Analytical Sciences

Abstract − Analytical Sciences, 17(12), 1401 (2001).

A Unified Ion Chromatographic System for the Determination of Acidity and Alkalinity
Wenzhi HU,*  Kiyoshi HASEBE,** Alexander ILES,** and Kazuhiko TANAKA***
*Division of Chemistry, Graduate School of Science, Hokkaido University, Sapporo 060-0810, Japan
**Division of Material Science, Graduate School of Environmental Earth Science, Hokkaido University, Sapporo 060-0810, Japan
***National Institute of Advanced Industrial Science and Technology at Seto, 110, Nishiibara-cho, Seto, Aichi 489-0884, Japan
A unified ion chromatographic (IC) system was developed for the determination of acidity or alkalinity. Separation column used was a reversed-phase ODS packed column, which had been modified by saturating it with lithium dodecylsulfate. A slightly acidified LiCl (50 mM LiCl and 0.05 mM H2SO4) aqueous solution was used as the eluent. By conditioning the separation column in this way, both H+ and Li+ ions became bound to the stationary phase. Dodecylsulfate groups with Li+ counterions acted as cation-exchange sites for the separation of hydrogen ions (free acidity determination). The remaining dodecylsulfate groups, with H+ counterions acted as a titrant, which reacted with basic species (total alkalinity determination). The acidity or alkalinity of each sample was measured according to the change in conductance from the eluent baseline level. A positive peak was observed from those samples with a free acidity greater than their total alkalinity, due to the separation/elution of free H+ ions. A negative peak was observed from those samples with a free acidity less than their total alkalinity. This was due to an equivalent amount of eluent H+ ions being re-supplied to the stationary phase while the ''solid titrant'' consumed by the acid-base reaction was regenerated. The retention time for the peak corresponding to the acidity or alkalinity was governed by the retention time for H+ ions in this IC system. Samples with a free acidity greater than 2.25 uM (tested by determination of H+ ions in pure water in equilibrium with atmospheric CO2) could be analyzed by this method. A very similar detection level was obtained for alkalinity (tested by analyzing standard aqueous NaHCO3 solutions). Aqueous solutions of some strong-acid/strong-base inorganic salts were found to be slightly alkaline. This was measured as a percentage, relative to an NaHCO3 solution at the same concentration. Solutions of NaClO4, Na2SO4, NaI, NaNO3, and NaCl, gave comparative alkalinity values of 8.75%, 1.83%, 0.42%, 0.35%, and 0.33%, respectively.