Arsenite precipitation

Many of the important chemical reactions controlling arsenic partitioning between solid and liquid phases in aquifers occur at particle-water interfaces. Several spectroscopic methods exist to monitor the electronic, vibrational, and other properties of atoms or molecules localized in the interfacial region. These methods provide information on valence, local coordination, protonation, and other properties that is difficult to obtain by other means. This chapter synthesizes recent infrared, x-ray photoelectron, and x-ray absorption spectroscopic studies of arsenic speciation in natural and synthetic solid phases. The local coordination of arsenic in sulfide minerals, in arsenate and arsenite precipitates, in secondary sulfates and carbonates, adsorbed on iron, manganese, and aluminium hydrous oxides, and adsorbed on aluminosilicate clay minerals is summarized. The chapter concludes with a discussion of the implications of these studies (conducted primarily in model systems) for arsenic speciation in aquifer sediments. 

Arsenite precipitates Ag3As03, bright yellow, insoluble in H2O, readily dissolved or transposed by both acids and bases. Arsenate precipitates Ag3As04, brown, insoluble in H2O, soluble in H3O and NH3. 

Arsenites precipitate from Pb ", bulky, white Pb3(As03)2 aq, difficultly soluble in water, readily soluble in dilute acids and OH . Arsenate precipitates white lead arsenate from neutral or shghtly alkaline Pb°, soluble in OH and HNO3 insoluble in CH3CO2H. It may be a mixture of Pb3(As04>2 and PbHAs04, depending on conditions. 

A widely used procedure for determining trace amounts of tellurium involves separating tellurium in (1 1) hydrochloric acid solution by reduction to elemental tellurium using arsenic as a carrier and hypophosphorous acid as reductant. The arsenic, reduced from an addition of arsenite to the solution, acts as a carrier for the tellurium. The precipitated tellurium, together with the carrier, is collected by filtration and the filter examined directly in the wavelength-dispersive x-ray fluorescence spectrometer. 

The Structure of AS2S5 is unknown. It is said to be formed as a yellow solid by passing a rapid stream of H2S gas into an ice-cold solution of an arsenate in cone HCl slower passage of H2S at room temperature results in reduction of arsenate to arsenite and consequent precipitation of AS2S3. It decomposes in air above 95° to give AS2S3 and sulfur. 

Sodium arsenite can be used to detect the presence of iron sulfide on the metal surface. Iron sulfide is the corrosion product of the reaction between hydrogen sulfide in drilling fluid and iron in the drillpipe. An acid solution of sodium arsenite reacts with the sulfide to form a bright yellow precipitate. 

Arsenites may also be determined by this procedure but must first be oxidised by treatment with nitric acid. Small amounts of antimony and tin do not interfere, but chromates, phosphates, molybdates, tungstates, and vanadates, which precipitate as the silver salts, should be absent. An excessive amount of ammonium salts has a solvent action on the silver arsenate. 

Excellent results are obtained by the following method, which is of wider applicability. When excess of standard sodium arsenite solution is treated with hydrogen sulphide solution and then acidified with hydrochloric acid, arsenic(III) sulphide is precipitated ... 

Perhaps the most obvious method of studying kinetic systems is to periodically withdraw samples from the system and to subject them to chemical analysis. When the sample is withdrawn, however, one is immediately faced with a problem. The reaction will proceed just as well in the test sample as it will in the original reaction medium. Since the analysis will require a certain amount of time, regardless of the technique used, it is evident that if one is to obtain a true measurement of the system composition at the time the sample was taken, the reaction must somehow be quenched or inhibited at the moment the sample is taken. The quenching process may involve sudden cooling to stop the reaction, or it may consist of elimination of one of the reactants. In the latter case, the concentration of a reactant may be reduced rapidly by precipitation or by fast quantitative reaction with another material that is added to the sample mixture. This material may then be back-titrated. For example, reactions between iodine and various reducing agents can be quenched by addition of a suitably buffered arsenite solution. 

The background of this study is the investigation at the site Bielatal (see Daus et al. this volume). The arsenic concentrations in the seepage water of this tailings pond are high (up to 4 mg/1) and natural arsenic precipitation processes are incomplete. The neutral pH, the presence of both arsenite and arsenate (sum 1 mg/L), and the oxygen saturation of the water are the boundary conditions of the described experiments. 

The mobilization of arsenic from the tailings material seems to be a slow and continuos process attributed to reduction of iron phases. The seepage water of the middle source contains arsenite as well as arsenate in high concentrations and seems to be the only water source in contact with the tailings material. The concentrations of arsenic downstream are still high and the immobilization process by precipitation of iron hydroxide and coprecipitation or sorption of arsenic is incomplete. A reason for this may be the slow kinetics of the oxidation process and the transport of fine grained hydroxide particles. These particles are mobile and can bind the arsenic (mainly as arsenate) too. 

The process can be used to immobilize heavy metals such as Cd, Zn, Cu, Pb, Ni and Co. Cr(VI) can be reduced by some metal-reducing bacteria to the less toxic and less soluble form Cr(III). Arsenate [As(V)] can be reduced to the more mobile arsenite [As(III)] which precipitates as AS2S3, and is insoluble at low pH. Several laboratory-scale tests (batch and column) are currently available to study the feasibility of this process. However, only a few field tests have been performed to date. Two such tests have been conducted in Belgium, one at a non-ferrous industrial site, where the groundwater was contaminated with Cd, Zn, Ni and Co, and the other which was treated by injection of molasses in order to reduce chromium (VI) to chromium (III). A third demonstration in The Netherlands has been performed at a metal surface treatment site contaminated by Zn. The outcomes of a batch test of a groundwater heavily contaminated by Zn, Cd, Co and Ni are presented in Table 5. The initial sulphate concentration was 506mg/l. With the addition of acetate, a nearly... 

The oxidized form of As, arsenate, As(V), which is present as HAs04 at neutral pH (p f values in Table 7.8), is sorbed on soil surfaces in a similar way to orthophosphate. The reduced form arsenite, As(lll), which is present in solution largely as H3As03(p fi = 9.29), is only weakly sorbed, hence mobility tends to increase under reducing conditions. Mobility will also increase without reduction of As(V) because, as for phosphate, reductive dissolution of iron oxides results in desorption of HAs04 into the soil solution. Under prolonged submergence As(lll) may be co-precipitated with sulfides. 

Arsenic acid reacts with metal salts forming their orthoarsenates, e.g., calcium orthoarsenate. Reaction with silver nitrate in neutral solution produces a chocolate-brown precipitate of silver orthoarsenate. It forms pyroarsenic acid (or pyroarsenate) on heating over 100°C. It is reduced to arsenous acid (or arsenites) when treated with reducing agents. 

Experimental. In order to study the nucleophilic properties of 13 it was necessary to add excess I " to the solutions to prevent precipitation of I2. The rate of formation of CoCCN I-3 was followed spectrophotometrically after the I3 " in aliquots of the solution taken at suitable time intervals was reduced to I by arsenite ion. A typical set of experiments was carried out at 40°C. and unit ionic strength, with all solutions containing 0.5/1/ 1 and variable I3 " at a maximum concentration of 0.28M, the approximate upper limit imposed by solubility restrictions. The results are presented in Figure 3 as a plot of k the symbol used for the pseudo first-order rate constant for this system, vs. l/(lf). It is apparent that 13 is a remarkably efficient nucleophile, with a reaction rate considerably greater than that found for I at comparable concentrations. The points in Figure 3 also show detectable deviation from linearity, despite the limited range of 13 " concentration which was available. 

Arsenates have been described in one case exploiting the fact that the zirconyl cation forms a water-soluble arsenite but insoluble arsenate. By adding nitric acid to a solution of zirconyl chloride and sodium arsenite, the arsenite was oxidized to arsenate by the nitric acid, precipitating the insoluble zirconyl arsenate [32]. As for phosphates (and probably more readily), arsenates might be reduced to arsenides. 

When dry arsenious oxide is fused with sodium thiosulphate a mixture of the di- and tri-sulphides results.13 In aqueous solution and in acidified solutions of arsenites the addition of aqueous sodium thiosulphate causes the precipitation of arsenious sulphide after a sharply defined induction period, the duration of which is in inverse proportion to the thiosulphate concentration and practically independent... 

A small quantity of arsenic is precipitated in each case. Sodium dihydrogen arsenite yields a considerable precipitate of arsenic and also of the red disulphide. The polythionates react similarly to thiosulphates, yielding sulphite, thioarsenate and arsenate.5 The per- 1 ites also cause oxidation to arsenate. Sodium hydrosulphite... 

Antimony Arsenite.—When powdered antimony is digested with a concentrated aqueous solution of arsenic acid, and the solution then diluted with water, a precipitate forms, which was described by Berzelius 6 as antimony arsenite. He obtained a similar product by heating a mixture of arsenic and antimony pentoxide it remained as a transparent vitreous mass. The exact composition of these products does not appear to have been investigated. 

Barium Metarsenite, Ba(As02)3, may be obtained by warming barium chloride with a solution of ammonium arsenite to which acetic acid has been added until arsenious acid is on the point of precipitation. The precipitate is then dried at 100° C.2 It is a white powder, easily soluble in water, but it can also be obtained as a gelatinous mass 3 when a mixture of barium chloride and potassium metarsenite in solution is left to stand for a few hours. On strongly heating it decomposes to form arsenate and free arsenic, but to a much less extent than is the case with the orthoarsenite.4... 

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