hosokawa et al. for the halocarbon etching of silicon and by Holland and Ojha for the oxygen plasma-etching of carbon. Several systems exhibiting this type of behavior have also been observed in our laboratory . 

Unlike the situation with hydrocarbons in zeolites, relatively few experimental and simulation data concerning the behavior of halocarbons in zeolites and analogous nanoporous materials have been reported so far. They include calorimetric [6] and isotherms measurements [7,4], FTIR/Raman [8] and NMR [9] spectroscopies studies, diffraction work [10], and generalized forcefield simulations [11] on a variety of sorbate/sorbent systems. However, there remains a great deal to be done in this emerging field. 

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