Phosphine toxicity

Suggested Alternatives for Differential Diagnosis Acute respiratory distress syndrome, congestive heart failure, pulmonary edema, AIDS, pneumonia, cardiogenic shock, septic shock, phosgene toxicity, phosphine toxicity, salicylate toxicity with pulmonary edema, influenza, plague, tularemia, and anthrax. 

Brautbar N and Howard J (2002) Phosphine toxicity Report of two cases and review of the literature. Toxicology and Industrial Health 18 71-75. 

Gas odor not unpleasant when pure, hut disagreeable when impure (due to phosphine). Toxic when inhaled, mp —8]° (snbl). At 0° liquifies at 21.5 atm helow 37 (crit temp) liquifies at 68 atm. One liter at O and 760 mm weighs 1.165 g d gas (air = I) 0.90. Burns brilliantly in air with very sooty flame. Heat of combustion 313 cal. Not explosive at ordinary atmospheric pressure, but at 2 atms or more it is explosive by spark Or decomposition. Mixture with air containing more than 3% or less than 65% gas is explosive, max being 1 vol gas and 12.5 vol air. Forms insoluble explosive compounds with copper and silver hence copper Or brass containers must be avoided. One vol dissolves in I vol water, in 6 vols glacial acetic acid or alcohol soluble in ether, benzene. Acetone dissolves 25 vols acetylene at 15" and 760 mm but 300 vols at 12 atm. LC in rats 900,000 ppm, Riggs, Proc. Soc. Exp. Biol. Med 22, 269 (1925). 

The reaction with sodium sulfite or bisulfite (5,11) to yield sodium-P-sulfopropionamide [19298-89-6] (C3H7N04S-Na) is very useful since it can be used as a scavenger for acrylamide monomer. The reaction proceeds very rapidly even at room temperature, and the product has low toxicity. Reactions with phosphines and phosphine oxides have been studied (12), and the products are potentially useful because of thek fire retardant properties. Reactions with sulfide and dithiocarbamates proceed readily but have no appHcations (5). However, the reaction with mercaptide ions has been used for analytical purposes (13)). Water reacts with the amide group (5) to form hydrolysis products, and other hydroxy compounds, such as alcohols and phenols, react readily to form ether compounds. Primary aUphatic alcohols are the most reactive and the reactions are compHcated by partial hydrolysis of the amide groups by any water present. 

The extremely toxic and flammable gas phosphine is safely and conveniently generated for the fumigation of grain in sacks or bins from 3-g tablets containing aluminum phosphide and ammonium carbamate which produce 1 g of phosphine in the presence of moisture. 

Although phosphine [7803-51-2] was discovered over 200 years ago ia 1783 by the French chemist Gingembre, derivatives of this toxic and pyrophoric gas were not manufactured on an industrial scale until the mid- to late 1970s. Commercial production was only possible after the development of practical, economic processes for phosphine manufacture which were patented in 1961 (1) and 1962 (2). This article describes both of these processes briefly but more focus is given to the preparation of a number of novel phosphine derivatives used in a wide variety of important commercial appHcations, for example, as flame retardants (qv), flotation collectors, biocides, solvent extraction reagents, phase-transfer catalysts, and uv photoinitiators. 

Toxicity. Lethality is the primary ha2ard of phosphine exposure. Phosphine may be fatal if inhaled, swallowed, or absorbed through skin. AH phosphine-related effects seen at sublethal inhalation exposure concentrations are relatively small and completely reversible. The symptoms of sublethal phosphine inhalation exposure include headache, weakness, fatigue, di22iness, and tightness of the chest. Convulsions may be observed prior to death in response to high levels of phosphine inhalation. Some data are given in Table 2. 

This route to acid chlorides is often preferred over the alternative use of phosphoms trichloride because the by-products, SO2 and HCl, are gaseous and easily removed. On the other hand, the use of phosphoms trichloride yields phosphorous acid as a by-product. This can decompose exothermically with evolution of toxic and flammable phosphine if overheated, however, phosphorous acid is saleable as a valuable by-product on a commercial scale. Ma.nufa.cture. Thionyl chloride may be made by any of the following reactions ... 

Phosphorus exists as white and red phosphorus. The former allotrope may be preserved in the dark at low temperatures but otherwise reverts to the more stable red form. The white form is a waxy, translucent, crystalline, highly-toxic solid subliming at room temperature and inflaming in air at 35°C, so it is handled under water. The red form is a reddish violet crystalline solid which vaporizes if heated at atmospheric pressure and condenses to give white phosphorus. The red form ignites in air at 260°C. Both are insoluble in water, and white phosphorus can be stored beneath it. Phosphorus forms a host of compounds such as phosphine, tri- and penta-halides, tri-, tetra- and penta-oxides, oxyacids including hypophosphorous, orthophosphorous and orthophosphoric acids. 

Phosphides are binary compounds containing anionic phosphorus (P ). Heavy metal, alkali, and alkaline earth metal phosphides exist but few of them are commercially important. Phosphides hydrolyze to the flammable and toxic gas phosphine (PH3). The hydrolysis reaction of aluminum phosphide is given below ... 

Chemical Reactivity - Reactivity with Water Reacts vigorously with water, generating phosphine, which is a poisonous and spontaneously flammable gas Reactivity with Common Materials Can react with surface moisture to generate phosphine, which is toxic and spontaneously flammable Stability During Transport Stable if kept dry Neutralizing Agents for Acids and Caustics Not pertinent Polymerization Not pertinent Inhibitor of Polymerization Not pertinent. 

Phosphine is highly toxic by inhalation and is a strong irritant. Tolerance 0.3ppm in air (Refs 10 11)... 

A major disadvantage of CVD (as opposed to PVD) is that many precursors are toxic and in some cases lethal even at low concentration (for instance nickel carbonyl, diborane, arsine, and phosphine). Some are also pyrophoric, such as silane, some alkyls, arsine, and phosphine. Very often the reaction is not complete and some of the precursor materials may reach the exhaust unreacted. In addition, many of the by-products of the reaction are also toxic and corrosive. This means that all these effluents must be eliminated or neutralized before they are released to the... 

Arsine (ASH3) and phosphine (PH3) are extremely toxic, so less hazardous substitutes such as tertiary butyl arsine, C4H1 j As, and tertiary butyl phosphine, C4H11P, are being considered. 

Phosphine is a coioriess, highiy toxic gas with bond angles of 93.6°. Describe the bonding in PH3. ... 

White phosphorus has an autoignition temperature only shghtly above ambient, dispersed it will soon heat itself to that by the slow oxidation responsible for its glow. Red is not spontaneously combustible, however if it does catch fire white will be produced, so that the fire, once extinguished, may spontaneously re-ignite. Both can produce phosphine, among other products, by slow reaction with water. Sealed containers of damp phosphorus (white is often stored under water) may pressurise with highly toxic, pyrophoric, gas mixtures [1]. 

Although no extensive data are available for evaluating the toxicity of phosphine selenides, these compounds are similar to organophosphates and -thiophosphates, many of which are insecticides and related to the so-called nerve gases. 3 A high toxicity for mammals has been noted in (RO)2P(Se)X compounds 3 Consequently, the phosphine selenides should be handled carefully. 

The hydrazine analogs P2H4, As2H4, and Sb2H4 are toxic and unstable, as indicated by the fact that P2H4 is spontaneously flammable in air, and phosphine burns readily. 

The cytotoxicity of Au(I) complexes is markedly dependent on the ligands. A large number of Au(I) phosphine complexes are toxic to cells in the micromolar concentration range. For example, some linear Au(I) phosphine complexes, including the antiarthritic complex aura-nofin (see Section VII), are potently cytotoxic toward cancer cells in culture (189). 

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