Crystalline Drying

When, in an aqueous system, the formation of the CD-inclusion complex can be detected, e.g., by NMR or circular dichroism or through a catalytic effect, this does not necessarily mean that a well-defined crystalline inclusion complex can be isolated. The two main components of the driving force of the inclusion process are the repulsive forces between the included water molecules and the apolar CD cavity on the one hand, and between the bulk water and the apolar guest, on the other hand. This second factor does not exist in the crystalline (dry) state. Therefore. it is common to find that the complex formation is convincingly proven in solution, but the isolated product is only a very fine dispersion of the CD and the guest. 

The film/shell formation of PVP makes it difficult to determine whether hot gas application is beneficial for the atomization of complex-viscous materials. At least materials with a strong surface film-forming mechanism are not suitable to be dried by the hot gas process. For materials with a crystalline drying mechanism, moisture can be transported through the crust more easily. Hot gas atomization may be used where rapid evaporation is necessary to create rough particle morphologies. 

Features Very mild good foaming props. good tolerance of water hardness creates a hard crystalline dry residue compat. with anionic, amphoteric, and nonionic surfactants not compat. with cationic surfactants Properties Bright yel, turbid paste (tends to precipitate) pH 6.5-7.5 (5% solids) ... 

CH2Br COOH. White crystalline solid, m.p. 50"C, b.p. 208 C. Soluble in water and alcohol. Prepared by the action of dry bromine on dry ethanoic acid in presence of small amounts of red phosphorus. Produces sores upon the skin used in chemical syntheses. See Reformatski reaction. 

Enzymes are obtained from plants, animals and micro-organisms by extraction with a suitable solvent, preferably after the cell structure has been destroyed by drying or grinding. They can be purified by precipitation and resolution and by fractional absorption and elution. Many enzymes have been obtained crystalline. 

CsHsO. Colourless, crystalline solid m.p. 115 C. Prepared by the dry distillation of tartaric acid or by reduction of itaconic or cilra-conic acids. Forms an anhydride when heated to 200"C. 

In corrosion, adsorbates react directly with the substrate atoms to fomi new chemical species. The products may desorb from the surface (volatilization reaction) or may remain adsorbed in fonning a corrosion layer. Corrosion reactions have many industrial applications, such as dry etching of semiconductor surfaces. An example of a volatilization reaction is the etching of Si by fluorine [43]. In this case, fluorine reacts with the Si surface to fonn SiF gas. Note that the crystallinity of the remaining surface is also severely disrupted by this reaction. An example of corrosion layer fonnation is the oxidation of Fe metal to fonn mst. In this case, none of the products are volatile, but the crystallinity of the surface is dismpted as the bulk oxide fonns. Corrosion and etching reactions are discussed in more detail in section A3.10 and section C2.9. 

Add in turn benzyl chloride (8 3 g., 8 o ml.) and powdered thiourea (5 gm.) to 10 ml. of 95% ethanol in a 100 ml. flask fitted with a reflux condenser. Warm the mixture on the water-bath with gentle shaking until the reaction occurs and the effervescence subsides then boil the mixture under reflux for 30 minutes. Cool the clear solution in ice-water, filter off the crystalline deposit of the benzylthiouronium chloride at the pump, wash it with ice-cold ethyl acetate, and dry in a desiccator. Yield, 11-12 g., m.p. 170-174°. The white product is sufficiently pure for use as a reagent. It is very soluble in cold water and ethanol, but can be recrystallised by adding ethanol dropwise to a boiling suspension in ethyl acetate or acetone until a clear solution is just obtained, and then rapidly cooling. 

Distil the filtered ethereal solution, using a 100 ml. flask fitted with a dropping-funnel and a side-arm for the condenser observe all the normal precautions for ether distillation (p. 162) and run the ethereal solution into the flask as fast as the ether distils over. When all the ether has distilled off, detach and cool the flask, when the oily colourless residue of saligenin will rapidly crystallise. Weight of product, 5-0 g. m.p. 75-82°. Recrystallise either from a mixture of benzene and petroleum (b.p. 60-80°), or from a minimum of water, allowing the stirred aqueous solution to cool to 65-70° before chilling. The dry crystalline saligenin has m.p. 85-86°. 

The crystalline sodium sulphide (NajS,9H20) used to prepare the disulphide is very deliquescent, and only a sample which has been kept in a well-stoppered bottle and therefore reasonably dry should be used. A sample from a badly-stoppered bottle may contain, in addition to the crystals, a certain amount of aqueous solution, in which hydrolysis and partial decomposition will have occurred such a sample should therefore be rejected. Add 4 2 g. of finely powdered sulphur to a solution of 16 g. of the crystalline sodium sulphide in 60 ml. of water, and boil the mixture gently for a few minutes until a clear solution of the disulphide is obtained. 

Arsonic acids, like carboxylic and sulphonic acids (pp. 349, 353), usually give crystalline benzylthiouronium salts. Add just sufficient dilute aqueous sodium hydroxide dropwise with shaking to a suspension of 0 5 g. of phenylarsonic acid in 10 ml. of water to give a clear solution. Then add 0 5 g. of benzylthiouronium chloride dissolved in 10 ml. of water. Filter off the precipitated benzylthiouronium salt, wash with water and dry m.p. 114-117° it tends to dissociate on attempted recrystallisation. 

Pyridine methiodide and ethiodide. Place 2 drops of dry pyridine in a test-tube, add 2 drops of methyl iodide and mix. A vigorous reaction occurs and on cooling, a colourless crystalline mass of pyridine methiodide, CjHjN.Mel, is formed cf. p. 377) when recrystallised from methylated spirit, the methiodide has m.p. 117. ... 

Cool the remainder of the filtrate and extract three times with ether, using 20 - 30 ml. for each extraction. Dry the combined ethereal extracts over powdered anhydrous sodium sulphate. Filter into a small flask and distil off the ether on a water-bath. Pour the residual oil into a small dish or beaker crystallisation takes place almost immediately. The salicyl alcohol so obtained is almost pure, but it may, if so desired, be recrystallised from a small quantity of benzene. It is a colourless crystalline solid, m.p. 86 , readily soluble in water it gives a violet coloration with ferric chloride. 

If the solvent constituting the crystallisation medium has a compara tively high boiling point, it is advisable to wash the solid with a solvent of low boiling point in order that the ultimate crystalline product may be easily dried it need hardly be added that the crystals should be insoluble or only very sparingly soluble in the volatile solvent. The new solvent must be completely miscible with the first, and should not be applied until the crystals have been washed at least once with the original solvent. 

In order to dry the crystals, the Buchner funnel is inverted over two or three thicknesses of drying paper (i.e., coarse-grained, smooth surfaced Alter paper) resting upon a pad of newspaper, and the crystalline cake is removed with the aid of a clean spatula several sheets of drying paper are placed on top and the crystals are pressed flrmly. If the sheets become too soiled by the mother liquor absorbed, the crystals should be transferred to fresh paper. The disadvantage of this method of rapid drying is that the recrystallised product is liable to become contaminated with the Alter paper flbre. 

For solids which melt above 100° and are stable at this temperature, drying may be carried out in a steam oven. The crystals from the Buchner funnel should then be placed on a clock glass or in an open dish. The substance may sometimes be dried in the Buchner funnel itself by utilising the device illustrated in Fig. 77, <33, 1. An ordinary Pyrex funnel is inverted over the Buchner funnel and the neck of the funnel heated by means of a broad flame (alternatively, the funnel may be heated by a closely-fltting electric heating mantle) if gentle suction is applied to the Alter flask, hot (or warm) air will pass over the crystalline solid. 

Pure pyridine may be prepared from technical coal-tar pyridine in the following manner. The technical pyridine is first dried over solid sodium hydroxide, distilled through an efficient fractionating column, and the fraction, b.p. 114 116° collected. Four hundred ml. of the redistilled p)rridine are added to a reagent prepared by dissolving 340 g. of anhydrous zinc chloride in a mixture of 210 ml. of concentrated hydrochloric acid and 1 litre of absolute ethyl alcohol. A crystalline precipitate of an addition compound (probable composition 2C5H5N,ZnCl2,HCl ) separates and some heat is evolved. When cold, this is collected by suction filtration and washed with a little absolute ethyl alcohol. The yield is about 680 g. It is recrystaUised from absolute ethyl alcohol to a constant m.p. (151-8°). The base is liberated by the addition of excess of concentrated... 

Add 0-5-1 ml. of the alcohol, cork the flask loosely, and heat on a water bath for 10 minutes secondary and tertiary alcohols require longer heating (up to 30 minutes). Cool the mixture, add 10 ml. of 5 per cent, (or saturated) sodium bicarbonate solution, break up the resulting solid ester with a stirring rod (alternatively, stir until crystalline), and filter at the pump wash with a little sodium bicarbonate solution, followed by water, and then suck as dry as possible. Dissolve the crude... 

Into a 500 ml. three-necked flask, provided with a mechanical stirrer, a gas inlet tube and a reflux condenser, place 57 g. of anhydrous stannous chloride (Section 11,50,11) and 200 ml. of anhydrous ether. Pass in dry hydrogen chloride gas (Section 11,48,1) until the mixture is saturated and separates into two layers the lower viscous layer consists of stannous chloride dissolved in ethereal hydrogen chloride. Set the stirrer in motion and add 19 5 g. of n-amyl cyanide (Sections III,112 and III,113) through the separatory funnel. Separation of the crystalline aldimine hydrochloride commences after a few minutes continue the stirring for 15 minutes. Filter oflF the crystalline solid, suspend it in about 50 ml. of water and heat under reflux until it is completely hydrolysed. Allow to cool and extract with ether dry the ethereal extract with anhydrous magnesium or calcium sulphate and remove the ether slowly (Fig. II, 13, 4, but with the distilling flask replaced by a Claisen flask with fractionating side arm). Finally, distil the residue and collect the n-hexaldehyde at 127-129°. The yield is 19 g. 

Prepare 10 ml. of saturated sodium bisulphite solution and add 4 ml. of the aldehyde shake thoroughly and observe the rise in temperature. Filter the crystalline precipitate at the pump, wash it with a little alcohol, followed by ether, and allow it to dry. 

Dissolve 2 5 g. of hydroxylamine hydrochloride and 4 g. of crystallised sodium acetate in 10 ml. of water in a small flask or in a test-tube. Warm the solution to about 40° and add 2 5 g. of cyclohexanone. Stopper the vessel securely with a cork and shake vigorously for a few minutes the oxime soon separates as a crystalline solid. Cool in ice, filter the crystals at the pump, and wash with a little cold water. RecrystaUise from light petroleum, b.p. 60-80°, and dry the crystals upon filter paper in the air. The yield of pure cycZohexanone oxime, m.p. 90°, is 2 -5 g. 

Xanthylamides. Dissolve 0 25 g. of xanthhydrol in 3-5 ml. of glacial acetic acid if an oil separates (as is sometimes the case with commercial material), allow to settle for a short time and decant the supernatant solution. Add 0-25 g. of the amide, shake and allow to stand. If a crystalline derivative does not separate in about 10 minutes, warm on a water bath for a period not exceeding 30 minutes, and allow to cool. Filter oflF the solid xanthylamide (9-acylamidoxanthen) and recrystallise it from dioxan - water or from acetic acid - water, dry at 80° for 15 minutes and determine the m.p. 

C. Fumaric acid from furfural. Place in a 1-litre three-necked flask, fitted with a reflux condenser, a mechanical stirrer and a thermometer, 112 5 g. of sodium chlorate, 250 ml. of water and 0 -5 g. of vanadium pentoxide catalyst (1), Set the stirrer in motion, heat the flask on an asbestos-centred wire gauze to 70-75°, and add 4 ml. of 50 g. (43 ml.) of technical furfural. As soon as the vigorous reaction commences (2) bvi not before, add the remainder of the furfural through a dropping funnel, inserted into the top of the condenser by means of a grooved cork, at such a rate that the vigorous reaction is maintained (25-30 minutes). Then heat the reaction mixture at 70-75° for 5-6 hours (3) and allow to stand overnight at the laboratory temperature. Filter the crystalline fumaric acid with suction, and wash it with a little cold water (4). Recrystallise the crude fumaric acid from about 300 ml. of iif-hydrochloric acid, and dry the crystals (26 g.) at 100°. The m.p. in a sealed capillary tube is 282-284°. A further recrystaUisation raises the m.p. to 286-287°. 

Introduce 197 g. of anhydrous brucine or 215 g. of the air-dried dihydrate (4) into a warm solution of 139 g. of dZ-acc.-octyl hj drogen phthalate in 300 ml. of acetone and warm the mixture vmder reflux on a water bath until the solution is clear. Upon cooling, the brucine salt (dA, IB) separates as a crystalline solid. Filter this off on a sintered glass funnel, press it well to remove mother liquor, and wash it in the funnel with 125 ml. of acetone. Set the combined filtrate and washings (W) aside. Cover the crystals with acetone and add, slowly and with stirriug, a slight excess (to Congo red) of dilute hydrochloric acid (1 1 by volume about 60 ml.) if the solution becomes turbid before the introduction of... 

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