Phosphine calcium

Phosphorus Silane Phosphine Calcium carbide Uranium carbide... 

Pyrophoric carbonyl metals Carbonylithium Phosphine Calcium carbide Uranium carbide mixo-T ributylborane Tributylphosphine ... 

Additional phosphonic acid is derived from by-product streams. In the manufacture of acid chlorides from carboxyUc acids and PCl, phosphonic acid or pyrophosphonic acid is produced, frequentiy with copious quantities of yellow polymeric LOOP. Such mixtures slowly evolve phosphine, particularly on heating, and formerly were a disposal problem. However, purification of this cmde mixture affords commercial phosphonic acid. By-product acid is also derived from the precipitate of calcium salts in the manufacture of phosphinic acid. As a consequence of the treatments of the salt with sulfuric acid, carbonate is Hberated as CO2 and phosphonic acid goes into solution. 

Commercially, phosphinic acid and its salts are manufactured by treatment of white phosphoms with a boiling slurry of lime. The desired product, calcium phosphinite [7789-79-9], remains ia solution andiasoluble calcium phosphite [21056-98-4] is precipitated. Hydrogen and phosphine are also formed, the latter containing sufficient diphosphine to make it spontaneously flammable. The details of this compHcated reaction, however, are imperfectly understood. Under some conditions, equal amounts of phosphoms appear as phosphine and phosphite, and the volume of the hydrogen Hberated is nearly proportional to the hypophosphite that forms. 

Excess calcium hydroxide is precipitated by usiag carbon dioxide and the calcium carbonate, calcium hydroxide, and calcium phosphite are removed by filtration. The filtered solution is treated with an equivalent amount of sodium sulfate or sodium carbonate to precipitate calcium sulfate or carbonate. Sodium hypophosphite monohydrate [10039-56-2] is recovered upon concentration of the solution. Phosphinic acid is produced from the sodium salt by ion exchange (qv). The acid is sold as a 50 wt %, 30—32 wt %, or 10 wt % solution. The 30—32 wt % solution is sold as USP grade (Table 12) (63). Phosphinic acid and its salts are strong reduciag agents, especially ia alkaline solution (65). 

Phosphine is also made as a by-product of the commercial calcium hypophosphite [7789-79-9]. Calcium phosphite [21056-98-4] is also produced. 

For many years a major route to the production of vinyl chloride was the addition of hydrochloric acid to acetylene (Figure 12.5). The acetylene is usually prepared by addition of water to calcium carbide, which itself is prepared by heating together coke and lime. To remove impurities such as water, arsine and phosphine the acetylene may be compressed to 15 Ibf/in (approx. 100 kPa), passed through a scrubbing tower and chilled to -10°C to remove some of the water present and then scrubbed with concentrated sulphuric acid. 

Aero Agro Chemical hidustries Ltd., 168 AERO , calcium cyanide, 9 Aerojet Fine Chemicals, 215, 229 AEROPHINE , phosphine, 9 AEROTHENE MM , methylene chloride, 9 AFFLAIR , luster pigments, 9 Aflatoxins, 9... 

Calcium-binding proteins, 6, 564, 572, 596 intestinal, 6, 576 structure, 6, 573 Calcium carbonate calcium deposition as, 6, 597 Calcium complexes acetylacetone, 2, 372 amides, 2,164 amino acids, 3, 33 arsine oxides, 3, 9 biology, 6, 549 bipyridyl, 3, 13 crown ethers, 3, 39 dimethylphthalate, 3, 16 enzyme stabilization, 6, 549 hydrates, 3, 7 ionophores, 3, 66 malonic acid, 2, 444 peptides, 3, 33 phosphines, 3, 9 phthalocyanines, 2,863 porphyrins, 2, 820 proteins, 2, 770 pyridine oxide, 3,9 Schiff bases, 3, 29 urea, 3, 9... 

Calcium and other phosphides on contact with water liberate phosphine, which usualy ignites in air, owing to the diphosphane content. 

Dry mixtures of barium phosphinate and potassium chlorate bum rapidly with a feeble report if unconfined, but even under the slight confinement of enclosing in paper, a sharp explosion occurs. The mixture is readily initiated by sparks, impact or friction. A mixture of calcium phosphinate, potassium chlorate and quartz exploded during mixing. Mixtures of various phosphinates and chlorates have been proposed as explosives, but they are very sensitive to initiation by sparks, friction or shock. Admixture of powdered magnesium causes a brilliant flash on initiating the mixture. 

Mixtures with calcium hydride or strontium hydride may explode readily, and interaction of the molten chlorate is, of course, violent. A mixture of syrupy sodium phosphinate ( hypophosphite ) and the powdered chlorate on heating eventually explodes as powerfully as glyceryl nitrate. Calcium phosphinate mixed with the chlorate and quartz detonates (the latter producing friction to initiate the mixture). Dried mixtures of barium phosphinate and the chlorate are very sensitive and highly explosive under the lightest confinement (screwed up in paper). 

Contact of phosphorus with boiling caustic alkalies or with hot calcium hydroxide evolves phosphine, which usually ignites in air. 

Phosphine is generated when phosphide salts (i.e., Aluminum phosphide Calcium phosphide Magnesium phosphide Magnesium aluminum phosphide Potassium phosphide Sodium phosphide Stannic phosphide Strontium phosphide Zinc phosphide) come into contact with water. 

Catalytic forms of copper, mercury and silver acetylides, supported on alumina, carbon or silica and used for polymerisation of alkanes, are relatively stable [3], In contact with acetylene, silver and mercury salts will also give explosive acetylides, the mercury derivatives being complex [4], Many of the metal acetylides react violently with oxidants. Impact sensitivities of the dry copper derivatives of acetylene, buten-3-yne and l,3-hexadien-5-yne were determined as 2.4, 2.4 and 4.0 kg m, respectively. The copper derivative of a polyacetylene mixture generated by low-temperature polymerisation of acetylene detonated under 1.2 kg m impact. Sensitivities were much lower for the moist compounds [5], Explosive copper and silver derivatives give non-explosive complexes with trimethyl-, tributyl- or triphenyl-phosphine [6], Formation of silver acetylide on silver-containing solders needs higher acetylene and ammonia concentrations than for formation of copper acetylide. Acetylides are always formed on brass and copper or on silver-containing solders in an atmosphere of acetylene derived from calcium carbide (and which contains traces of phosphine). Silver acetylide is a more efficient explosion initiator than copper acetylide [7],... 

Ammonium sulfate, 4574 Barium sulfate, 0217 Calcium sulfate, 3939 Chromium(II) sulfate, 4244 Copper(II) phosphinate, 4272 Copper(II) sulfate, 4282 Iron(II) sulfate, 4399... 

Calcium phosphinate, 3931 Copper(II) phosphinate, 4272 Dipotassium phosphinate, 4431 Iron(III) phosphinate, 4394 Lead(II) phosphinate, 4531 Magnesium phosphinate, 4517 Manganese(II) phosphinate, 4519 Potassium phosphinate, 4431 Silver phosphinate, 0017 Sodium phosphinate, 4473 See other reducants... 

Aluminium, 0048 Ammonium phosphinate, 4554 Barium phosphinate, 0210 f Benzaldehyde, 2731 1,4-Benzenediol, 2333 Bis(hydrazine)tin(II) chloride, 4070 Calcium acetylide, 0585 Calcium phosphinate, 3931 Chromium(II) chloride, 4052 Chromium(II) oxide, 4241 Chromium(II) sulfate, 4244 Copper(I) bromide, 0265 Diacetatotetraaquocobalt, 1780 Diisobutylaluminium hydride, 3082 f 1,2-Dimethylhydrazine, 0955... 

Phosphine produced by the reaction of water on calcium phosphide always contains a quantity of the liquid hydrogen phosphide sufficient to make the gas spontaneously inflammable. Use of this property is made in the Holmes Light used at sea as a distress signal, and also as a marker at torpedo practice. 

For the laboratory preparation of phosphine, only a few of the many methods of formation are suitable. Among these the hydrolyses of calcium phosphide 8o- 3) jnagnesium phosphide aluminium phosphide zinc phos-... 

Together with phosphine, noticeable amounts of diphosphine and higher phosphines are formed by the hydrolysis of calcium phosphide thus, this reaction can be used for the preparation of such compounds. Quesnel reported that the formation of diphosphine can be avoided when aqueous hydrochloric acid is added drop-wise to a mixture of calcium phosphide and copper chloride (proportions by weight, CaaPj CuClj = 10 1) in boiling alcohol, for example, methanol, or in dioxane. 

When the calcium phosphide is formed by the reduction of Ca3(P04)2 with carbon, the phosphine obtained on hydrolysis usually contains up to 3% acetylene. 

Baudler and her co-workers have described in detail the preparation of larger quantities of phosphine by the hydrolysis of calcium phosphide. Higher phosphines (see page 51) formed simultaneously, are thermally decomposed to phosphorus, phosphine and hydrogen. It is noteworthy that, on storage in steel cylinders the diphosphine concentration in phosphine, originally less than 1%, increases. It is, even after several months, so small that the gas is not spontaneously inflammable in contact with air, whereas, after about one year, it is spontaneously inflammable. 

In the course of mass spectroscopic investigations of the hydrolysis products of calcium phosphide, Baudler and her co-workers could find no evidence for the existence of OPH3 as an oxidation product of PH3 In contrast, oxides of higher phosphines were observed, even when the hydrolysis of calcium phosphide was carried out with the strictest exclusion of oxygen. The... 

Calcium reacts with phosphine in an analogous manner as the alkali metals. In liquid ammonia, solid Ca(PH2)2 nNHs is formed with hydrogen evolution 128,280) -pjjg corresponding reaction with a solution of elemental strontium in liquid ammonia does not lead to a uniform product. ... 

Diphosphine is formed by the hydrolysis of calcium phosphide 22.424,425, 428,429) gjgQ jy hydrolysis of other phosphides when these contain P—P linkages. Thus, for example, it is reported that the phosphine obtained by the hydrolysis of aluminium phosphide, which has been prepared from the elements with phosphorus in excess, is spontaneously inflammable. This is caused by the diphosphine formed at the same time. When the aluminium phosphide is prepared using stoichiometric or even excess amounts of aluminium, the formation of diphosphine is not observed on hydrolysis. The diphosphine, formed in large quantities by the hydrolysis of calcium phosphide, can be separated from the phosphine and hydrogen evolved simultaneously by cool-... 

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