Phosphorus bottles

Phosphorus Bottles. Put 12 grains phosphorus with k ounce olive oil in a 1 ounce phial and place it, loosely corked, in a basin or hot water as soon as the phosphorus is melted, remove the phial, cork it securely, and agitate it until nearly cold. On being uncorked it emits sufiScient light in the dark to see the time by a watch, and will retain is property for some years if not too firequeiitly employed. 

The invention of phosphorus matches was gradual. Peyla, in Turin in 1779, used wax tapers tipped with phosphorus and sulphur and sealed up in glass tubes on breaking the tube and drawing out the taper elle s allumait d elle meme . These were made by Count di Challant and called Turin tapers . Lichtenberg (1784) used a mixture of phosphorus, sulphur, and a little oil of cloves or turpentine in a stoppered bottle a roll of paper or a slip of wood was dipped into it, and inflamed when taken out. Derosne (1816) used a tube coated inside with phosphorus, rubbed this with the sulphured head of a match, and then rubbed the head on cork or leather. These phosphorus bottles or briquets phosphoriques were sold and used in London and Paris in the 1820 s. Matches with heads of sulphur and phosphorus were used about 1825 by J. T. Cooper in London. 

Red phosphorus. Commercial red phosphorus is usually contaminated with small quantities of acidic products. It should be boiled for 15 minutes with distilled water, allowed to settle, decanted through a Buchner funnel, and then washed two or three times with boiling water by decantation. Finally, the phosphorus is completely transferred to the Buchner funnel and washed with hot water untU the washings are neutral. It is dried at 100°, and kept in a desiccator or in a tightly stoppered bottle. 

Treat the distillate with 2 drops of glacial acetic acid (to destroy the phosphorus esters present) and redistil using the same apparatus as before except that the separatory funnel is replaced by a thermometer. Collect the liquid which passes over at 50-56°. Transfer the acetyl chloride to a weighed glass-stoppered bottle (since cork and rubber stoppers are attacked) and determine the weight. The yield is 22 g. 

Liquid aliphatic halides are obtained alcohol-free by distillation from phosphorus pentoxide. They are stored in dark bottles to prevent oxidation and, in some cases, the formation of phosgene. 

A. Triphenylmethylphosphonium bromide. A solution of 55 g. (0.21 mole) of triphenylphosphine dissolved in 45 ml. of dry benzene is placed in a pressure bottle, the bottle is cooled in an ice-salt mixture, and 28 g. (0.29 mole) of previously condensed methyl bromide is added (Note 1). The bottle is sealed, allowed to stand at room temperature for 2 days, and is reopened. The white solid is collected by means of suction filtration with the aid of about 500 ml. of hot benzene and is dried in a vacuum oven at 100° over phosphorus pentoxide. The yield is 74 g. (99%), m.p. 232-233°. 

The phosphorus pentoxide is introduced into a small distilling flask (200 c.c.) attached to a short condenser. As the pentoxide absorbs moisture rapidly and becomes sticky, it is convenient to push the neck of the distilling flask through a cork which fits the phosphorus pentoxide bottle, and then to shake in the oxide until the required weight is obtained. The powdered acetamide is immediately introduced and shaken up, and the mixture distilled over a small flame, which is constantly moved about. Add to the distillate about half its volume of water, and then solid potassium carbonate, until no more dissolves. The upper layer of liquid, which consists of methyl cyanide, is separated and distilled over a little fresh phosphorus pentoxide with thermometer. Yield, about 5 grams. 

Commercial acetonitrile is treated with solid sodium carbonate until no more carbon dioxide is evolved. The nitrile is then distilled over phosphorus pentoxide and stored in tightly stoppered bottles. Before use, the nitrile is redistilled over phosphorus pentoxide. 

The apparatus shown in Fig. 16 is set up in the fume hood. The equipment is flushed with dry nitrogen, then a 200-ml. portion (314.8 g., 2.29 mols) of phosphorus trichloride is placed in the 2-1. reaction flask. The flask is partially immersed in the Dry Ice-isopropyl alcohol bath the clamp to the alkylamine container is opened and a stream of dry nitrogen is passed through the system at a rate of about 30 cc./minute measured at S.T.P. The nitrogen stream sweeps the anhydrous amine (200 g.) from the bottle into the reactor. The amine usually condenses on one of the two cold fingers of the reactor and drips into the chilled stirred phosphorus trichloride solution. Finely divided dimethylammonium chloride precipitates immediately. 

Environmental water samples to be analyzed for phosphate are not stored in plastic bottles unless kept frozen, because phosphates can be absorbed onto the walls of plastic bottles. Mercuric chloride, used as a preservative and acid (such as the nitric acid suggested for metals above), should not be used unless total phosphorus is determined. All containers used for water samples to be used for phosphate analysis should be acid rinsed, and commercial detergents containing phosphates should not be used to clean sample containers or laboratory glassware. 

Phosphoryl chloride from Fluka Chemical Corporation or Aldrich Chemical Company, Inc., and methylene chloride (purum) from Merck Company, Inc., were used. Unless the contents of a freshly opened bottle were used, methylene chloride was distilled from phosphorus pentoxide (20 g/L) before use. The amine (Fluka or Aldrich) was distilled from and stored over potassium hydroxide. The best yields were obtained with once-recovered amine. 

Procedure (extraction). Transfer 2.5 g air-dry soil, 2 mm mesh size, into a 250 ml polypropylene screw-cap centrifuge bottle/tube and add 100 ml acetic acid - 8-hydroxyquinoline reagent. Cap the tube and shake overnight (17 h) on a reciprocating shaker, at approximately 275 strokes of 25 mm length per minute at a constant temperature (20°C). Centrifuge for 15 min at 2800 rpm and remove an aliquot for the determination of acid extractable inorganic phosphorus (a). 

Phosphorus(V) oxide is very hygroscopic and the bottle must be closed except when an addition is made. The reactor is cooled with ice water so that the reaction temperature is maintained at 5-10°. Methanol (125 mL)is added drop-wise to the stirred solution to precipitate the crude ammonium tetrametaphos-phate, which is collected by suction filtration, washed with methanol, and dried in vacuum over anhydrous CaS04. The product weighs 33 g and contains about 65% of its phosphorus as tetrametaphosphate. The remainder is a mixture of ortho-, trimeta- and short-chain phosphates. Any lumps are crushed and the crude ammonium tetrametaphosphate is spread in a no. 1 porcelain evaporating dish and heated for 2 hours at 240° in a slow stream,of anhydrous ammonia (about 100 mL/min or 3-5 g/hr). Care is taken to avoid absorption of moisture before or during heating, as this adversely affects the formation of the product. 

Phosphorus-Ignited Molotov Cocktail used a bottle 9% inches long 2-1/8 inches diam, which contd 9.5 oz of 15% soln of polymethylmethacrylate in benzene and sealed with a crown type cap. An adjustable rubber harness held a flat circular glass igniter capsule, contg 1 oz... 

Experience with many preparations of this acid chloride has shown that it is desirable to use, during the distillation under reduced pressure, a safety water-bottle between the receiving flask and the manometer. This avoids the passage of vapors of phosphorus oxychloride or acid chloride into the pump. 

Explosions, Unexpected. POCl3 Explodes in Lab, A severe and unexplained expln of a bottle contg recovered phosphorus oxychloride occurred at the Uni of Arizona chem lab. Dr L. Plummer was prepg the diacid chloride of ferrocene-l,l-dicarboxyIic acid, using a mixt of PC15 phosphorus oxychloride. He had just distilled (under reduced press) the oxychloride from the reaction mixt. The recovered phosphorus oxychloride was poured into a 500-ml brown bottle contg some of the compd recovered from earlier, similar reactions. Some of the recovered compd had been standing for ca 3 months... 

Reaction of Chlorine with Non-Metals. 1. Put several grains of red phosphorus into a spoon for burning, ignite it, and introduce it into a bottle with chlorine. What occurs Write the equation of the reaction. 

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