Tributyl phosphate as a sensitivity-enhancing solvent for organotin in carbon furnace atomic absorption spectrometry.

Tributyl phosphate (TBP) has been found to be a sensitivity-enhancing solvent for organotin compounds in graphite furnace atomic absorption spectrometry; (C(4)H(9))(2)Sn(O(2)CCH(3))(2), (C(4)H(9))(2)Sn(O(2)CC(11)H(23))(2), (C(4)H(9))(3)SnCl, and (C(4)H(9))(4)Sn all give 1 order of magnitude higher sensitivities in TBP than in toluene or ethyl acetate. The sensitivities are enhanced further 1-2 orders of magnitude in TBP, when PdCl(2)(CH(3)CN)(2) is added as a matrix modifier in the organic solvent. Among the four organotin compounds, (C(4)H(9))(2)Sn(O(2)CCH(3))(2) and (C(4)H(9))(2)Sn(O(2)CC(11)H(23))(2) give better sensitivities than (C(4)H(9))(3)SnCl and (C(4)H(9))(4)Sn in the absence of palladium in any organic solvent, which suggests that the oxygen atom in the tin compound might form tin oxides that are resistant to volatilization loss during ashing. Scanning electron microscopic, electrothermal vaporization ICPMS, and powder X-ray diffraction studies show that the final products before atomization include phosphorus-containing compounds Sn(2)P(2)O(7), SnP(2)O(7), and Pd(9)P(2), besides tin-palladium alloys, PdSn, Pd(3)Sn, Pd(2)Sn, Pd(3)Sn(2), and PdSn(3). These phosphorus-containing compounds would more efficiently stabilize tin and suppress tin vaporization loss during ashing, to give higher sensitivity.