An extraction-chromogenic system for vanadium(IV,V) based on 2,3-dihydroxynaphtahlene

A liquid-liquid extraction-chromogenic system for vanadium(IV, V) containing 2,3-dihydroxynaphtahlene (DN), 2,3,5-triphenyl-2H-tetrazolium chloride (TTC), water and chloroform was studied in detail. When the vanadium is in the oxidation state of IV, the extracted species are aggregates containing three 1:2:1 (V:DN:TTC) ion-pair units composed of triphenyltetrazolium cations (TT+) and chelate anions {[VIVO(DN)(DNH)]− (I) and/or [VIV(OH)(DN)2]− (II)}. When the initial oxidation state of vanadium is V and the DN concentration is high, vanadium(V) is reduced by DN to a lower oxidation state, V(IV). However, at low DN concentration, vanadium(V) can enter the organic phase as a part of an ion-pair consisting of TT+ and [VVO2(DN)]− (III). The ground-state equilibrium geometries of the anions I, II, and III were optimized by quantum chemical calculations using BLYP/6-31++G⋆. The following characteristics were determined under the optimum conditions for VIV extraction: absorption maximum λmax = 333 nm, molar absorptivity ε333= 2.1x104 dm3 mol−1 cm−1, Sandell’s sensitivity SS = 2.4 ng cm−2, and fraction extracted E = 98%. The conditional extraction constant was calculated by two independent methods. The calibration graph was linear in the range 0.1-3.1 μg cm−3 (R2=0.9994) and the limit of detection was 0.03 μg cm−3.