Arsenious

Arsenic(III) (arsenious) acid, H3ASO3.—When arsenic(III) oxide is dissolved in water the corresponding acid is formed ... 

Required Arsenious oxide, 27 g. aniline, 20 ml. (20 g.) anhydrous sodium carbonate, 55 g. crystalline copper sulphate,... 

Add in turn 55 g. of anhydrous sodium carbonate, 27 g. of powdered arsenious oxide and i g. of hydrated copper sulphate to 175 ml. of water in a 2 litre beaker, and heat the stirred mixture until an almost clear solution is obtained then immerse the stirred solution in ice-water, and cool it to 5°. 

In a 1-litre three-necked flask, mounted on a steam bath and provided respectively with a separatory funnel, mechanical stirrer and double surface condenser, place 165 g. of bromoform (96 per cent.). Add 10 ml. of a solution of sodium arsenite made by dissolving 77 g. of A.R. arsenious oxide and 148 g. of A.R. sodium hydroxide in 475 ml. of water. Warm the mixture gently to start the reaction, and introduce the remainder of the sodium arsenite solution during 30-45 minutes at such a rate that the mixture refluxes gently. Subsequently heat the flask on the steam bath for 3-4 hours. Steam distil the reaction mixture (Fig. 11, 41, 1) and separate the lower layer of methylene bromide (79 g.). Extract the aqueous layer with about 100 ml. of ether a further 3 g. of methylene bromide is obtained. Dry with 3-4 g. of anhydrous calcium chloride, and distil from a Claisen flask with fractionating side arm. The methylene bromide boils constantly at 96-97° and is almost colourless. 

In a 1-litre three-necked flask, fitted with a mechanical stirrer, reflux condenser and a thermometer, place 200 g. of iodoform and half of a sodium arsenite solution, prepared from 54-5 g. of A.R. arsenious oxide, 107 g. of A.R. sodium hydroxide and 520 ml. of water. Start the stirrer and heat the flask until the thermometer reads 60-65° maintain the mixture at this temperature during the whole reaction (1). Run in the remainder of the sodium arsenite solution during the course of 15 minutes, and keep the reaction mixture at 60-65° for 1 hour in order to complete the reaction. AUow to cool to about 40-45° (2) and filter with suction from the small amount of solid impurities. Separate the lower layer from the filtrate, dry it with anhydrous calcium chloride, and distil the crude methylene iodide (131 g. this crude product is satisfactory for most purposes) under diminished pressure. Practically all passes over as a light straw-coloured (sometimes brown) liquid at 80°/25 mm. it melts at 6°. Some of the colour may be removed by shaking with silver powder. The small dark residue in the flask solidifies on cooling. 

Concurrently with the preparation of the phenyldiazonium chloride solution, prepare a cold suspension of sodium arsenite. Place 250 ml. of water in a 3-htre round-bottomed flask equipped with a mechanical stirrer. Heat the water to boding, add 125 g. of anhydrous sodium carbonate, and, as soon as the carbonate has dissolved, introduce 62 5 g. of pure arsenious oxide and 3 g. of crystallised copper sulphate with stirring. When all the solids have dissolved, cool the solution with stirring under a stream of tap water until the temperature has fallen to 15°. 

Alternatively, prepare the sodium meta-arsenite solution by dissolving 39 6 g. A.R. arsenious oxide and 32 g. of A.R. sodium hydroxide in 600 ml. of water. 

It is usually preferable to oxidise the compound directly as follows. Intimately mix 0 02-0 05 g. of the eompound with 3 g. of sodium peroxide and 2 g. of anhydrous sodium carbonate in a niekel erucible. Heat the crueible and its eontents with a small flame, gently at first, afterwards more strongly until the eontents are fused, and eontinue heating for a further 10 minutes. Allow to stand, extract the contents of the crucible with water, and filter. Add exeess of eoneentrated nitrie acid to the filtrate and test with ammonium molybdate reagent as above. A yellow preeipitate indicates the presenee of phosphorus. It must be borne in mind that the above treatment 1 eonvert any arsenie present into arsenate. 

Arsenic. The presence of arsenie in an organie eompound is generally revealed by the formation of a dull grey mirror of arsenic on the walls of the test-tube when the eompound is fused with sodium in the Lassaigne teat. Usually sufficient arsenic is found in the fusion solution to give a yellow precipitate of arsenic trisulphide when the solution is acidified with hydrochloric acid and treated with hydrogen sulphide. 

Cm ORINE OXYGEN ACIDS AND SALTS - Cm ORIC ACID AND Cm ORATES] (Vol 5) Arsenious acid anhydride... 

Arsenious oxide, trivalent antimony (73), sulfurous acid (74), hydrogen sulfide (75), stannous ion, and thiocianate (76) have been recommended for the titration of iodine. However, none of these appears to have a greater sensitivity for the deterrnination of minute quantities of iodine than thiosulfate. Organic compounds such as formaldehyde (77), chloral hydrate (78), aldoses (79), acetone (70,80), and hydroquinone have also been suggested for this purpose. 

Arsenic Peroxides. Arsenic peroxides have not been isolated however, elemental arsenic, and a great variety of arsenic compounds, have been found to be effective catalysts ia the epoxidation of olefins by aqueous hydrogen peroxide. Transient peroxoarsenic compounds are beheved to be iavolved ia these systems. Compounds that act as effective epoxidation catalysts iaclude arsenic trioxide, arsenic pentoxide, arsenious acid, arsenic acid, arsenic trichloride, arsenic oxychloride, triphenyl arsiae, phenylarsonic acid, and the arsenates of sodium, ammonium, and bismuth (56). To avoid having to dispose of the toxic residues of these reactions, the arsenic can be immobi1i2ed on a polystyrene resia (57). 

Elemental phosphoms from the electrothermal process is a distilled product of high purity and yields phosphoric acid pure enough for most industrial uses without any further treatment. The main impurity is ca 20—100 ppm arsenic present in the phosphoms as the element and in the phosphoric acid as arsenious acid. To remove the arsenic, the phosphoric acid destined for food, pharmaceutical, and some industrial-grade appHcations is treated with excess hydrogen sulfide, filtered, and blown with air to strip out excess H2S. This treatment generally reduces the arsenic content of the phosphoric acid to less than 0.5 ppm. The small amount of filter cake is disposed of in approved chemical landfills. 

The demand for metallic arsenic is limited and thus arsenic is usually marketed in the form of the trioxide, referred to as white arsenic, arsenious oxide, arsenious acid anhydride, and also by the generally accepted misnomer arsenic. 

The toxicity of arsenic ranges from very low to extremely high depending on the chemical state. Metallic arsenic and arsenious sulfide [1303-33-9] AS2S2, have low toxicity. Arsine is extremely toxic. The toxicity of other organic and inorganic arsenic compounds varies (28). 

Chlorate Analysis. Chlorate ion concentration is determined by reaction with a reducing agent. Ferrous sulfate is preferred for quaHty control (111), but other reagents, such as arsenious acid, stannous chloride, and potassium iodide, have also been used (112). When ferrous sulfate is used, a measured excess of the reagent is added to a strong hydrochloric acid solution of the chlorate for reduction, after which the excess ferrous sulfate is titrated with an oxidant, usually potassium permanganate or potassium dichromate. 

Heteroeyeles eontaining the less-common heteroatoms sueh as phosphorus, arsenie, antimony are dealt with in Volume 1. 

Nitrophenylarsonic acid has been prepared by heating p-nitrobenzenediazonium chloride with arsenious acid in hydrochloric acid, by the action of -nitrobenzenediazonium chloride on sodium arsenite, by the action of sodium arsenite on sodium -nitrobenzeneisodiazo oxide, by the diazotization of -nitro-aniline in acetic acid in the presence of arsenic chloride and cuprous chloride, and by the reaction of -nitrobenzenediazonium borofluoride with sodium arsenite in the presence of cuprous chloride. ... 

Arsenic III oxide (arsenic trioxide, arsenious oxide) [1327-53-3] M 197.8, three forms m 200°(amorphous glass), m 275°(sealed tube, octahedral, common form, sublimes > 125° without fusion but melts under pressure), m 312°, pKj 9.27, pK 13.54, pK 13.99 (for H3ASO3). Crystd in octahedral form from H2O or from dil HCl (1 2), washed, dried and sublimed (193°/760mm). Analytical reagent grade material is suitable for use as an analytical standard after it has been dried by heating at 105° for l-2h or has been left in a desiccator for several hours over cone H2SO4. POISONOUS (particulary the vapour, handle in a ventilated fume cupboard). 

Bromine is a dark red volatile liquid with a pungent odour. The vapour attaeks the eyes and mueous memhranes. It eomhines spontaneously and with deflagration with phosphorus, arsenie and potassium and with many other elements when warmed. It hleaehes litmus and turns stareh paper orange/yellow. 

Heat a very small quantity of potassium acetate with an equal bulk of arsenious oxide. The disagreeable and poisonous vapour of cacodyl oxide is evolved. 

Mining Waste Estimated 10-20 eaneers aiuiually, largely due to arsenie. Remote loeations and small population exposure reduee overall risk though individual risk may be high. 

The solubility of AS2O3 in water, and the species present in solution, depend markedly on pH. In pure water at 25°C the solubility is 2.16 g per lOOg this diminishes in dilute HCl to a minimum of 1.56g per lOOg at about 3 m HCl and then increases, presumably due to the formation of chloro-complexes. In neutral or acid solutions the main species is probably pyramidal As(OH)3, arsenious acid , though this compound has never been isolated either from solution or otherwise (cf. carbonic acid, p. 310). The solubility is much greater in basic solutions and spectroscopic evidence points to... 

Arsenil aure, /, arsenic acid. — unvollkom-mene —, /. arsenious acid,... 

Chlor-. of or combined with chlorine, chloro (as Chlorbenzoeadure, chlorobenzoic acid), chloride of (as Chlorzink, zinc chloride), chlorahnlich, a. like chlorine, chlorinous. Chlor-alaun, m. chloralum, -alkalien, n.pl. alkali-metal chlorides, -allyl, n, allyl chloride, -aluminium, n. aluminum chloride, -ammon, m., -ammonium, n. ammonium chloride, -amyl, n, amyl chloride, -antimon, n, antimony chloride, -arsenlk, n. chloride of arsenic, -arsenikldsung, /, (Pkarm.) solution of arsenious add, hydrochloric solution of arsenic, -arsinkampfstoff, m. chlorodi-phenylarsine, adamsite, chlorartig, a. like chlorine, chlorinous,... 

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