This paper demonstrates the use of the first on‐line capillary electrophoresis instrument with continuously flowing electrolyte solutions and sequentially applied sample introduction. The system was used in on‐line determination of chloride, sulfate, and carbonate concentrations of process waters at a pulp mill. The module constructed for on‐line feeding of the solvents is described. Separations were performed in a pyromellitic acid‐hexamethonium hydroxide‐triethanol amine mixture at pH 7.7 with indirect‐UV detection at 254 nm. Two standard mixtures were used to show the repeatability of the analysis and to estimate the accuracy of the on‐line system. The analytes could be separated within 240 s. Sampling from a pulp machine could be accomplished on‐line at 6‐minute intervals. On‐line tests gave a limit of detection and a limit of determination in the low mg/L range.

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An online high temperature capillary electrophoresis instrument (HotUCE), a potentiometer and an ion chromatograph were used in studies on corrosive ions and changes in potential at normal pulping process temperatures in experimental liquors modelling pulp cooking processes at mills. The aim was to evaluate the stress corrosion cracking (SCC) susceptibility of stainless steels. The HotUCE instrument and the potentiometer were online coupled with an autoclave, where welded duplex stainless steel samples were immersed for 500 h in simulated high ionic strength hot black liquor (HBL), hot white liquor (HWL) or green liquor (GL) at 130, 150 or 170 8C, respectively.The results showed that only minor amounts of oxidized sulphur compounds were formed. The concentrations of corrosive sulphur anions were calculated against sulphur standards. Amounts of sulphur species in the liquor correlated with the changes in the potential of the duplex stainless steel specimens during the cooking experiments. The formation of sulphite during cooking was greater in HWL than in HBL. Changes in the potential showed that reduction processes occurred during the SCC tests. The results indicate that the SCC risk is enhanced at higher temperatures, probably, due to the increased formation of thiosulphate.