Cyanides, solution pressure

Together with Ni(CO)4 andFe(CO)5, dicobaltoctacarbonyl, Co2(CO)g (1), was among the earliest metal carbonyls (see Metal Carbonyls) to be detected and characterized by Mond and coworkers." It was prepared from frnely divided metal (or by hydrogen reduction of the oxide, CoO) in a Cu-lined autoclave made from Ni steel at 150 °C and a CO pressure of 30-40 bar. Other preparations employ reductive carbonylation of cobalt salts, mainly Co(OAc)2, or the carbonylation of an alkaline cobalt cyanide solution. The acetate salt is also the common precursor for Co2(CO)g or Co(CO)4H in the Cocatalyzed hydroformylation (see Hydroformylation) process (Section HCo(CO)4 in Hydroformylation Reactions ). 

IV. Vapor Pressure Method. —If the free weak acid or weak base is appreciably volatile, it is possible to determine its concentration or, more correctly, its activity, from vapor pressure measurements. In practice the actual vapor pressure is not measured, but the volatility of the substance in the hydrolyzed salt solution is compared with that in a series of solutions of known concentration. In the case of an alkali cyanide, for example, the free hydrogen cyanide produced by hydrolysis is appreciably volatile. A current of air is passed at a definite rate through the alkali cyanide solution and at exactly the same rate through a hydrogen cyanide solution the free acid vaporizing with the air in each case is then absorbed in a suitable reagent and the amounts are compared. The concentration of the hydrogen cyanide solution is altered until one is found that vaporizes at the same rate as does the alkali cyanide solution. It may be assumed that the concentrations, or really activities, of the free acid are the same in both solutions. The concentration of free acid cha in the solution of the hydrolyzed salt of the weak acid may be put equal to cx (cf. p. 374) and hence x and kh can be calculated. 

The absorption of ozone by unagitated batch cyanide solutions at atmospheric pressure involves the sequence of initially complete absorption, followed by a period when ozone appears in the exhaust gas and cyanides are still present in the batch reactor. A countercurrent absorption tower was indicated to provide more intimate contact and better mass transfer where the last traces of ozone in the carrier gas would come in contact with the fresh solution at the top of the tower, and the weakest solution leaving at the bottom of the tower would come in contact with gas of the highest ozone content entering at that point. To investigate the characteristics of such a system, an all-glass absorption tower was constructed to study the effects of gas and liquid rates, tower height, and pH. Some of the data from these tests are presented in Tables I, II, and III. 

Five hundred grams of powdered copper(II) sulfate 5-hydrate (2 mols) is placed in the reaction vessel, and the latter is attached to the remaining apparatus with the stirrer just under the top of the solid. A saturated solution of sodium cyanide (500 ml.), which has been freshly prepared and filtered, is placed in the dropping funnel, and the pressure equalizer is attached. A slow stream of nitrogen is passed through the apparatus, and the sodium cyanide solution is added sufficiently slowly so that the temperature in the reaction vessel is maintained at 50... 

Equip a 1-litre three-necked flask with a mechanical stirrer, a separatory funnel and a thermometer. Place a solution of 47 g. of sodium cyanide (or 62 g. of potassium cyanide) in 200 ml. of water in the flask, and introduce 58 g. (73-5 ml.) of pure acetone. Add slowly from the separatory fumiel, with constant stirring, 334 g. (275 ml.) of 30 per cent, sulphuric acid by weight. Do not allow the temperature to rise above 15-20° add crushed ice, if necessary, to the mixture by momentarily removing the thermometer. After all the acid has been added continue the stirring for 15 minutes. Extract the reaction mixture with three 50 ml. portions of ether, dry the ethereal extracts with anhydrous sodium or magnesium sulphate, remove most of the ether on a water bath and distil the residue rapidly under diminished pressure. The acetone cyanohydrin passes over at 80-82°/15 mm. The yield is 62 g. 

Fit a 1500 ml. bolt-head flask with a reflux condenser and a thermometer. Place a solution of 125 g. of chloral hydrate in 225 ml. of warm water (50-60°) in the flask, add successively 77 g. of precipitated calcium carbonate, 1 ml. of amyl alcohol (to decrease the amount of frothing), and a solution of 5 g. of commercial sodium cyanide in 12 ml. of water. An exothermic reaction occurs. Heat the warm reaction mixture with a small flame so that it reaches 75° in about 10 minutes and then remove the flame. The temperature will continue to rise to 80-85° during 5-10 minutes and then falls at this point heat the mixture to boiling and reflux for 20 minutes. Cool the mixture in ice to 0-5°, acidify with 107-5 ml. of concentrated hydrochloric acid. Extract the acid with five 50 ml. portions of ether. Dry the combined ethereal extracts with 10 g. of anhydrous sodium or magnesium sulphate, remove the ether on a water bath, and distil the residue under reduced pressure using a Claiseii flask with fractionating side arm. Collect the dichloroacetic acid at 105-107°/26 mm. The yield is 85 g. 

P-Phenylethylamine is conveniently prepared by the hydrogenation under pressure of benzyl cyanide with Raney nickel catalyst (see Section VI,5) in the presence of either a saturated solution of dry ammonia in anhydrous methyl alcohol or of liquid ammonia the latter are added to suppress the formation of the secondary amine, di- P phenylethylamine ... 

Preparation of benzyl cyanide. Place 100 g. of powdered, technical sodium cyanide (97-98 per cent. NaCN) (CAUTION) and 90 ml. of water in a 1 litre round-bottomed flask provided with a reflux condenser. Warm on a water bath until the sodium cyanide dissolves. Add, by means of a separatory funnel fitted into the top of the condenser with a grooved cork, a solution of 200 g. (181-5 ml.) of benzyl chloride (Section IV.22) in 200 g. of rectified spirit during 30-45 minutes. Heat the mixture in a water bath for 4 hours, cool, and filter off the precipitated sodium chloride with suction wash with a little alcohol. Distil off as much as possible of the alcohol on a water bath (wrap the flask in a cloth) (Fig. II, 13, 3). Cool the residual liquid, filter if necessary, and separate the layer of crude benzyl cyanide. (Sometimes it is advantageous to extract the nitrile with ether or benzene.) Dry over a little anhydrous magnesium sulphate, and distil under diminished pressure from a Claisen flask, preferably with a fractionating side arm (Figs. II, 24, 2-5). Collect the benzyl cyanide at 102-103°/10 mm. The yield is 160 g. 

This product is sufficiently pure for the preparation of phenylacetic acid and its ethyl ester, but it contains some benzyl tso-cyanide and usually develops an appreciable colour on standing. The following procedure removes the iso-cyanide and gives a stable water-white compound. Shake the once-distilled benzyl cyanide vigorously for 5 minutes with an equal volume of warm (60°) 60 per cent, sulphuric acid (prepared by adding 55 ml. of concentrated sulphuric acid to 100 ml. of water). Separate the benzyl cyanide, wash it with an equal volume of sa+urated sodium bicarbonate solution and then with an equal volume of half-saturated sodium chloride solution- Dry with anhydrous magnesium sulphate and distil under reduced pressure. The loss in washing is very small (compare n-Butyl Cyanide, Section 111,113, in which concentrated hydrochloric acid is employed). 

Indoleacetic acid In a 1-litre flask, fitted with a reflux condenser, place a solution of 35 2 g. of sodium cyanide in 70 ml. of water, then add 25 g. of gramine and 280 ml. of 95 per cent, ethanol. Reflux the mixture (steam bath) for 80 hours. Dilute the cooled reaction mixture with 35 ml. of water, shake with a little activated charcoal (e.g., Norit), filter and concentrate to about 350 ml. imder reduced pressure (water pump) in order to remove most of the alcohol. Cool to about 5°, filter off the solid and wash it with a little cold water keep the filtrate (A). Recrystallise the solid from alcohol-ether to give 5-0 g. of 3-indoleacetamide, m.p. 150-151°. 

Minor and potential new uses include flue-gas desulfurization (44,45), silver-cleaning formulations (46), thermal-energy storage (47), cyanide antidote (48), cement additive (49), aluminum-etching solutions (50), removal of nitrogen dioxide from flue gas (51), concrete-set accelerator (52), stabilizer for acrylamide polymers (53), extreme pressure additives for lubricants (54), multiple-use heating pads (55), in soap and shampoo compositions (56), and as a flame retardant in polycarbonate compositions (57). Moreover, precious metals can be recovered from difficult ores using thiosulfates (58). Use of thiosulfates avoids the environmentally hazardous cyanides. 

---