Synthesis and characterization of arsenate antimonic acid AAAc(1 : 1)

Abstract

The AAAc(1 : 1) was synthesized in water by As₂O₃ and Sb₂O₃ with molar ratio of 1 : 1. AAAc(1 : 1) was characterized by Raman, IR, TG/DTG, DSC, XPS and XRD. The results show that there are four peaks to v_s of As-OH, As-O-Sb, Sb-OH and Sb-O-Sb in Raman spectra of AAAc(1 : 1) at 100 – 1 000 cm⁻¹. The solution of AAAc(1 : 1) was also titrated with KOH solution. The titration results show that AAAc(1 : 1) is a hexabasic acid with dissociation constants of k₁=3.62 × 10⁻², k₂=3.05 × 10⁻³, k₃=6.43 × 10⁻⁶, k₄ =9.78 × 10⁻⁸, k₅=1.32 × 10⁻¹¹, k₆=3.87 × 10⁻¹². AAAc(1 : 1) has a good solubility and stability in water, its solid obtained by free volatilizing water from its solution under air at ambient temperature is amorphous. Chemical and thermal analysis show that the composition of AAAc(1 : 1) is As₂O₅ · Sb₂O₅ · 8H₂O in air at 25 °C. AAAc(1 : 1) has the structure of AsO(OH)₂-OH-Sb(OH)₄-O-Sb(OH)₄-OH-AsO(OH)₂ or As(OH)₃-O-Sb(OH)₄-O-Sb(OH)₄-O-As(OH)₃ (isomerism) through experimental determination and geometry optimization.

Keywords

arsenic acid / antimonic acid / arsenate antimonic acid

References

[1] ToyA D FPhosphorus, Chapter 20 of Comprehensive Inorganic Chemistry [M], 1975, Oxford, Pergamon Press

[2] WangX W, ChenQ Y, YinZ L, et al.. Removal of impurities from copper electrolyte with adsorbent containing antimony[J]. Hydrometallurgy, 2003, 69: 39-44

[3] WangX W, ChenQ Y, LongZ P, et al.. Application of antimony in purification of copper electrolyte[J]. The Chinese Journal of Nonferrous Metals, 2002, 12: 1277-1280

[4] WangXue-wenStudy on the Mechanism of the Formation and Action of Arsenate Antimonic Acid in Copper Electrorefining[D], 2003, Changsha, Central South University

[5] WangXue-wen, ChenQi-yuan, YinZhou-lan, et al.. Discovery of arsenato antimonic acid[J]. Journal of Central South University (Science and Technology), 2004, 35(S1): 130-133(in Chinese)

[6] CutterG A, CutterL S, FeatherstoneA M, et al.. Antimony and arsenic biogeochemistry in the western atlantic ocean[J]. Deep-Sea Research II, 2001, 48: 2895-2915

[7] MatthewsG PExperimental Physical Chemistry[M], 1985, Oxford, Clarendon Press

[8] WangYu-wen, LiangYi-zeng, ChenQi-yuan, et al.. Modification to the processing of nonlinear problems with linear fit[J]. Computers and Applied Chemistry, 2005, 22(4): 295-300

[9] NoggleJ HPhysical Chemistry[M], 1985, Boston, Little, Brown and Company

[10] SmithJ DArsenic, Antimony and Bismuth, Chapter 21 of Comprehensive Inorganic Chemistry[M], 1975, Oxford, Pergamon Press

[11] MyneniS C B, TrainaS J, WaychunasG A, et al.. Experimental and theoretical vibrational spectroscopic evaluation of arsenate coordination in aqueous solutions, solids, and at mineral-water interfaces [J]. Geochim Cosmochim Acta, 1998, 62(19/20): 3285-3300

[12] Herzog-CanceM H, HerzogJ F, PotierA, et al.. Raman spectroscopy study of species responsible for the fast proton conductivity in H₂Sb₄O₁₁ · 3H₂O[J]. J Mol Struct, 1986, 143: 67-70

[13] ColombanP, Doremieux-MorinC, PiffardY, et al.. Equilibrium between protonic species and conductivity mechanism in antimonic acid H₂Sb₄O₁₁ · nH₂O[J]. J Mol Struct, 1989, 213: 83-96

[14] MattiodaA, FrechA R. Vibrational spectra, thermal analysis and conductivity of phases of ammonium hydrazinium (2⁺) sulfate[J]. J Phys Chem Solids, 1998, 59: 353-362

[15] NaïliH, MhiriT. X-ray structural, vibrational and calorimetric studies of a new rubidium pentahydrogen arsenate RbH₅(AsO₄)₂[J]. J Alloys Comp, 2001, 315: 143-149

[16] LosillaE R, SalvadóM A, ArandaM A G, et al.. Layered acid arsenates α-M(HAsO₄)2 · H₂O(M=Ti, Sn, Pb): synthesis optimization and crystal structures[J]. J Mol Struct, 1998, 470: 93-104

[17] ZhaoT CThe Metallurgy of Antimony[M], 1988, Changsha, Central South University of Technology Press

[18] BarbaroA, LarrondoS, DuhaldeS, et al.. Effect of titanium-doping on the properties of vanadium antimonate catalysts[J]. Applied Catalysis A, 2000, 193: 277-283

[19] GhidaouiD, LyonS B, ThompsonG E, et al.. Oxide formation during etching of gallium arsenide[J]. Corrosion Science, 2002, 44: 501-509

[20] WangJ Q, WuW H, FengD MThe Introduction of Electron Spectroscopy (XPS/XAES/UPS) [M], 1992, Beijing, National Defence Industry Press