Graduate Thesis Or Dissertation
 

The distribution of organic bases in reverse phase liquid chromatography : a study of mechanisms

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  • The distribution of hydrophobic ionogenic organic compounds (HIOC's) between aqueous and nonaqueous phases has been investigated. The HIOC's are aniline and methyl substituted anilines. The aqueous phases are methanol-water mixed solvents with varying pH and ionic strength. The nonaqueous phases are silica and alkyl derivatized silica with ethyl- (C-2), octyl- (C-8), and octadecyl- (C-18) silanes. A gas-liquid equilibration method has been developed to determine the Henry's law constants and the activity coefficients of methyl anilines in methanol-water mixed solvents. The logarithm of the Henry's law constants vary quadratically with the volume fraction of methanol. The chromatographic study has been performed to investigate the effect of three mobile phase factors, fraction of methanol, pH, and ionic strength, on the retention of methyl anilines on different stationary phases. The logarithm of mass distribution ratios, log k's, of methyl anilines vary linearly with the volume fraction of methanol. The ratios of H / k' of methyl anilines increase with increase in methanol in the mobile phase, indicating an increase in the activity coefficients in the stationary phases. This observation is found to be true for different methyl anilines in different stationary phases. A partition model is presented to describe the effect of pH and ionic strength on the retention of HIOC's in the mobile phase. The variation in log k' among neutral and ionic methyl anilines can be explained by linear free energy relationships. Equations are established to predict retention of neutral or ionized methyl anilines from their octanol-water partition coefficients at any methanol content in the mobile phase. Acid dissociation constants of methyl anilines determined from the dependence of log k' on pH are in close agrement with those determined by potentiometric titrations. The effect of ionic strength on the retention of both neutral and ionic species of methyl anilines is negligible. That is, the contribution from electrostatic energy and salting out effect are not significant. The chromatographic study is extended to study the retention of methyl anilines on silica as a function of pH and methanol at a constant ionic strength. The dependence of retention on pH is qualitatively interpreted from an ion exchange reaction between the dissociated silanol groups in the surface and the ionized methyl anilines. The effect of methanol on the retention of methyl anilines and of pyridine on silica is described by a quadratic relationship between the log k' and volume fraction of methanol.
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