A novel sensitive and relatively selective kinetic method is presented for the determination of V(V) based on its catalytic effect on the oxidation reaction of Celestine blue by potassium bromate in the presence of ...A novel sensitive and relatively selective kinetic method is presented for the determination of V(V) based on its catalytic effect on the oxidation reaction of Celestine blue by potassium bromate in the presence of citric acid as an activator. The reaction was monitored spectropho- tometrically by measuring the decrease in absorbance of Celestine blue at a maximum absorption wavelength of 540 nm between 0.5 and 9 min (the fixed-time method) in an H3PO4 medium at 45℃. The effect of various parameters such as concentrations of H3PO4, citric acid, potassium bromate and Celestine blue, ionic strength, reaction temperature and time on the rate of V(V) catalyzed reaction was studied. The method is free from the most interferences, especially from large amounts of V(IV). The decrease in absorbance is proportional to the concentration of V(V) over the entire concentration range tested (0.025-1.25 lag.mL^-1) with a detection limit of 6.80 tag.L^-1 (according to statistical 3Sblank/k criterion) and a coefficient of variation (CV) of 1.78% (for ten replicate measurements at 95% confidence level). The proposed method suffers from a few interferences such as Cr(VI) and Hg(Ⅱ) ions. The method was successfully applied to the determination of V(V) in river water, lake water, tap water, natural drinking water samples and a certified standard reference material such as SRM-1640 with satis- factory results. The vanadium contents of natural water samples were detected by using both linear calibration curve and standard addition curve methods. The recoveries of spiked vanadium (V) into the certified standard water sample were found to be quantitative, and the reproducibility was satisfactory. It was observed that the results of the SRM 1640 were in good agreement with the certified value.展开更多
A novel catalytic kinetic method is proposed for the determination of Se(Ⅳ), Se(Ⅵ), and total inorganic selenium in water based on the catalytic effect of Se(Ⅳ) on the reduction of Celestine blue by sodium su...A novel catalytic kinetic method is proposed for the determination of Se(Ⅳ), Se(Ⅵ), and total inorganic selenium in water based on the catalytic effect of Se(Ⅳ) on the reduction of Celestine blue by sodium sulfide at pH 7.0 phosphate buffer. The fixed-time method was adopted for the determination and speciation of inorganic selenium. Under the optimum conditions, the two calibration graphs are linear with a good correlation coefficient in the range 2-20 and 20-200 μg·L-1 of Se(Ⅳ) for the fixed-time method at 30℃. The experimental and theo- retical detection limits of the developed kinetic method were found to be 0.21 and 2.50 μg·L-1 for the fixed-time method (3 min). All of the variables that affect the sensitivity at 645 nm were investigated, and the optimum conditions were established. The interference effect of various cations and anions on the Se(Ⅳ) determination was also studied. The selectivity of the selenium determination was greatly improved with the use of the strongly cation exchange resin such as Amberlite IR120 plus as long as chelating agents of thiourea and thiosulphate. The proposed kinetic method was validated statistically and through recovery studies in natural water samples. The relative standard deviations (RSDs) for ten replicate measurements of 2, 10, and 20 μg·L-1 of Se(Ⅳ) change between 0.35% and 5.58%, while the RSDs for ten replicate measurements of 3, 6, and 12 μg·L-1 of Se(Ⅵ) change between 0.49% and 1.61%. Analyses of a certified standard reference material (NIST SRM 1643e) for selenium using the fixed-time method showed that the proposed kinetic method has good accuracy. The Se(Ⅳ), Se(Ⅵ), and total inorganic selenium in lake and river water samples have been successfully determined by this method after selective reduction of Se(Ⅵ) to Se(Ⅳ).展开更多
文摘A novel sensitive and relatively selective kinetic method is presented for the determination of V(V) based on its catalytic effect on the oxidation reaction of Celestine blue by potassium bromate in the presence of citric acid as an activator. The reaction was monitored spectropho- tometrically by measuring the decrease in absorbance of Celestine blue at a maximum absorption wavelength of 540 nm between 0.5 and 9 min (the fixed-time method) in an H3PO4 medium at 45℃. The effect of various parameters such as concentrations of H3PO4, citric acid, potassium bromate and Celestine blue, ionic strength, reaction temperature and time on the rate of V(V) catalyzed reaction was studied. The method is free from the most interferences, especially from large amounts of V(IV). The decrease in absorbance is proportional to the concentration of V(V) over the entire concentration range tested (0.025-1.25 lag.mL^-1) with a detection limit of 6.80 tag.L^-1 (according to statistical 3Sblank/k criterion) and a coefficient of variation (CV) of 1.78% (for ten replicate measurements at 95% confidence level). The proposed method suffers from a few interferences such as Cr(VI) and Hg(Ⅱ) ions. The method was successfully applied to the determination of V(V) in river water, lake water, tap water, natural drinking water samples and a certified standard reference material such as SRM-1640 with satis- factory results. The vanadium contents of natural water samples were detected by using both linear calibration curve and standard addition curve methods. The recoveries of spiked vanadium (V) into the certified standard water sample were found to be quantitative, and the reproducibility was satisfactory. It was observed that the results of the SRM 1640 were in good agreement with the certified value.
基金Cumhuriyet University Scientific Research Council (with F-225 code) for financial support of the present work
文摘A novel catalytic kinetic method is proposed for the determination of Se(Ⅳ), Se(Ⅵ), and total inorganic selenium in water based on the catalytic effect of Se(Ⅳ) on the reduction of Celestine blue by sodium sulfide at pH 7.0 phosphate buffer. The fixed-time method was adopted for the determination and speciation of inorganic selenium. Under the optimum conditions, the two calibration graphs are linear with a good correlation coefficient in the range 2-20 and 20-200 μg·L-1 of Se(Ⅳ) for the fixed-time method at 30℃. The experimental and theo- retical detection limits of the developed kinetic method were found to be 0.21 and 2.50 μg·L-1 for the fixed-time method (3 min). All of the variables that affect the sensitivity at 645 nm were investigated, and the optimum conditions were established. The interference effect of various cations and anions on the Se(Ⅳ) determination was also studied. The selectivity of the selenium determination was greatly improved with the use of the strongly cation exchange resin such as Amberlite IR120 plus as long as chelating agents of thiourea and thiosulphate. The proposed kinetic method was validated statistically and through recovery studies in natural water samples. The relative standard deviations (RSDs) for ten replicate measurements of 2, 10, and 20 μg·L-1 of Se(Ⅳ) change between 0.35% and 5.58%, while the RSDs for ten replicate measurements of 3, 6, and 12 μg·L-1 of Se(Ⅵ) change between 0.49% and 1.61%. Analyses of a certified standard reference material (NIST SRM 1643e) for selenium using the fixed-time method showed that the proposed kinetic method has good accuracy. The Se(Ⅳ), Se(Ⅵ), and total inorganic selenium in lake and river water samples have been successfully determined by this method after selective reduction of Se(Ⅵ) to Se(Ⅳ).