Low temperature condensation

Can the loss of useful material in the purge be avoided or reduced by additional separation on the purge The roles of refrigerated condensation, low-temperature distillation, absorption, adsorption and membranes in this respect have already been discussed. 

The appropriate alkene (1 mol) and benzal chloride (10.6 g, 0.066 mol) were placed in a flame-dried, 250-mL three-neck flask, equipped with a dry-ice condenser, low-temperature thermometer, addition funnel and magnetic stirrer. All operations were carried out under a small positive N2 pressure. MeLi (0.10 mol) in EtjO was added over a period of 2.5 h at — 40"C. After completion of the addition, the mixture was stirred for an additional and then poured onto ice. The product was washed with H O and dried (Na2S04), and the excess alkene was allowed to evaporate. The EtjO and remaining alkene were removed under reduced pressure, and the residue was distilled from bulb-to-bulb under vacuum. The analysis of the product was carried out by GC. Cyclopropanes prepared in this manner are compiled in the above table. 

The critical temperature of methane is 191°K. At 25°C, therefore, the reduced temperature is 1.56. If the dividing line is taken at T/T = 1.8, methane should be considered condensable at temperatures below (about) 70°C and noncondensable at higher temperatures. However, in process design calculations, it is often inconvenient to switch from one method of normalization to the other. In this monograph, since we consider only equilibria at low or moderate pressures in the region 200-600°K, we elect to consider methane as a noncondensable component. 

Condensable hydrocarbon components are usually removed from gas to avoid liquid drop out in pipelines, or to recover valuable natural gas liquids where there is no facility for gas export. Cooling to ambient conditions can be achieved by air or water heat exchange, or to sub zero temperatures by gas expansion or refrigeration. Many other processes such as compression and absorption also work more efficiently at low temperatures. 

It has long been known from statistical mechanical theory that a Bose-Einstein ideal gas, which at low temperatures would show condensation of molecules into die ground translational state (a condensation in momentum space rather than in position space), should show a third-order phase transition at the temperature at which this condensation starts. Nonnal helium ( He) is a Bose-Einstein substance, but is far from ideal at low temperatures, and the very real forces between molecules make the >L-transition to He II very different from that predicted for a Bose-Einstein gas. 

Recent research (1995-) has produced at very low temperatures (nanokelvins) a Bose-Einstein condensation of magnetically trapped alkali metal atoms. Measurements [41] of the fraction of molecules in the ground... 

Clalsen aldol condensation. This consists in the condensation of an aromatic aldehyde and an ester R—CHjCOOCjHj in the presence of finely divided sodium and a trace of alcohol at a low temperature. The catalyst is the alkoxide ion aqueous alkalis caimot be employed since they will hydrolyse the resulting ester. The product is an ap-unsaturated ester, for example ... 

In 1902, von Braun (76) showed that ammonium N-phenyldithio-carbamate condensed at low temperature to give ethyl N-phenyldithio-carbamylacetate (52) which, on heating, led to N-phenylrhodanine (53). 

For example, when an N-methylthioacetamide (96), R, = R — Me, was condensed with chloroacetone, a 2,3,4-trimethylthiazolium chloride was obtained in quantitative yield. The reaction is usually run in aqueous or alcoholic solution at room temperature. At low temperature, with N-phenylthioacetamide (96), Rj = Me, R2 = Ph and chloroacetone, an acyclic intermediate (98) was isolated and characterized (Scheme 43). It was easily converted to 2,4-dimethyl-3-phenylthiazolium chloride (97), R, = Rs = Me, Rj -Ph, by heating (99,102, 145). 

Liquid Helium-4. Quantum mechanics defines two fundamentally different types of particles bosons, which have no unpaired quantum spins, and fermions, which do have unpaired spins. Bosons are governed by Bose-Einstein statistics which, at sufficiently low temperatures, allow the particles to coUect into a low energy quantum level, the so-called Bose-Einstein condensation. Fermions, which include electrons, protons, and neutrons, are governed by Fermi-DHac statistics which forbid any two particles to occupy exactly the same quantum state and thus forbid any analogue of Bose-Einstein condensation. Atoms may be thought of as assembHes of fermions only, but can behave as either fermions or bosons. If the total number of electrons, protons, and neutrons is odd, the atom is a fermion if it is even, the atom is a boson. 

Condensable hydrocarbons are removed from natural gas by cooling the gas to a low temperature and then by washing it with a cold hydrocarbon hquid to absorb the condensables. The uncondensed gas (mainly methane with a small amount of ethane) is classified as natural gas. The condensable hydrocarbons (ethane and heavier hydrocarbons) are stripped from the solvent and are separated into two streams. The heavier stream, which largely contains propane with some ethane and butane, can be Hquefied and is marketed as Hquefied petroleum gas (LPG) (qv). The heavier fractions, which consist of and heavier hydrocarbons, are added to gasoline to control volatihty (see Gasoline and other motor fuels). 

Water. Latices should be made with deionized water or condensate water. The resistivity of the water should be at least lO Q. Long-term storage of water should be avoided to prevent bacteria growth. If the ionic nature of the water is poor, problems of poor latex stabiUty and failed redox systems can occur. Antifreeze additives are added to the water when polymerization below 0°C is required (37). Low temperature polymerization is used to limit polymer branching, thereby increasing crystallinity. 

Several crystalline condensed phosphates may also be formed by the dehydration of monosodium phosphate (MSP). Maddrell s salt exists as Form 11 (high temperature MaddreU, NaPO -ll, insoluble metaphosphate-11) and Form 111 (low temperature MaddreU, NaPO -lll, insoluble metaphosphate-111). Both forms are highly polymerized and difficult (slow) to dissolve in water. Mixtures of the two forms are marketed as a dental abrasive for toothpaste formulations containing soluble fluoride. Maddrell s salt is also used with disodium phosphate as a cheese emulsifying aid. 

A low temperature catalytic process has been reported (64). The process involves the divalent nickel- or zero-valent palladium-catalyzed self-condensation of halothiophenols in an alcohol solvent. The preferred halothiophenol is -bromothiophenol. The relatively poor solubiHty of PPS under the mild reaction conditions results in the synthesis of only low molecular weight PPS. An advantage afforded by the mild reaction conditions is that of making telecheHc PPS with functional groups that may not survive typical PPS polymerization conditions. 

Ammonia has low miscibility in mineral oils, alkylbenzenes, and polyol ester lubricants, particularly at low temperatures. A typical ammonia system uses a coalescing separator that removes all oil in droplet or aerosol form and drains it back to the compressor. Sometimes separators are equipped with some means of cooling the discharge gas to condense any oil that is discharged as a vapor. 

Of the four commercial processes for the purification of carbon monoxide two processes are based on the absorption of carbon monoxide by salt solutions, the third uses either low temperature condensation or fractionation, and the fourth method utilizes the adsorption of carbon monoxide on a soHd adsorbent material. AH four processes use similar techniques to remove minor impurities. Particulates are removed in cyclones or by scmbbing. Scmbbing also removes any tars or heavy hydrocarbon fractions. Acid gases are removed by absorption in monoethanolamine, hot potassium carbonate, or by other patented removal processes. The purified gas stream is then sent to a carbon monoxide recovery section for final purification and by-product recovery. 

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