Other
Scientific paper
Mar 1991
adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=1991gecoa..55..769m&link_type=abstract
Geochimica et Cosmochimica Acta, vol. 55, Issue 3, pp.769-776
Other
5
Scientific paper
Gold(III)-chloride and gold(I)-thiosulfate adsorption by goethite was investigated as a function of pH (4 to 8), Cl - concentration (0 to 0.1 M), and ionic strength (0.01 and 0.1 M). Several observations suggest that Au(III)-chloride hydrolysis species with <4 Cl ligands are preferentially adsorbed by goethite and that at low surface coverages these species are adsorbed in an inner-sphere, bidentate fashion. At pH 4.0 and in 0.01 M NaNO 3 , adsorption isotherms have a shape and maximum adsorption densities (210 mol Au/g) similar to those previously observed for phosphate. In addition, excess Cl - appears in solution after adsorption, and an ionic strength increase to 0. l M NaNO 3 has little effect on adsorbed amounts below 25% of maximum surface coverage. In 0.01 and 0. l M NaCl, however, adsorption increases as pH increases from 4 to 7, which is opposite to typical behavior for anion adsorption onto oxide surfaces. This "retrograde" adsorption trend is probably due to a shift in Au(III)-chloride species dominance from AuCl 4 - at pH 4 to preferentially adsorbed hydroxyl-substituted species such as AuCl(OH) 3 - at higher pH values. Maximum adsorption densities for Au(S 2 O 3 ) 2 3- at pH 4.0 in 0.01 M NaNO 3 are only 35 mol Au/g and decrease to 15 / mol/g in 0.1 M NaNO 3 . Also, adsorption decreases as pH is increased from 4 to 8. This behavior suggests Au(I)-thiosulfate adsorption occurs primarily via a non-specific or outer-sphere mechanism. Moreover, the contrast in adsorption behavior of these two gold species demonstrates the importance of steric factors to adsorption processes. Gold(III)-chloride species are square planar, and the distance along an edge of this square (3.23 Å) closely matches the distance between A-type hydroxyl groups on the goethite surface (3.04 Å). Thus, these hydroxyl groups form an ideal "template" for bidentate coordination. Conversely, Au(S 2 O 3 ) 2 3- is a large, linear anion, and consequently it is difficult for this species to coordinate specifically with goethite surface hydroxyl groups.
Andrade Wilson O.
Machesky Michael L.
Rose Arthur W.
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