Analysis of hydroxide, inorganic sulphur species and organic anions in kraft pulping liquors by capillary electrophoresis

Abstract

A new method has been developed for the determination of hydroxide, sulphide, thiosulphate, sulphate, sulphite, chloride, oxalate and formate in kraft green, white and black liquors by capillary electrophoresis. The method provides baseline resolution of all analytes of interest using an electrolyte composed of 10 mM sodium chromate and 2 mM tetradecyltrimethylammonium hydroxide. Separations are conducted under constant current conditions at 25 °C and analytes are quantified by indirect UV-detection at 275 nm. A brief, post run wash of the capillary with 0.5 M NaOH and water gave improved inter- and intra-run repeatability of both migration times and peak areas. Sulphide and other oxysulphur species were relatively stable in white and green liquors diluted in helium-sparged water. However, sulphide present in black liquor samples diluted in the same solvent underwent rapid oxidation to form sulphite and thiosulphate, thereby precluding the measurement of all three anions. We discovered that quinone-type compounds present in black liquor catalyze the oxidation of sulphide and that the addition of reduced glutathione at a concentration of 1 mg/mL during black liquor dilution completely stabilized sulphide, sulphite and thiosulphate for at least one hour, thus allowing for quantitative analysis of the analytes. A mechanism is proposed to explain the action of both quinones and that of glutathione. Results obtained by the new method compared well with those obtained by ion chromatography, titrimetry, and from spike-recovery experiments.