Generator column method, water

Water solubility determined by the generator column method by van Haelst et al. [244]. n-Octanol/water partition coefficients determined by Van Haelst et al. using the slow stirring method [245]. 

The experimental approaches are similar to those for solubility, i.e., employing shake flask or generator-column techniques. Concentrations in both the water and octanol phases may be determined after equilibration. Both phases can then be analyzed by the instrumental methods discussed above and the partition coefficient is calculated from the concentration ratio Q/Cw. This is actually the ratio of solute concentration in octanol saturated with water to that in water saturated with octanol. 

Wasik, S. P., Miller, M. M., Tewari, Y. B., May, W. E., Sonnefeld, W. J., DeVoe, H., Zoller, W. H. (1983) Determination of the vapor pressure, aqueous solubihty, and octanol/water partition coefficient of hydrophobic substances by coupled generator column/ liquid chromatographic methods. Res. Rev. 85, 29 42. 

Reza, J., Trejo, A., Vera-Avila, L.E. (2002) Determination of the temperature dependence of water solubilities of polycyclic aromatic hydrocarbons by a generator column-on-line solid-phase extraction-liquid chromatographic method. Chemosphere 47, 933-945. 

Accurate values of Pow are clearly necessary for the ultimate calibration of all surrogate systems, but, in practice, direct measurements of Powby the traditional shake-flask method are seldom used. Particularly for compounds with low water solubility, experimental difficulties may arise from problems in phase separation without carryover, sorption to glass surfaces, or from formation of emulsions. All of these introduce serious uncertainties into the concentrations in the appropriate phases, and may consequently lead to substantial errors in the estimates of partition coefficients. The problem is particularly acute for compounds with extremely low solubility in water such as the chlorinated dibenzo[l,4]dioxins for which widely varying values have been reported (Marple et al. 1986 Shiu et al. 1988). For such compounds, use of a generator column has been advocated (De Voe et al. 1981 Woodburn et al. 1984). In essence, the following steps are carried out (1) a solution of the test substance in octanol is equilibrated with water and the concentration in the octanol phase is determined, (2) the octanol phase is... 

The column method also has several steps which may result in a negative bias on measured aqueous solubility. The lack of water-solute equilibrium in the generator column itself may produce an outlet concentration lower than the "true solubility according to Stolzenburg and Andren (8). This result also has been modeled with a beta distribution (93-percent confidence level of -3 percent). 

Generator Column This method is the same as that used to measure vapor pressure with the exception that water rather than air is passed through the column containing inert support material coated with the compound in question. This procedure avoids the mechanical action that generates the dispersed aggregates, however, if insufficient contact time is provided to establish equilibrium an underestimate of the solubility would result. Solubility data reported for some polynuclear... 

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