Luminol Chemiluminescence with Heteropoly Acids and its Application to the Determination of Arsenate, Germanate, Phosphate and Silicate by Ion Chromatography

Abstract

A flow-injection chemiluminescence (CL) method has been proposed for sensitive determination of arsenate, germanate, phosphate and silicate, after separation by ion chromatography (IC). The post-column detection system involved formation of heteropoly acid in a H 2 SO 4 medium before the CL reaction with luminol in an NaOH medium. For separation, heteropoly acid formation and the CL detection reaction, pH requirements were not compatible. When present as a heteropoly acid complex with molybdenum(VI), germanium(IV) and silicon(IV) caused CL emission from oxidation of luminol, and such a CL oxidation of luminol was observed analogously for arsenic(V) and phosphorus(V) but with the addition of metavanadate ion to the acid solution of molybdate. Good sensitivity for the three analytes arsenic(V), germanium(IV) and phosphorus(V) could be given by a single set of reagent conditions, chosen carefully. Another set was suitable for determining phosphorus(V) and silicon(IV). The minimum detectable concentrations of arsenic(V), germanium(IV), phosphorus(V) and silicon(IV) were 10, 50, 1 and 10 (μg 1 -1 , respectively. Linear calibrations for arsenic(V), germanium(IV), phosphorus(V) and silicon(IV) were established over the respective concentration ranges of 10-1000, 50-25000, 1-1000 and 50-10000 μg1 -1 . The proposed IC-CL method was successfully applied to analyses of a seaweed reference material, rice wine and water samples.