Stoppering

Spillages during dispensing are often overlooked since liquid product is invariably transparent. However any spilled liquid on the freeze-drier shelf will dry to form a thin, friable layer of powder which will be readily disseminated from the chamber when the vacuum is released and the product batch removed. 

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Iodine is a dark-coloured solid which has a glittering crystalline appearance. It is easily sublimed to form a bluish vapour in vacuo. but in air, the vapour is brownish-violet. Since it has a small vapour pressure at ordinary temperatures, iodine slowly sublimes if left in an open vessel for the same reason, iodine is best weighed in a stoppered bottle containing some potassium iodide solution, in which the iodine dissolves to form potassium tri-iodide. The vapour of iodine is composed of I2 molecules up to about 1000 K above this temperature, dissociation into iodine atoms becomes appreciable. 

When a more delicate fractional vacuum-distillation is required, the flask and column shown in Fig. ii(b), p. 26, may be used, the side-arm of the column being fitted directly into receiver C (Fig. 14). A rubber stopper must then be used to fit the flask on to the fractionating column, and it should also carry a capillary tube leading to the bottom of the flask, to provide the usual fine stream of bubbles to prevent bumping. 

Never use unprotected bark corks for an apparatus ih which a carefully dried liquid is to be distilled, etc., as these corks always contain appreciable quantities of water, which is exuded when the cork comes into contact with a hot liquid. Rubber stoppers should therefore be used in these circumstances. 

When boring rubber stoppers, lubricate the borer well, either with aqueous glycerine or with vaseline. Then clean well and dry before using. 

Round-bottomed flasks (Fig. 22(A)) of various sizes and having necksof various lengths and widths. They can be closed with stoppers (Fig. 22(B)), or fitted with any of the following units reflux air-condensers (Fig. 22(C)) or water condensers (Fig. 22(D)) distillation heads, of the simple knee-tube type (Fig. 22(E)), or with a vertical joint (Fig. 22(F)) for thermometers, etc., or with... 

Fig. 23(B) shows a modification of the reflux assembly to allow a gas to be passed through the boiling liquid cf. Fischer-Speier esterification, p. 104). The inlet-tube A fits into a three-necked adaptor shown in Fig. 22(J). The stopper B can be replaced by a dropping-funnel, etc.

The absolute ethanol obtained in this way should have d., o 794, It is very hygroscopic, and the bottle in which it is stored should preferably have a well fitting ground-glass stopper alternatively, the bottle can be closed with a tightly fitting rubber stopper but not with a cork, as corks contain appreciable quantities of water. 

Fit a 250 ml. round-bottomed flask with a refllix water-condenser down which pieces of sodium may be dropped alternatively, use a flask having a short straight stoppered side-arm for this purpose. 

Dissolve 1 g. of powdered benzophenone in 6-7 ml. of cold isopropanol with shaking, add 1 drop of glacial acetic acid, and then confine the solution either in a glass receiver having a ground-glass stopper, or in a tube which is sealed... 

Aluminium isopropoxide can be obtained as a fine powder from technical sources. When the bottle has once been opened however, the stopper should be firmly replaced and covered with wax more conveniently, the stoppered bottle can be kept in an atmospheric desiccator over calcium chloride or sodium hydroxide, preferably in the dark. 

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. 

Picric acid if stored in bulk should, for safety, first be damped. Smaller quantities may be safely kept whilst dry, but should be stored in bottles having cork or rubber stoppers glass stoppers should never be used for potentially explosive substances, because on replacing the stopper some of the material may be ground between the neck of the flask and the stopper, and so caused to explode. 

Dissolve 2 g. of anthranilic acid in 12 8 ml. of 5% aqueous sodium hydroxide, or in 16 ml. of A -NaOH solution in a 50 ml. conical flask. (It is essential that the concentration of the hydroxide solution is accurately known.) Add i-6 ml. of dimethyl sulphate, and shake the securely-stoppered flask vigorously. 

For this reduction use preferably a i litre round-bottomed flask having 3 necks (Fig. 23(G), p. 46), the two necks at the flanks being straight (to avoid the obstruction, during the addition of sodium, which a curved neck might cause). Fit the central neck with a stirrer, one of the side necks with a reflux water-condenser, and the other with a glass or rubber stopper. 

Both the primary amine (D) and the tertiary amine (E) are reasonably strong bases, and will absorb carbon dioxide if exposed to the air. They should therefore be stored in ground-glass stoppered bottles or in sealed tubes. 

Assemble in a fume-cupboard the apparatus shown in Fig. 67(A). Place 15 g. of 3,5-dinitrobenzoic acid and 17 g. of phosphorus pentachloride in the flask C, and heat the mixture in an oil-bath for hours. Then reverse the condenser as shown in Fig. 67(B), but replace the calcium chloride tube by a tube leading to a water-pump, the neck of the reaction-flask C being closed with a rubber stopper. Now distil off the phosphorus oxychloride under reduced pressure by heating the flask C in an oil-bath initially at 25-30, increasing this temperature ultimately to 110°. Then cool the flask, when the crude 3,5-dinitro-benzoyl chloride will solidify to a brown crystalline mass. Yield, 16 g., i.e,y almost theoretical. Recrystallise from caibon tetrachloride. The chloride is obtained as colourless crystals, m.p. 66-68°, Yield, 13 g Further recrystallisation of small quantities can be performed using petrol (b.p. 40-60°). The chloride is stable almost indefinitely if kept in a calcium chloride desiccator. 

Fit a 750 ml, bolt-head flask (also by a rubber stopper) to a reflux water-condenser closed at the top by a calcium chloride tube ensure that flask and condenser are quite dr). Place 150 ml. of the dried ethyl acetate in the flask and add 15 g. of sodium. The sodium for this purpose should preferably be added in the form of wire directly from a sodium press (Fig. 55, p. 82) alternatively the sodium may be added as thin slices, but in this case each slice should be quickly pressed between drying-paper before being added to the acetate to remove the wet film which may have formed during the weighing and cutting of the metal. 

After 3 hours, replace the separating-funnel by a reflux condenser, and the thermometer by a stopper. Add 11 g. of zinc dust in small portions by rapid removal of the stopper at such a rate that the liquid is first brought to the boil (usually about 2 portions of 2 g. each) and is then maintained gently boiling. A ooid too rapid addition of the zinc, otherwise the reaction will become too vigorous, and rapid immersion of the flask in ice-water will be necessary to control the effervescence. 

Preparation of the Reagent. Grind thoroughly together in a dry mortar 25 g. of pure anhydrous ( Analar ) sodium carbonate and 50 g. of the purest obtainable zinc dust. Preserve the reagent in a wide-necked stoppered bottle until required. 

Dinitrobenzoyl-glycine. Dissolve 0 4 g. of glycine in 10 ml. of TV.NaOH solution in a small stoppered bottle. And i-i g. of finely powdered 3 5-dinitrobenzoyl chloride (preparation, p. 242) and shake vigorously for about 1 minute. Filter if necessary and acidify with dil. 

Meanwhile, the organic compound can be prepared for analysis whilst the sealed end C (Fig. 72) of the Carius tube has been cooling dow n. For this purpose, thoroughly clean and dry a small tube, which is about 6 cm. long and 8-10 mm. w ide. Weigh it carefully, supporting it on the balance pan either by means of a small stand of aluminium foil, or by a short section of a perforated rubber stopper (Fig. 73 (A) and (B) respectively) alternatively the tube may be placed in a small beaker on the balance pan, or suspended above the pan by a small hooked wire girdle. 

The liquid in B rapidly volatilises at the bottom of the tube T, the stopper being thrown off, and bubbles of air escape from D into the tube C. Continue boiling the liquid in J steadily until no more bubbles escape into C. Then carefully slip the end of D from under the tube C, close the end of C securely with the finger, and then transfer the tube to a gas-jar of water, so that the level of the water inside and outside C can be equalised. Measure the volume of air in C, and note the room temperature and the barometric pressure. The vapour density can now be calculated (see p. 428). 

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