Arsenic III oxide

This is formed when arsenic burns in air (cf. phosphorus which gives P4O10). It can exist in two crystalline modifications the stable one at room temperature, which also occurs naturally as arsenolite, has an octahedral form. Solid arsenic(III) oxide is easily reduced, for example by heating with charcoal, when arsenic deposits as a black shiny solid on the cooler parts of the tube. 

Arsenic(III) oxide is slightly soluble in water, giving a solution with a sweetish taste—but as little as 0.1 g can be a fatal dose (The antidote is freshly-precipitated iron(III) hydroxide.) The solution has an acid reaction to litmus, due to the formation of arsenic(III) acid ... 

Unlike phosphorus pentoxide, this oxide cannot be made directly. Arsenic(V) acid, H3ASO4 (strictly, tetraoxoarsenic acid), is first prepared by oxidising arsenic(III) oxide with concentrated nitric acid or some other strong oxidising agent ... 

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

Since arsenic is often found in nature associated with sulphide ores, sulphur dioxide obtained by this method may contain some arsenic(III) oxide as impurity, and in certain processes this is a distinct disadvantage. 

Arsenic trioxide [1327-53-3] (arsenic(III) oxide, arsenic sesquioxide, arsenous oxide, white arsenic, arsenic), AS2O2, is the most important arsenic compound of commerce. The octahedral or cubic modification, arsenoHte [1303-24-8], 298 1313.9 kJ/mol (—314 kcal/mol) 214 J/(mol-K)... 

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). 

Other examples are the use of osmium(VIII) oxide (osmium tetroxide) as catalyst in the titration of solutions of arsenic(III) oxide with cerium(IV) sulphate solution, and the use of molybdate(VI) ions to catalyse the formation of iodine by the reaction of iodide ions with hydrogen peroxide. Certain reactions of various organic compounds are catalysed by several naturally occurring proteins known as enzymes. 

Sublimation. This process is employed to separate volatile substances from non-volatile impurities. Iodine, arsenic(III) oxide, ammonium chloride and a number of organic compounds can be purified in this way. The material to be purified is gently heated in a porcelain dish, and the vapour produced is condensed on a flask which is kept cool by circulating cold water inside it. 

In this connection it must be pointed out that standard samples which have been analysed by a number of skilled analysts are commercially available. These include certain primary standards (sodium oxalate, potassium hydrogenphthalate, arsenic(III) oxide, and benzoic acid) and ores, ceramic materials, irons, steels, steel-making alloys, and non-ferrous alloys. 

Method A With arsenic(III) oxide. This procedure, which utilises arsenic(III) oxide as a primary standard and potassium iodide or potassium iodate as a catalyst for the reaction, is convenient in practice and is a trustworthy method for the standardisation of permanganate solutions. Analytical grade arsenic(III) oxide has a purity of at least 99.8 per cent, and the results by this method agree to within 1 part in 3000 with the sodium oxalate procedure (Method B, below). 

Procedure. Dry some arsenic(III) oxide at 105-110 °C for 1-2 hours, cover the container, and allow to cool in a desiccator. Accurately weigh approximately... 

Notes. (1) For elementary students, it is sufficient to weigh out accurately about 1.25 g of arsenic(III) oxide, dissolve this in 50 mL of a cool 20 per cent solution of sodium hydroxide, and make up to 250 mL in a graduated flask. Shake well. Measure 25.0 mL of this solution by means of a burette and not with a pipette (caution — the solution is highly poisonous) into a 500 mL conical flask, add 100 mL water, 10 mL pure concentrated hydrochloric acid, one drop potassium iodide solution, and titrate with the permanganate solution to the first permanent pink colour as detailed above. Repeat with two other 25 mL portions of the solution. Successive titrations should agree within 0.1 mL. 

Calculation. It is evident from the equation given above that if the weight of arsenic(III) oxide is divided by the number of millilitres of potassium permanganate solution to which it is equivalent, as found by titration, we have the weight of primary standard equivalent to 1 mL of the permanganate solution. 

Method A Standardisation with arsenic (III) oxide. Discussion. The most trustworthy method for standardising cerium(IV) sulphate solutions is with pure arsenic(III) oxide. The reaction between cerium(IV) sulphate solution and arsenic(III) oxide is very slow at the ambient temperature it is necessary to add a trace of osmium tetroxide as catalyst. The arsenic(III) oxide is dissolved in sodium hydroxide solution, the solution acidified with dilute sulphuric acid, and after adding 2 drops of an osmic acid solution prepared by dissolving 0.1 g osmium tetroxide in 40mL of 0.05M sulphuric acid, and the indicator (1-2 drops ferroin or 0.5 mL /V-phenylanthranilic acid), it is titrated with the cerium(IV) sulphate solution to the first sharp colour change orange-red to very pale blue or yellowish-green to purple respectively. 

Procedure. Weigh out accurately about 0.2 g of arsenic(III) oxide, previously dried at 105-110 °C for 1-2 hours, and transfer to a 500 mL beaker or to a 500 mL conical flask. Add 20 mL of approx. 2M sodium hydroxide solution, and warm the mixture gently until the arsenic(III) oxide has completely dissolved. Cool to room temperature, and add 100 mL water, followed by 25 mL 2.5M sulphuric acid. Then add 3 drops 0.01 M osmium tetroxide solution (0.25 g osmium tetroxide (CARE FUME CUPBOARD) dissolved in 100 mL 0.05M sulphuric acid) and 0.5 mL AT-phenylanthranilic acid indicator (or 1-2 drops of ferroin). Titrate with the 0.1 M cerium(IV) sulphate solution until the first sharp colour change occurs (see Discussion above). Repeat with two other samples of approximately equal weight of arsenic(III) oxide. 

For the preparation of standard iodine solutions, resublimed iodine and iodate-free potassium iodide should be employed. The solution may be standardised against pure arsenic(III) oxide or with a sodium thiosulphate solution which has been recently standardised against potassium iodate. 

A) With arsenic(III) oxide Discussion. As already indicated (Section 10.94), arsenic(III) oxide which has been dried at 105-110 °C for two hours is an excellent primary standard. The reaction between this substance and iodine is a reversible one ... 

Procedure. Wdgh out accurately about 2.5g of finely powdered arsenic(III) oxide, transfer to a 500 mL beaker, and dissolve it in a concentrated solution of sodium hydroxide, prepared from 2g of iron-free sodium hydroxide and 20 mL of water. Dilute to about 200 mL, and neutralise the solution with 1M hydrochloric add, using a pH meter. When the solution is faintly add transfer the contents of the beaker quantitatively to a 500 mL graduated flask, add 2 g of pure sodium hydrogencarbonate, and, when all the salt has dissolved, dilute to the mark and shake well. 

If it is desired to base the standardisation directly upon arsenic(III) oxide, proceed as follows. Weigh out accurately about 0.20 g of pure arsenic(III) oxide into a conical flask, dissolve it in 10 mL of 1M sodium hydroxide, and add a small excess of dilute sulphuric acid (say, 12-15 mL of 0.5M acid). Mix thoroughly and cautiously. Then add carefully a solution of 2 g of sodium hydrogencarbonate in 50 mL of water, followed by 2 mL of starch solution. Titrate slowly with the iodine solution to the first blue colour. Repeat with two other similar quantities of the oxide. 

The excess of arsenic(III) oxide is determined with 0.05M iodine and starch. 

Potassium iodate is a powerful oxidising agent, but the course of the reaction is governed by the conditions under which it is employed. The reaction between potassium iodate and reducing agents such as iodide ion or arsenic(III) oxide in solutions of moderate acidity (0.1-2.0M hydrochloric acid) stops at the stage when the iodate is reduced to iodine ... 

To assay a sample of arsenic(III) oxide the following procedure may be used. 

To determine the purity of a sample of arsenic(III) oxide follow the general procedure outlined in Section 10.127 but when the 25 mL sample of solution is being prepared for titration, add 25 mL water, 15 mL of concentrated hydrochloric acid and then two drops of indicator solution (xylidine ponceau or naphthalene black 12B see Section 10.125). Titrate slowly with the standard 0.02M potassium bromate with constant swirling of the solution. As the end point approaches, add the bromate solution dropwise with intervals of 2-3 seconds between the drops until the solution is colourless or very pale yellow. If the colour of the indicator fades, add another drop of indicator solution. (The immediate discharge of the colour indicates that the equivalence point has been passed and the titration is of little value.)... 

Notes. (1) A suitable solution for practice in this determination is prepared by dissolving about 0.3 g of arsenic(III) oxide, accurately weighed, in 9M hydrochloric acid. 

Prepare a 0.02 M solution of potassium permanganate and standardise it against arsenic(III) oxide. 

Standard arsenic solution. Dissolve 1.320 g arsenic(III) oxide in the minimum volume of 1M sodium hydroxide solution, acidify with dilute hydrochloric acid, and make up to 1 L in a graduated flask 1 mL contains 1 mg of As. A solution containing 0.001 mg As per mL is prepared by dilution. 

Arsenic/antimony solution. Prepare a mixed solution containing approximately 115 mg arsenic and 160 mg antimony in 1 L by dissolving about 150 mg arsenic(III) oxide and 300 mg antimony(III) chloride in 6M hydrochloric acid. 

Apparent indicator constant 264, 267 Apparent stability constant 59 Aqua regia 111 Arc alternating current, 764 direct current, 763, 771 sensitivities of elements, (T), 766 Aromatic hydrocarbons analysis of binary mixtures, 715 Arsenates, D. of (ti) 357 Arsenic, D. of as silver arsenate, (ti) 357 as trisulphide, (g) 448 by iodine, (am) 634, (ti) 397 by molybdenum blue method, (s) 681 by potassium bromate, (ti) 406 by potassium iodate, (ti) 401 in presence of antimony, (s) 724 Arsenic(III) oxide as primary standard, 261... 

A sample of industrial waste was analyzed for the presence of arsenic(III) oxide by titration with 0.0100 M KMn04. It took 28.15 mL of the titrant to reach the stoichiometric point. How many grams of arsenic(III) oxide did the sample contain ... 

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. 

Toumassat C, Chartel L, Bosbach D, Manceau A (2002) Arsenic (III) oxidation by bimessite and precipitation of manganese (II) arsenate. Environ Sci Technol 36 493-500... 

Webb, D.R., S.E. Wilson, and D.E. Carter. 1986. Comparative pulmonary toxicity of gallium arsenide, gallium (III) oxide, or arsenic (III) oxide intratracheally instilled into rats. Toxicol. Appl. Pharmacol. 82 405-416. 

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