ELSEVIER Journal of Chromatography A, 753 (1996) 253-260
JOURNALOF
CHROMATOGRAPHY A
Mixed-mode liquid chromatography of carboxylic acids and
inorganic anions on a latex-based pellicular stationary phase 1
Gabriella Rrvrsz, Prter Haj6s*, Hortenzia Csiszfir
Department of Analytical Chemistry, University of Veszpr#m, P.O. Box 158, Veszpr~m H-8201, Hungary
Received 26 February 1996; revised 9 July 1996; accepted 17 July 1996
Abstract
The retention behaviour of mono-, dicarboxylate and inorganic anions on latex-based pellicular anion-exchanger was
investigated. This paper is focused on the possible retention mechanism providing a retention database on a variety of mobile
phase compositions. It has been demonstrated that anions can interact with the cation-exchange layer on the highly
crosslinked latex-based pellicular phase as well as with the anion-exchange sites. A hypothesis is proposed to explain a
mixed-mode retention of the series of analytes. A combination of two mechanisms has been found responsible for the
enhanced selectivity: ion-exchange and ion-exclusion. Applications include the separation of formate, acetate, propionate,
lactate, pyruvate, oxalate, malonate, succinate, tartrate, fumarate, maleate, chloride, nitrate and sulphate with NaOH eluent
using suppressed conductivity detection. The study effectively characterizes the behaviour of different analytes under elution
conditions of practical importance.
Keywords: Inorganic anions; Carboxylic acids
1. Introduction
Both carboxylic acids and their carboxylate salts
are widely used in chemistry and in commercial
products [1-3]. In the pharmaceutical industry,
organic acids are used as antioxidants, preservatives,
acidifiers and drug adsorption modifiers. Various
diseases have been correlated with increased con-
centrations of organic acids in biological fluids.
Organic acids are also fundamental components of
fruits. Therefore a rapid and simple method for
determining these compounds is required.
Carboxylic acids are usually separated by three
*Corresponding author.
' Paper presented at the International Ion Chromatography Sym-
posium 1995, Dallas, TX, USA, 1-5 October 1995.
different liquid chromatographic methods: anion-ex-
change [4,5], ion-exclusion and reversed-phase chro-
matography [6-8]. Traditional high-performance liq-
uid chromatography methods use refractive index
(RI), ultraviolet (UV) absorption and derivatization
fluorescence techniques for the detection of the
acids. The most common application is the ion-
exclusion technique. It is especially attractive as an
adjunct to ion-exchange chromatography since selec-
tivities obtained by these methods are quite different.
Strong inorganic acid anions are excluded from the
resin phase in a single peak according to the Donnan
principle and elute at the void volume. Weaker and
protonated species existing largely in the molecular
form are retained on the stationary phase by a
combination of ion-exclusion and hydrophobic inter-
actions. For low-molecular-mass components, ion-
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