Deliquescence Distillation

Antimony trichloride [10025-91-9] M 228.1, m 73", b 283", pK 1.4, pK j ll.O (11.8), PKI 12.95 (for Sb " " aquo). Dried over P2O5 or by mixing with toluene or xylene and distilling (water is carried off with the organic solvent), then distd twice under dry nitrogen at 50mm, degassed and sublimed twice in a vacuum into ampoules. Can be crystd from CS2. Deliquescent. Fumes in moist air. 

The distilled product can be used as a catalyst, although it usually has a relatively strong phenylphosphine odor. It is quite deliquescent, and it has not been satisfactorily recrystallized. If rigorous purification and deodorization are desired, the product is dissolved in water, a small amount of hydrogen peroxide is added to oxidize the phosphines, the solution is reneutralized, saturated with salt, and extracted with chloroform, and the product is refractionated. One cycle is normally enough. Pure product is essentially odorless, very hygroscopic, and soluble in polar solvents. 

B. Pyridine-N-oxide. The acetic acid solution is evaporated on the steam bath under the pressure of a water aspirator, and the residue (180-190 g.) is distilled at a pressure of 1 mm. or less in an apparatus suitable for collecting a solid distillate (Note 5). The vacuum pump must be protected with a Dry Ice trap capable of holding about 60 ml. of acetic acid, which distils as the pyridine-N-oxide acetate dissociates at low pressure. Heat is provided by an oil bath, the temperature of which is not allowed to rise above 130° (Note 6). The product is collected at 100-105°/1 mm. (95-98°/0.5 mm.). The yield is 103-110 g. (78-83%) of colorless solid, m.p. 65-66° (sealed capillary). The base is deliquescent and must be stoppered immediately. 

CH3COONH4-CH3COOH An acid salt resulting from the distillation of the neutral salt or from Its solution in hot acetic acid crystallizes in deliquescent needles. 

Rather more than its own weight of phosphoric anhydride is added in small quantities at a time to nitric acid, HN03, cooled in a freezing mixture so as to avoid any consider-able rise in the temperature, which should not at any time be above zero. The pasty mass thus obtained is then rapidly transferred to a tubulated retort capable of containing 5 or 6 times the quantity, and distilled very slowly, collecting the product in stoppered bottles surrounded with ice. The anhydride condenses in long, transparent, colourless crystals which, when exposed to the air, slowly evaporate without deliquescing. 

Palladium chloride can be distilled at a low red heat in a current of chlorine. It then yields a sublimate of dark red, needle-shaped crystals4 which deliquesce in the air. 

The Butter of Antimony has a ravenous appetite for the moisture in the air and will deliquesce even on a hot sunny day. The water distilled from it is said to carry a truly Universal Fire which can be set to operate in any of the three kingdoms. 

Now distil the concentrated vinegar but discard the first 1/4 to 1/3 as it is mostly water. Distil to near dryness and collect the distillate. This is the Fixed Spirit. Combine all of the residual solids from both the wine and vinegar processing, and calcine them. Then leach out the salts and crystallize several times. Allow the salts to deliquesce for some time between crystallizations. 

Pour the sulphuric acid into a retort, gradually adding the muriate of soda, and oxide of antimony, previously mixed. Then perform the distillation in a sand bath. Expose the distilled matter for several days to the air, that it may deliquesce, and then pour the liquor from the feces. 

The liquid gives a few drops of forerun on distillation and then yields a clear liquid distillate (4 g) boiling at 66-69 C (0.6 mm), which partially crystallizes on standing. About half is pure white crystals and the other half clear liquid (which crystallizes slightly below room temperature). The infrared spectra of both are very similar to a standard spectrum of trichloroacetic acid. The solid is deliquescent and is identified as trichloroacetic acid. Anal. Calcd. for C2HO2CI3 Cl, 65.1. Found Cl, 63.9. The liquid fraction contains 55.3 % Cl, which is close to theoretical for dichloroacetic acid, but its infrared spectrum shows it to be predominantly trichloroacetic acid, contaminated with lesser amounts of dichloroacetic acid (yield ca. 25%). 

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