Sublimate Liquid

All reagents were reagent-grade chemicals. Hydrocarbon solvents were dried over sodium wire. TMEDA was dried over sodium wire and then distilled under reduced pressure. TED was tried under vacuum to the point of sublimation. Liquid tertiary amines and diamines were... 

Separations involving phase transfer distillation, sublimation, liquid-liquid distribution, gas-solid, and liquid-solid adsorption, both single and multi-stage. 

If the product is a solid, recrystallization is in most cases a highly selective process, and is applied directly upon removal of the ether or pentane. If the desired substance will not crystallize well at this stage, distillation, sublimation, liquid chromatography (with <30 g), preparative gas chromatography (with <20 g), or countercurrent distribution (with <100 g) may effect sufficient purification themselves, or they may be followed by recrystallization to give sufficiently pure material. For extreme purity (>99.99% has been claimed in some cases), zone refining can be used as a final step. 

Thermally induced phase separation Similar to the previous technique, this phase separation procedure requires the use of a solvent with a low melting point that is easy to sublime. Liquid-liquid phase separation presents the same drawbacks of emulsification/freeze-drying. 

It was first described in 1608 when it was sublimed out of gum benzoin. It also occurs in many other natural resins. Benzoic acid is manufactured by the air oxidation of toluene in the liquid phase at 150°C and 4-6 atm. in the presence of a cobalt catalyst by the partial decarboxylation of phthalic anhydride in either the liquid or vapour phase in the presence of water by the hydrolysis of benzotrichloride (from the chlorination of toluene) in the presence of zinc chloride at 100°C. 

The oxime is freely soluble in water and in most organic liquids. Recrystallise the crude dry product from a minimum of 60-80 petrol or (less suitably) cyclohexane for this purpose first determine approximately, by means of a small-scale test-tube experiment, the minimum proportion of the hot solvent required to dissolve the oxime from about 0-5 g. of the crude material. Then place the bulk of the crude product in a small (100 ml.) round-bottomed or conical flask fitted with a reflux water-condenser, add the required amount of the solvent and boil the mixture on a water-bath. Then turn out the gas, and quickly filter the hot mixture through a fluted filter-paper into a conical flask the sodium chloride remains on the filter, whilst the filtrate on cooling in ice-water deposits the acetoxime as colourless crystals. These, when filtered anddried (either by pressing between drying-paper or by placing in an atmospheric desiccator) have m.p. 60 . Acetoxime sublimes rather readily when exposed to the air, and rapidly when warmed or when placed in a vacuum. Hence the necessity for an atmospheric desiccator for drying purposes. 

The term distillation is applied to vaporisation and subsequent condensation according to (i) it should also be applied to (ii) since it is really the liquid which is converted into vapour and is first formed by condensation. Strictly speaking, the term sublimation should be applied to changes according to (iii). However, in practice, a substance when heated may first melt and then boil, but on cooling it may pass directly from the vapour to the solid the process is then also called sublimation. Indeed the mode of vaporisation, whether directly from solid to vapour or through the intermediate formation of a liquid, is of secondary importance it is the direct conversion of vapour to solid which is really the outstanding feature of sublimation in the laboratory. 

To understand the conditions which control sublimation, it is necessary to study the solid - liquid - vapour equilibria. In Fig. 1,19, 1 (compare Fig. 1,10, 1) the curve T IF is the vapour pressure curve of the liquid (i.e., it represents the conditions of equilibrium, temperature and pressure, for a system of liquid and vapour), and TS is the vapour pressure curve of the solid (i.e., the conditions under which the vapour and solid are in equili-hrium). The two curves intersect at T at this point, known as the triple point, solid, liquid and vapour coexist. The curve TV represents the... 

The theory of sublimation, t.e. the direct conversion from the vapour to the sohd state without the intermediate formation of the liquid state, has been discussed in Section 1,19. The number of compounds which can be purified by sublimation under normal pressure is comparatively small (these include naphthalene, anthracene, benzoic acid, hexachloroethane, camphor, and the quinones). The process does, in general, yield products of high purity, but considerable loss of product may occur. 

Place 0-5 g. of the amino acid and 1 0 g. of phthalic anhdride in a Pyrex test-tube and immerse the lower part of the tube in an oil bath, which has previously been heated to 180-185°. Stir the mixture occasionally during the first 10 minutes and push down the phthalic anhydride which sublimes on the walls into the reaction mixture with a glass rod. Leave the mixture undisturbed for 5 minutes. After 15 minutes, remove the test-tube from the bath when the liquid mass solidifies, invert the test-tube and scrape out the excess of phthalic anhydride on the walls. RecrystaUise the residue from 10 per cent ethanol or from water. 

Separations based upon differences in the physical properties of the components. When procedures (1) or (2) are unsatisfactory for the separation of a mixture of organic compounds, purely physical methods may be employed. Thus a mixture of volatile liquids may be fractionally distilled (compare Sections 11,15 and 11,17) the degree of separation may be determined by the range of boiling points and/or the refractive indices and densities of the different fractions that are collected. A mixture of non-volatile sohds may frequently be separated by making use of the differences in solubilities in inert solvents the separation is usually controlled by m.p. determinations. Sometimes one of the components of the mixture is volatile and can be separated by sublimation (see Section 11,45). 

Enthalpy of Vaporization (or Sublimation) When the pressure of the vapor in equilibrium with a liquid reaches 1 atm, the liquid boils and is completely converted to vapor on absorption of the enthalpy of vaporization ISHv at the normal boiling point T. A rough empirical relationship between the normal boiling point and the enthalpy of vaporization (Trouton s rule) is ... 

When the sample is a solid, a separation of the analyte and interferent by sublimation may be possible. The sample is heated at a temperature and pressure below its triple point where the solid vaporizes without passing through the liquid state. The vapor is then condensed to recover the purified solid. A good example of the use of sublimation is in the isolation of amino acids from fossil mohusk shells and deep-sea sediments. ... 

Vapor pressure is the most important of the basic thermodynamic properties affec ting liquids and vapors. The vapor pressure is the pressure exerted by a pure component at equilibrium at any temperature when both liquid and vapor phases exist and thus extends from a minimum at the triple point temperature to a maximum at the critical temperature, the critical pressure. This section briefly reviews methods for both correlating vapor pressure data and for predicting vapor pressure of pure compounds. Except at very high total pressures (above about 10 MPa), there is no effect of total pressure on vapor pressure. If such an effect is present, a correction, the Poynting correction, can be applied. The pressure exerted above a solid-vapor mixture may also be called vapor pressure but is normallv only available as experimental data for common compounds that sublime. 

If the pump is a filter pump off a high-pressure water supply, its performance will be limited by the temperature of the water because the vapour pressure of water at 10°, 15°, 20° and 25° is 9.2, 12.8, 17.5 and 23.8 mm Hg respectively. The pressure can be measured with an ordinary manometer. For vacuums in the range lO" mm Hg to 10 mm Hg, rotary mechanical pumps (oil pumps) are used and the pressure can be measured with a Vacustat McLeod type gauge. If still higher vacuums are required, for example for high vacuum sublimations, a mercury diffusion pump is suitable. Such a pump can provide a vacuum up to 10" mm Hg. For better efficiencies, the pump can be backed up by a mechanical pump. In all cases, the mercury pump is connected to the distillation apparatus through several traps to remove mercury vapours. These traps may operate by chemical action, for example the use of sodium hydroxide pellets to react with acids, or by condensation, in which case empty tubes cooled in solid carbon dioxide-ethanol or liquid nitrogen (contained in wide-mouthed Dewar flasks) are used. 

Common impurities found in aldehydes are the corresponding alcohols, aldols and water from selfcondensation, and the corresponding acids formed by autoxidation. Acids can be removed by shaking with aqueous 10% sodium bicarbonate solution. The organic liquid is then washed with water. It is dried with anhydrous sodium sulfate or magnesium sulfate and then fractionally distilled. Water soluble aldehydes must be dissolved in a suitable solvent such as diethyl ether before being washed in this way. Further purification can be effected via the bisulfite derivative (see pp. 57 and 59) or the Schiff base formed with aniline or benzidine. Solid aldehydes can be dissolved in diethyl ether and purified as above. Alternatively, they can be steam distilled, then sublimed and crystallised from toluene or petroleum ether. 

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