Equilibrium Modeling of Mixtures of Methanol and Water

• Published in: Applied spectroscopy Vol. 59; no. 3; pp. 329 - 334
• Main Authors: Puxty, Graeme, Maeder, Marcel, Radack, Kyle P., Gemperline, Paul J.
• Format: Journal Article
• Language: English
• Published: London, England SAGE Publications 01-03-2005
• Subjects: Chromatography, High Pressure Liquid - methods; Complex Mixtures - analysis; Complex Mixtures - chemistry; Computer Simulation; Methanol - analysis; Methanol - chemistry; Models, Chemical; Reproducibility of Results; Sensitivity and Specificity; Spectrophotometry, Infrared - methods; Water - analysis; Water - chemistry; EFA; Equilibrium modeling; Evolving factor analysis; Hydrogen bonding equilibria; High-performance liquid chromatography; Methanol/water mixtures; HPLC; Near-infrared spectroscopy
• ISSN: 0003-7028; 1943-3530
• DOI: 10.1366/0003702053585444

An understanding of the species that form in mixtures of alcohol and water is important for their use in liquid chromatography applications. In reverse-phase liquid chromatography the retention of solutes on a chromatography column is influenced by the composition of the mobile phase, and in the case of alcohol and water mobile phases, the amount of free alcohol and water present. Previous and similar modeling studies of methanol (MeOH) and water mixtures by near-infrared (NIR) spectroscopy have found up to four species present including free MeOH and water and MeOH and water complexes formed by hydrogen bonding associations. In this work an equilibrium model has been applied to NIR measurements of MeOH and water mixtures. A high-performance liquid chromatography (HPLC) pump was coupled to an NIR flow cell to produce a gradual change in mixture composition. This resulted in a greater mixture resolution than has been achieved previously by manual mixture preparation. It was determined that five species contributed to the data. An equilibria model consisting of MeOH, H2O, MeOH(H2O) (log KMeOHH2O = 0.10 ± 0.03), MeOH(H2O)4 (log KMeOH4H2O = −2.14 ± 0.08), and MeOH(H2O)9 (log KMeOH9H2O = −8.6 ± 0.1) was successfully fitted to the data. The model supports the results of previous work and highlights the progressive formation of MeOH and water complexes that occur with changing mixture composition. The model also supports that mixtures of MeOH and water are not simple binary mixtures and that this is responsible for observed deviations from expected elution behavior.