Arsenic oxidation-reduction

The reactions discussed above show that arsenic(fV) is of redox amphoteric character and a stronger reducing agent than arsenic(in), but at the same time it is a stronger oxidant than arsenic(V). Partners of the oxidation-reduction reactions of arsenic(fV) known so far can be seen in Table 13. It follows from the redox amphoteric character that the oxidation potentials of couples involving arsenic species are in the order... 

All four dissolution procedures studied were found to be suitable for arsenic determinations in biological marine samples, but only one (potassium hydroxide fusion) yielded accurate results for antimony in marine sediments and only two (sodium hydroxide fusion or a nitricperchloric-hydrofluoric acid digestion in sealed Teflon vessels) were appropriate for determination of selenium in marine sediments. Thus, the development of a single procedure for the simultaneous determination of arsenic, antimony and selenium (and perhaps other hydride-forming elements) in marine materials by hydride generation inductively coupled plasma atomic emission spectrometry requires careful consideration not only of the oxidation-reduction chemistry of these elements and its influence on the hydride generation process but also of the chemistry of dissolution of these elements. 

Rau, M. Rieck, D. Evans, J.W. (1987) Investigation of iron oxide reduction by TEM. Metallurgical Transactions 188 257-278 Raven, K.P. Jain, A. Loeppert, R.H. (1998) Ar-senite and arsenate adsorption on ferrihy-drite Kinetics, equilibrium, and adsorption envelopes. Environ. Sci. Techn. 32 344-349 Rea, B.A. Davis, J.A. Waychunas, G.A. (1994) Studies of the reactivity of the ferrihydrite surface by iron isotopic exchange and Moss-bauer spectroscopy. Clays Clay Min. 42 23-34... 

The reaction commences at a temperature above 400° C., before the melting temperature is reached, and the fused product therefore always contains some arsenious oxide.1 When heated in hydrogen, the pentoxide is reduced first to arsenious oxide and then to free arsenic. Similar reduction occurs when it is heated with carbon or phosphorus with sulphur, arsenious sulphide is formed. Arsenic and metallic arsenides result when the pentoxide is heated with alkali metals,2 zinc, lead, iron or most other heavy metals mercury and silver react only at high temperature gold and platinum do not react. 

Introduction to arsenic oxidation and reduction 2.5.1 Arsenic oxidation... 

In natural waters, arsenic may exist as one or more dissolved species, whose chemistry would depend on the chemistry of the waters. Over time, arsenic species dissolved in water may (1) interact with biological organisms and possibly methylate or demethylate (Chapter 4), (2) undergo abiotic or biotic oxidation, reduction, or other reactions, (3) sorb onto solids, often through ion exchange, (4) precipitate, or (5) coprecipitate. This section discusses the dissolution of solid arsenic compounds in water, the chemistry of dissolved arsenic species in aqueous solutions, and how the chemistry of the dissolved species varies with water chemistry and, in particular, pH, redox conditions, and the presence of dissolved sulfides. Discussions also include introductions to sorption, ion exchange, precipitation, and coprecipitation, which have important applications with arsenic in natural environments (Chapters 3 and 6) and water treatment technologies (Chapter 7). 

Precipitation refers to dissolved species (such as As(V) oxyanions) in water or other liquids reacting with other dissolved species (such as Ca2+, Fe3+, or manganese cations) to form solid insoluble reaction products. Precipitation may result from evaporation, oxidation, reduction, changes in pH, or the mixing of chemicals into an aqueous solution. For example, As(V) oxyanions in acid mine drainage could flow into a nearby pond and react with Ca2+ to precipitate calcium arsenates. The resulting precipitates may settle out of the host liquid, remain suspended, or possibly form colloids. Like sorption, precipitation is an important process that affects the movement of arsenic in natural environments and in removing arsenic from contaminated water (Chapters 3 and 7). 

Pfeifer, H.-R., Gueye-Girardet, A., Reymond, D. et al. (2004) Dispersion of natural arsenic in the Malcantone watershed, southern Switzerland Field evidence for repeated sorption-desorption and oxidation-reduction processes. Geoderma, 122(2-4 SPEC. IIS.), 205-34. 

Oxidation of arsenic-bearing pyrite with adsorption onto iron oxides and/or other metal (oxy)(hydr)oxides Nitrate reduction by pyrite oxidation (note that Appelo and Postma, 1999 referred to pure rather than arsenian pyrite) Manganese oxide reduction and release of sorbed arsenic Fe(lll) reduction on oxide surfaces changes net charge leading to arsenic desorption Iron oxide reductive dissolution and release of sorbed arsenic catalyzed by NOM degradation... 

Butler [3] determined inorganic arsenic species in non saline waters by ion exclusion chromatography with electrochemical detection. Two species were separated by ion exclusion chromatography using 0.10M orthophosphoric acid eluent. Arsenic(III) was detected by its oxidation at a platinum wire electrode. Measurement of total inorganic arsenic after reduction of arsenic(V) to arsenic(III) by sulphur dioxide enabled... 

Henry and Thorpe [14] separated monomethylarsonic acid, dimethylarsenic acid, As(III) and As(IV) on an ion exchange column from samples of pond water receiving fly ash from a coal-fired power station. They then determined these substances by differential pulse polarography. The above four arsenic species were present in non saline water systems. Moreover, a dynamic relationship exists whereby oxidation-reduction and biological methylation-dimethylation reactions provide the pathways for the intercoversions of the arsenicals. 

The Irradiated uranium soln 1b added to a standardized arsenlte carrier In dilute HgS04, oxidized to arsenate (V) with KBt03 and reduced again vlth potassium metahlsulflte (This oxidation-reduction procedure is carried out to Insure the complete exchange of As-activ ity with the trlvalent As carrier.)... 

Arsenic(III), antimony(III), and tin(II) ions can be oxidized to arsenic(V), antimony(V), and tin(IV) ions respectively. On the other hand, the latter three can be reduced by proper reducing agents. The oxidation-reduction potentials of the arsenic(V)-arsenic(III) and antimony(V)-antimony(III) systems vary with pH, therefore the oxidation or reduction of the relevant ions can be assisted by choosing an appropriate pH for the reaction. 

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