Redox substoichiometric isotope dilution analysis of metallic arsenic for antimony

In 1 M HCl solution Sb(III) reacts with N-benzoyl-N-phenylhydroxylamine (BPHA) to form a complex extractable into chloroform while the extraction of Sb(V) is negligible. The redox substoichiometric isotope dilution analysis based on this reaction was applied to the determination of antimony in metallic arsenic. After the dissolution of metallic arsenic, Sb(V) was separated from As(V) by a tribenzylamine extraction from 8 M HCl solution and the extracted Sb(V) was stripped into 0.5 M NaOH solution. Thereafter, all the Sb(V) were completely reduced to Sb(III) by bubbling SO2 gas through 3 M HCl solution. As the substoichiometric reaction, the oxidation of Sb(III) to Sb(V) by a substoichiometric amount of potassium dichromate was used, followed by separation of these species by the BPHA extraction of Sb(III). The substoichiometric oxidation of Sb(III) was found to be quantitative over HCl concentration range from 0.8 to 1.2 M. The amount of antimony was determined by isotope dilution analysis using the method of carrier amount variation. By the present method the determination of as small as 0.36 μg antimony was accomplished with a good accuracy (relative error; 5.6%) and also the method was successfully applied to the determination of antimony in arsenic samples containing known amounts of Sb(III) and in metallic arsenic. The present method gives reliable results with the good accuracy and precision. (author)