Surface-Cooling Crystallisation

A typical design feature is the way supersaturation is controlled and kept within the metastable range. The method is independently from the crystallisation process. Figure 9.6 explains this method based on the vacuum cooling crystallisation principle. This principle is also valid for the vacuum evaporation, surface cooling and reaction crystallisation. 

Vacuum-cooling crystallisation is the preferred cooling crystallisation method under continuous operation. Because cooling is generated by adiabatic expansion of the solvent no cooling surfaces can be incrusted. Vacuum-cooling becomes uneconomical only if cooling has to be effected at very lotv temperatures. 

In a 2-litre round-bottomed flask, equipped with a double surface condenser, place 60 g. of triniethylene dicyanide (Section 111,114) and 900 g. of 50 per cent, sulphuric acid (by weight). Reflux the mixture for 10 hours and allow to cool. Saturate the solution with ammonium sul phate and extract wit-h four 150 ml. portions of ether dry the ethereal extracts with anhydrous sodium or magnesium sulphate. Distil off the ether on a water bath the residual glutaric acid (69 g.) crystallises on cooling and has m.p. 97-97-5°. Upon recrystalhsation from chloroform, or benzene, or benzene mixed with 10 per cent, by weight of ether, the m.p. is 97 -5-98°. 

Into a 1-litre beaker, provided with a mechanical stirrer, place 36 - 8 g. (36 ml.) of aniline, 50 g. of sodium bicarbonate and 350 ml. of water cool to 12-15° by the addition of a little crushed ice. Stir the mixture, and introduce 85 g. of powdered, resublimed iodine in portions of 5-6 g, at intervals of 2-3 minutes so that all the iodine is added during 30 minutes. Continue stirring for 20-30 minutes, by which time the colour of the free iodine in the solution has practically disappeared and the reaction is complete. Filter the crude p-iodoaniline with suction on a Buchner funnel, drain as completely as possible, and dry it in the air. Save the filtrate for the recovery of the iodine (1). Place the crude product in a 750 ml. round-bottomed flask fitted with a reflux double surface condenser add 325 ml. of light petroleum, b.p. 60-80°, and heat in a water bath maintained at 75-80°. Shake the flask frequently and after about 15 minutes, slowly decant the clear hot solution into a beaker set in a freezing mixture of ice and salt, and stir constantly. The p-iodoaniline crystallises almost immediately in almost colourless needles filter and dry the crystals in the air. Return the filtrate to the flask for use in a second extraction as before (2). The yield of p-iodoaniline, m.p. 62-63°, is 60 g. 

Method 1 (with acetyl chloride). Equip a dry 500 ml. round-bottomed or bolt-head flask with a reflux condenser, and fit the top of the condenser with a two hole cork, one opening for a separatory funnel and the other for a delivery tube connected to an inverted funnel which dips just below the surface of about 200 ml. of water in a beaker (compare Fig. II, 13, 8). Place 40 g. of anhydrous, finely-powdered aluminium chloride (see Section IV,2) and 88 g. (100 ml.) of dry A.R. benzene in the flask and cool the latter in a bath of cold water (not ice water since benzene may crystallise). Through the separatory funnel at the top of the condenser add 29 g. (27 ml.) of redistilled acetyl chloride slowly during half an hour and shake the flask frequently to ensure thorough mixing of the... 

This situation is identical to the previous one and occurs for example when paraffin wax is mixed into rubber above the melting point of the wax. On cooling, the wax starts to crystallise, some of it forming a bloom on the rubber surface. Such a bloom assists in protecting a diene rubber from ozone attack. 

The dissolved substances (especially if the solution is very concentrated) often crystallises in the funnel on account of local cooling and in this way filtration is hindered. This trouble can be partially met by using a funnel (Fig. 3) with the delivery tube cut short (0 5-l-0 cm.). But it is much more satisfactory to use a so-called hot water funnel (Fig. 4) in which the filtering surface of the funnel is heated with boiling water in a metal jacket. When inflammable solvents are used, the flame must be extinguished before filtration. 

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