P Reduced pressur

T = reduced temperature of the mixture P = reduced pressure of the mixture... 

P,. = reduced pressure = absolute pressure/ absolute critical pressure. 

P = reduced pressure p = reduced density T = reduced temperature... 

Q - generalized van der Waals partition function, dimensionless P - reduced pressure (=P/P ), dimensionless... 

Isocroionic acid, -crotonic acid, cis-croionic acid. Colourless needles m.p. 14 C, b.p. 169 C. Prepared by distilling -hydroxy-glutaric acid under reduced pressure. Converted to a-crotonic acid by heating at 180 C, or by the action of bromine and sunlight on an aqueous solution. 

It is a liquid, b,p. 363 K, but if heated it decomposes and hence must be distilled under reduced pressure decomposition may occur with explosive violence and this can occur even at room temperature if impurities are present. Combustible material, for example paper and wood, ignite spontaneously with explosive violence on contact with the acid, and it can produce painful blisters on the skin,... 

Distillation under reduced pressure. The student should first read details of this operation on a macro-scale (p. 28). For micro-scale work the apparatus shown in Fig. 40 is very convenient. A small pear-... 

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. 

Physical properties. All are colourless crystalline solids except formic acid, acetic acid (m.p. 18 when glacial) and lactic acid (m.p. 18°, usually a syrup). Formic acid (b.p. loo ") and acetic acid (b.p. 118 ) are the only members which are readily volatile lactic acid can be distilled only under reduced pressure. Formic and acetic acids have characteristic pungent odours cinnamic acid has a faint, pleasant and characteristic odour. 

Selection of solvents. The choice of solvent will naturally depend in the first place upon the solubility relations of the substance. If this is already in solution, for example, as an extract, it is usually evaporated to dryness under reduced pressure and then dissolved in a suitable medium the solution must be dilute since crystallisation in the column must be avoided. The solvents generally employed possess boiling points between 40° and 85°. The most widely used medium is light petroleum (b.p. not above 80°) others are cycZohexane, carbon disulphide, benzene, chloroform, carbon tetrachloride, methylene chloride, ethyl acetate, ethyl alcohol, acetone, ether and acetic acid. 

Formamide. Commercial formamide may contain excess of formic acid. It is purified by passing ammonia gas into the mixture until a slight alkaline reaction is obtained. The ammonium formate thus formed is precipitated by the addition of acetone the filtrate, after drying over anhydrous magnesium sulphate, is distilled under reduced pressure. Pure formamide has b.p. IO571I mm. 

For alcohols of b.p. below 150°, mix 0- 5 g. of 3-nitrophthalic anhydride (Section VII,19) and 0-5 ml. (0-4 g.) of the dry alcohol in a test-tube fitted with a short condenser, and heat under reflux for 10 minutes after the mixture liquefies. For alcohols boiling above 150°, use the same quantities of reactants, add 5 ml. of dry toluene, heat under reflux until all the anhydride has dissolved and then for 20 minutes more remove the toluene under reduced pressure (suction with water pump). The reaction product usually solidifies upon cooling, particularly upon rubbing with a glass rod and standing. If it does not crystallise, extract it with dilute sodium bicarbonate solution, wash the extract with ether, and acidify. Recrystallise from hot water, or from 30 to 40 per cent, ethanol or from toluene. It may be noted that the m.p. of 3-nitrophthalic acid is 218°. 

Trimethylene Di-iodide. Use 76 g. of trimethylene glycol, 27 - 52 g. of pmified red phosphorus and 254 g. of iodine. Lag the arm C (Fig. Ill, 40, ) with asbestos cloth. Stop the heating immediately all the iodine has been transferred to the fiask. Add water to the reaction mixture, decolourise with a httle sodium bisulphite, filter, separate the crude iodide, wash it twice with water, dry with anhydrous potassium carbonate and distU under reduced pressure. B.p. 88-89°/6 mm. Yield 218 g. (a colourless liquid). 

Redistil laboratory grade ethylene glycol under reduced pressure and collect the fraction of b.p. 85-90°/7 mm. for use as a solvent for the potassium fluoride. 

Equip a 1-litre three-necked flask with a powerful mechanical stirrer, a separatory funnel with stem extending to the bottom of the flask, and a thermometer. Cool the flask in a mixture of ice and salt. Place a solution of 95 g. of A.R. sodium nitrite in 375 ml. of water in the flask and stir. When the temperature has fallen to 0° (or slightly below) introduce slowly from the separatory funnel a mixture of 25 ml. of water, 62 5 g. (34 ml.) of concentrated sulphuric acid and 110 g. (135 ml.) of n-amyl alcohol, which has previously been cooled to 0°. The rate of addition must be controlled so that the temperature is maintained at 1° the addition takes 45-60 minutes. AUow the mixture to stand for 1 5 hours and then filter from the precipitated sodium sulphate (1). Separate the upper yellow n-amyl nitrite layer, wash it with a solution containing 1 g. of sodium bicarbonate and 12 5 g. of sodium chloride in 50 ml. of water, and dry it with 5-7 g. of anhydrous magnesium sulphate. The resulting crude n-amyl nitrite (107 g.) is satisfactory for many purposes (2). Upon distillation, it passes over largely at 104° with negligible decomposition. The b.p. under reduced pressure is 29°/40 mm. 

Method B. Reflux a mixture of 101 g. of sebacic acid, 196 g. (248 ml.) of absolute ethjd alcohol and 20 ml. of concentrated sulphuric acid for 12 hours. Distil oft about half of the alcohol on a water bath dilute the residue with 500-750 ml. of water, remove the upper layer of crude ester, and extract the aqueous layer with ether. Wash the combined ethereal extract and crude ester with water, then with saturated sodium bicarbonate solution until effervescence ceases, and finally with water. Dry with anhydrous magnesium or sodium sulphate, remove the ether on a water bath, and distil the residue under reduced pressure. B.p. 155-157°/6 mm. Yield llOg. 

Commercial 2 4-dichlorophenoxyacetic acid may be recrystallised from benzene m.p. 139-140°. Reflux 10 g. of the acid with 15 ml. of thionyl chloride on a steam bath for 1 hour, distil off the excess of thionyl chloride at atmospheric pressure and the residue under reduced pressure 2 4-dichlorophenoxyacetyl chloride (8 g.) passes over at 155-157°/22-23 mm. It occasionally crystallises (m.p. 44-5-45-5°), but usually tends to remain as a supercooled liquid. 

The following is a modification of the process described and gives quite satisfactory results. Wash the crude mixture of benzonitrile and dibromopentane with sodium carbonate solution until the latter remains alkaline, and then with water. Distil it under reduced pressure and collect the fraction boiling up to 120°/18 mm. Dissolve this in twice its volume of light petroleum, b.p. 40-60°, which has previously been shaken with small volumes of concentrated sulphuric acid until the acid remains colourless. Shake the solution with 6 per cent, of its volume of concentrated sulphuric acid, allow to settle, and run ofi the sulphuric acid layer repeat the extraction until the acid is colourless or almost colourless. Wash successively with water, sodium carbonate solution and water, dry over anhydrous calcium chloride or calcium sulphate, and distil off the solvent. Distil the residue under diminished pressure and collect the 1 6-dibromopentane at 98- 100°/13 mm. 

The apparatus required is similar to that described for Diphenylmelhane (Section IV,4). Place a mixture of 200 g. (230 ml.) of dry benzene and 40 g. (26 ml.) of dry chloroform (1) in the flask, and add 35 g. of anhydrous aluminium chloride in portions of about 6 g. at intervals of 5 minutes with constant shaking. The reaction sets in upon the addition of the aluminium chloride and the liquid boils with the evolution of hydrogen chloride. Complete the reaction by refluxing for 30 minutes on a water bath. When cold, pour the contents of the flask very cautiously on to 250 g. of crushed ice and 10 ml. of concentrated hydrochloric acid. Separate the upper benzene layer, dry it with anhydrous calcium chloride or magnesium sulphate, and remove the benzene in a 100 ml. Claisen flask (see Fig. II, 13, 4) at atmospheric pressure. Distil the remaining oil under reduced pressure use the apparatus shown in Fig. 11,19, 1, and collect the fraction b.p. 190-215°/10 mm. separately. This is crude triphenylmethane and solidifies on cooling. Recrystallise it from about four times its weight of ethyl alcohol (2) the triphenylmethane separates in needles and melts at 92°. The yield is 30 g. 

Pour the resulting dark reddish-brown liquid into 500 ml. of water to which 17 ml. of saturated sodium bisulphite solution has been added (the latter to remove the excess of bromine). Steam distil the resulting mixture (Fig. II, 41,1) , collect the first portion of the distillate, which contains a little unchanged nitrobenzene, separately. Collect about 4 litres of distillate. Filter the yellow crystalline solid at the pump, and press well to remove the adhering liquid. The resulting crude m-bromonitrobenzene, m.p. 51-52°, weighs 110 g. If required pure, distil under reduced pressure (Fig. II, 19, 1) and collect the fraction of b.p. 117-118°/9 mm. it then melts at 56° and the recovery is about 85 per cent. 

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