A facile method has been developed for the highly sensitive and selective determination of ultratrace Be(II) ion using a new fluorimetric reagent, 10-hydroxybenzo[h]quinoline-7-sulfonate (HBQS), under extremely alkaline conditions, at pH 12.0. This reagent is quite suitable for the very small ion, Be(II), to form a 6-membered chelate ring, compatible with a high fluorescence yield. The stoichiometry of the chelate is 1:1 for Be-HBQS at pH 12.0. The calibration graph gave a wide linear dynamic range, 2-100 nmol dm(-3) of Be(II) ion with the detection limit (3s blank) of 0.52 nmol dm(-3), or 4.7 pg cm(-3). The excellent sensitivity and toughness toward the matrix influence were demonstrated using the artificial sample solutions for air-dust. Coupled with the simple masking procedure using EDTA, the method enables one to determine Be(II) ion at nanomolar levels in the presence of metals at the natural abundance levels in air-dust samples, typically Al, Ca, Cu, Fe, Mg, Pb, and Zn at 130, 150, 1.0, 70, 33, 3.0, and 8.0 micromol dm(-3), respectively, in the final solution. The proposed method was successfully applied to the determination of Be in urban air.
The solvolytic dissociation rate constants of 1:2 complexes of Al3+ and Ga3+ with an azo dye ligand, 2,2'-dihydroxyazobenzene-5,5'-disulfonate (DHABS, H2L2-), have been evaluated with a capillary electrophoretic reactor (CER) system. This CER system is based on the fact that metal complexes encounter an overwhelming force to dissociate when apart from the ligand by CE resolution. Treatment of a capillary with a slightly acidic buffer solution, e.g., pH 5, reduces the double-layer potential (zeta) of the inner silica wall. Owing to slow relaxation of the deprotonation equilibria of superficial silanol groups known as the pH hysteresis, this zeta potential can be actually retained during the electrophoresis of the metal complexes in question with a neutral buffer at pH 7.0. This method enables one to manipulate migration times, namely, residence times in a capillary tube, from 5 to 90 min, depending on the prescribed conditioning pH, without changing any other operation conditions such as buffer composition and electric field strength. The excellent performance of the CER is exemplified by the accurate estimation of the dissociation degree of the complexes. The dissociation degree-time profiles for the complexes are quantitatively described using both internal and external standards; the very inert complex of [Co(III)L2]5- for the peak signal standardization and methyl orange for the injection volume correction. The solvolytic dissociation rate constants of the 1:2 complexes of Al3+ and Ga3+ ions with DHABS [AlL2]5- and [GaL2]5- into the 1:1 ones have been determined as (4.9+/-1.0) x 10(-4) and (3.7+/-0.3) x 10(-3) s(-1) at 303 K, respectively.
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