Arsine Liquid

Phenyldichloro-arsine. Liquid Data not available Data not available Data not available Data not available... 

Methylarsine, trifluoromethylarsine, and bis(trifluoromethyl)arsine [371-74-4] C2HAsF, are gases at room temperature all other primary and secondary arsines are liquids or solids. These compounds are extremely sensitive to oxygen, and ia some cases are spontaneously inflammable ia air (45). They readily undergo addition reactions with alkenes (51), alkynes (52), aldehydes (qv) (53), ketones (qv) (54), isocyanates (55), and a2o compounds (56). They also react with diborane (43) and a variety of other Lewis acids. Alkyl haUdes react with primary and secondary arsiaes to yield quaternary arsenic compounds (57). 

Osmium(II) forms no hexaaquo complex and [Os(NH3)g] +, which may possibly be present in potassium/liquid NH3 solutions, is also unstable. [Os(NH3)5N2] and other dinitrogen complexes are known but only ligands with good 7r-acceptor properties, such as CN, bipy, phen, phosphines and arsines, really stabilize Os , and these form complexes similar to their Ru analogues. 

Substances with high vapor pressure evaporate rapidly. Those with low vapor pressure evaporate slowly. The impact of vapor pressure on the rate of evaporation makes vapor pressure a very important property in considering the tactical use and duration of effectiveness of chemical agents. A potential chemical agent is valuable for employment when it has a reasonable vapor pressure. One with exceptionally high vapor pressure is of limited use. It vaporizes and dissipates too quickly. Examples are arsine and carbon monoxide. On the other hand, mechanical or thermal means may effectively aerosolize and disseminate solid and liquid agents of very low vapor pressure. Vapor pressure and volatility are related. Translated into volatility, vapor pressure is most understandable and useful. 

Tris(dimethylamino)arsine (d2o 1.1248 nd 1.4848)3 is a colorless liquid which is readily hydrolyzed to form arsenic (III) oxide and dimethylamine when brought into contact with water. The compound is soluble in ethers and hydrocarbons. The product is at least 99.5% pure (with respect to hydrogen-containing impurities) as evidenced by the single sharp peak at —2.533 p.p.m. (relative to tetramethylsilane) seen in the proton nuclear magnetic resonance spectrum of the neat liquid. 

The simplest analytical method is direct measurement of arsenic in volatile methylated arsenicals by atomic absorption [ 11 ]. A slightly more complicated system, but one that permits differentiation of the various forms of arsenic, uses reduction of the arsenic compounds to their respective arsines by treatment with sodium borohydride. The arsines are collected in a cold trap (liquid nitrogen), then vaporised separately by slow warming, and the arsenic is measured by monitoring the intensity of an arsenic spectral line, as produced by a direct current electrical discharge [1,12,13]. Essentially the same method was proposed by Talmi and Bostick [10] except that they collected the arsines in cold toluene (-5 °C), separated them on a gas chromatography column, and used a mass spectrometer as the detector. Their method had a sensitivity of 0.25 xg/l for water samples. 

Caution Arsine is a flammable and highly toxic gas that does not provide adequate warning of hazardous levels. Inhalation is the major route of arsine exposure, although there is little information about absorption through the skin or toxic effects on the skin or eyes. Contact with liquid arsine may result in frostbite. 

Dot Marking Toxic liquids, n.o.s. Dichloro-(2-chlorovinyl)arsine UN 2810 Dot Placard Poison... 

The equilibria between the liquid and vapour of binary mixtures of phosphine and arsine were investigated by Devyatykh et at. 

Birchall and Jolly used H NMR data for phosphine, arsine, and germane and some of their alkyl derivatives to determine the relative acidities in liquid ammonia Spin-lattice relaxation time (Ti) measurements for the H nuclei in PH3 are.reported by Armstrong and Courtney o) ... 

Arsine is produced by the reaction of arsenic trichloride, arsenic trioxide or any inorganic arsenic compound with zinc and sulfuric acid. It is also made by treating a solution of sodium arsenide or potassium arsenide in liquid ammonia with ammonium bromide ... 

Calcium carbide desulfurization slag has a distinctive odor. Since pure acetylene is odorless, the odor must be produced by other trace constituents in the off-gases. A calcium carbide desulfurization slag sample from one ductile foundry was treated with water at a 1 1 solid-to-liquid ratio, and the gas was collected in a Tedlar bag for analysis by GC-MS. Several trace gases were identified, including arsine, divinyl sulfide (CHj-CH S, ethanethiol (ethyl mercaptan), methane, phosphine, and carbon monoxide. 

Robinson and his co-workers 6 prepared pure arsine in pure hydrogen by slowly dropping (during 2 hours) a solution of arsenious oxide (20 g.) in freshly boiled hydrochloric acid (250 c.e. acid 50 c.c. water) on pure magnesium turnings (50 g.) in a 750-c.c. round-bottomed flask cooled in water. The reaction products passed through aqueous potash into successive tubes containing potash pellets, fused calcium chloride and phosphorus pentoxide, and thence to a vessel immersed in liquid air. The pure arsine was finally obtained by careful fractionation. 

Durrant, Pearson and Robinson, J. Ohem. Soc., 1934, p. 730. Por the preparation of arsine by the action of ammonium bromide on sodium arsenides in liquid ammonia, see Johnson and Pechukas, J. Amer. Ohem. Soc., 1937, 59, 2065. 

Olszewsky 2 found the boiling point to be - 54-8° C., and by cooling the liquid to -118-9° C. he obtained a white crystalline mass which melted at -113-5° C.8 The solid arsine is quite stable in air at -170° C.4... 

The Ramsay-Shields and Trouton constants indicate that arsine is a normal liquid and differs from phosphine and to a greater extent from ammonia in not being associated. 

The dielectric constants and molecular rotations of solid and liquid arsine have been determined 6 from the temperature of liquid hydrogen to the boiling point over the frequency range 0-5 to 50 kilocycles. The molecule rotates freely down to 80-1° Abs. 

The gas reacts vigorously with the halogens. When mixed with chlorine a flame is produced and arsenic and hydrogen chloride are formed 12 with excess of chlorine arsenic trichloride is produced, and in the presence of water arsenious and arsenic acids result. Bromine13 reacts similarly, the oxidation in the presence of water to arsenic acid being quantitative.14 With liquid chlorine, arsine reacts at temperatures as low as -140° C., forming reddish products, apparently containing... 

When arsine is passed over a heated metal, such as the alkali and alkaline earth metals, zinc or tin, the decomposition of the gas is accelerated and the arsenide of the metal is formed. If platinum is used, the removal of arsenic from the gas is complete.3 The action of sodium or potassium on arsine in liquid ammonia yields 4 the dihydrogen arsenide (MHgAs). Heated alkali hydroxides in the solid form quickly decompose the gas, forming arsenites, and at higher temperatures arsenates and arsenides of the metals.5 The aqueous and alcoholic solutions have no appreciable action.6 When the gas is passed over heated calcium oxide the amount of decomposition is not more than that due to the action of heat alone. Heated barium oxide, however, is converted into a dark brown mixture of barium arsenite and arsenate, hydrogen being liberated.7 The gas is absorbed by soda-lime.8... 

The action of arsine on silver and mercury salts has attracted much attention owing to the important application to analytical methods for arsenic (p. 319). The action of arsine on a dilute aqueous solution of silver nitrate has long been known to yield metallic silver, arsenious acid and nitric acid.9 With more concentrated solutions the introduction of a few bubbles of arsine produces a deep lemon-yellow coloration, the liquid also acquiring an acid reaction. The coloration disappears after one or two days, silver is precipitated and the colourless solution contains arsenious and arsenic acids.10 If a rapid stream of arsine be passed into a concentrated solution of silver nitrate at 0° C. the whole liquid solidifies to a yellow crystalline mass which rapidly blackens with separation of silver. Lassaigne represented the reaction with the dilute solution by the equation... 

The tetrakis-phosphino and -arsino complexes reported in Table 3 have very different thermal and air stabilities. In general, complexes with alkyl-phosphines and -arsines are air-unstable or pyrophoric. The tetrakis(arylphosphino) complexes (but not the bis or tris derivatives) are moderately air- and heat-stable, and the tetrakis phosphites may be handled in the atmosphere. Ni(PF3)4 is a stable liquid compound, whereas Ni(PCl3)4 and Ni(PBr3)4 are solids and stable only in dry air. 

A fairly large number of mixed carbonyl phosphine and arsine complexes have been reported so far. They are generally prepared by displacement of CO from Ni(CO)4. Owing to the high stability of Ni(CO)4, when it is reacted with phosphines and arsines at room temperature and atmospheric pressure, only a partial displacement of CO usually occurs. Most of the mixed phosphine (or arsine) carbonyl compounds have the general formula [Ni(CO) (PR3)4 ] (n = 3, 2) and [Ni(CO)2(L—L)] (L—L is a diphosphine or diarsine). These complexes are colourless or yellow-orange solids or liquids. Many of them are thermally stable but decompose in air. The most relevant mixed carbonyl complexes with common phosphines are reported in Table 4. 

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