The impact of perchlorate ions and acetonitrile medium on copper redox couple was investigated. The acetonitrile solvent and perchlorate ions were found to synergistically increase the redox potential of Cu(II)-Cu(I) couple, thereby increasing its ability to oxidize more systems and expand the copper redoxi metric analysis window. The difference in the behavior of thiourea towards copper(II) salts in aqueous and non aqueous media was also explored. Based on the synergistic effect, an electroanalytical method for com position analysis of copper(I) thiourea complexes was proposed. Kinetic and quantum chemical studies have been used for mechanistic insight into synergistic effect of acetonitrile and perchlorate ions on copper redox couple.
Abstract. The objective of this study is to develop a simple, environmentally benign alternate analytical method for simultaneous estimation of iron oxidation states. This proposed method of iron speciation is based on 1,10-phenanthroline (phen) modified redox potential of transition metal ions. In a pre-step excess cerium(IV) oxidizes iron(II) in sample to iron(III). Initial back titration of un-reacted cerium(IV) with cobalt(II) in presence of phen gives amount of iron(II) in sample, reduction of iron(III) with cobalt(II) is then used to estimate total iron as iron(III). The potentiometric titration method has been successfully tested for determinations of iron(II) and total iron in synthetic and natural samples and represents a distinctively green alternative to other reported protocols of iron speciation analysis.
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