Sodium arsenide

Arsine is formed when any inorganic arsenic-bearing material is brought in contact with zinc and sulfuric acid. The arsenides of the electropositive metals are decomposed with the formation of arsine by water or acid. Calcium arsenide [12255-53-7] Ca2As2, treated with water gives a 14% yield of arsine. Better yields (60—90%) are obtained by decomposing a solution of sodium arsenide [12044-25-6] Na As, in Hquid ammonia with ammonium bromide (14,15). Arsine may be accidentally formed by the reaction of arsenic impurities in commercial acids stored in metal tanks, so that a test should be made for... 

Sodium arsenide can be prepared by the reaction of the elements, and it reacts with water to produce arsine according to the following equation ... 

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 ... 

Uranium Arsenide, U3As4, may be obtained i by passing hydrogen over a fused mixture of sodium uranous chloride and sodium arsenide. It is a greyish powder which readily burns in the air. Sometimes it is obtained in a pyrophoric condition. An aluminium-containing product results when the aluminothermic process, using an oxide of uranium and arsenious oxide, is employed. The purest arsenide is obtained, in the crystalline form, when a mixture of hydrogen and arsenic vapour is passed over sodium uranium chloride. It is rapidly decomposed by nitric acid. 

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. 

Sodium arsenide, Na3As, has a hexagonal crystal structure with two molecules per cell, C%v, P63cm, a0 = 8.7838, and c0 = 8.999A. There are double IP layers occupied by As and Na, followed by two adjacent T layers, each occupied by Na ... 

Sodium arsenide, Na3As, has been studied by Hugot.3... 

The few known plumbylarsines have been prepared by the reaction of the organolead halide with the sodium arsenide in liqnid anunonia (eqnation 63). ... 

Trimethylarsine, (CH3)3As.— This compound was first mentioned by Cahours and Hofmann, who stated that it was obtained by the action of potassium hydroxide on the double salt derived from arsenic trichloride and zinc dimethyl. In 1859 Cahours isolated this ansine by distilling tetramethylarsonium iodide or its double salts with potas.sium hydroxide, after having obtained only small yields by treating sodium arsenide with methyl iodide. Auger in 1904 stated that the brown polymer formed when arsenomethane is treated with a trace of hydrogen chloride yields trimethylarsine when distilled in an atmosphere of... 

Tetramethylarsonium iodide, (CH3)4AsI.— The double compound of the iodide with arsenic tri-iodide is formed when powdered arsenic and methyl iodide are heated together at 160° to 200° C. If this reaction is carried out at ordinary temperatures or on the w ater-bath, the principal products are methyldi-iodoarsine and tetramethylarsonium iodide arsenic tri-iodide and a small quantity of cacodyl iodide arc also produced. When methyl iodide is ded to sodium arsenide in an atmosphere of carbon dioxide, the mixture on distillation gives cacodyl and tetramethylarsonium iodide, Cacodyl and methyl iodide react with evolution of heat, yielding the arsonium compound and cacodyl iodide according to the equation ... 

By heating together sodium arsenide and alkyl iodides in a carbon dioxide atmosphere. This method gives only poor yields. 

Tetra-ethyldiarsine, Ethyl cacodyl, (C2H6)2As.As(C2H6)2. — Onc part of sodium arsenide is mixed with four to five times its weiglit of quartz sand and treated with ethyl iodide, the operation being conducted in a carbon dioxide atmosphere. Sufficient heat is developed to cause distillation of the ethyl iodide, which has to be replaced until the action is complete. The mass is then distilled, when a mixture of ethyl cacodyl and triethylarsine is obtained. Etliyl cacodyl has also been obtained by distillation of diethyliodoorsinc with zinc amalgam. ... 

Sodium diphenylarsenide in liquid ammonia reacts with tetra(chloromethyl)methane to form tetrakis(diphenylarsinomethyl)methane (275). The tetra-sodium arsenide (276), obtained by cleavage of (275) with sodium in liquid ammonia, on hydrolysis and oxidation by air yields the spiro-system (277) (Scheme 45) <70ZAAC(378)303>. 

The primary arsine (89) was synthesized from sodium arsenide (NaAsH2) and (3-chloro-propyl)phenyl sulfide in liquid ammonia. Without isolation, (89) was converted into the bis(3-chloropropyl)arsine (90) and subsequently into the 14-membered crystalline heterocycle (91) under the usual conditions with bis(2-thiolethyl) sulfide (Scheme 15). 

Alkyl iodides also react with metal arsenides on heating. Thus tetra-methyldiarsine, trimethylarsine, and tetramethylarsonium iodide are obtained from methyl iodide and sodium arsenide 168). Alkyl iodides and the arsenides of zinc, cadmium, or mercury give mainly compounds of the type (R4As)2Znl4 and R4AsHgl3 219, 220). These reactions are related to those described in Section II, A, 2 and probably to those in Section II, A, 5. 

Reaction of sodium arsenide with ammonium bromide in liquid ammonia... 

This substance is formed as a brown silky mass when sodium arsenide, AsNa, is decomposed 1 water. The brown powder produced by leaving the gaseous compound in contact with moist air, or by decomposing one part of arsenic and five of zinc by hydrochlotio acid, which was formerly supposed to be this substance, has been wn to be nothing but the metal in a finely divided state. 

SolvH" represents a hydron donor such as water, ammonia or an alcohol, and "Solv-Na+" its sodium salt.) Attractive features of the use of sodium to destroy chemical warfare agents are mentioned in the poster abstracts of Sokolowski and Bilger and of Bunnett (this volume). A potential problem is that adventitious acids that might somehow mix with the products will convert sodium arsenide (Na3As) to the extremely toxic arsine (ASH3). Conversion of Na3As to a much less toxic arsenic compound should immediately follow the sodium treatment. 

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