Limonene in Arizona liquid systems used in countercurrent chromatography. II Polarity and stationary-phase retention

The previous article in this series described the physico-chemical properties and chemical compositions of the two phases of the limonene–ethyl acetate–ethanol–water biphasic liquid system. This system was designed to be a “green” version of the so-called Arizona (AZ) scale of heptane–ethyl acetate–methanol compositions in which the heptane–ethyl acetate volume ratio is exactly the same as the methanol–water ratio. The first major difference between the standard and “green” AZ systems is the difference in upper and lower phase densities. The higher density of limonene compared with heptane greatly reduces the density difference of the “green” system: half the compositions have a density difference lower than 0.06 g mL^?1, precluding their use in hydrodynamic CCC columns. The other major difference is the phase polarity. The better distribution of ethanol between the upper organic and lower aqueous phases of the “green” AZ scale renders them more polar than their counterparts in standard heptane-based compositions. The test solutes aspirin and coumarin have higher distribution constants in the “green” AZ compositions. It is revealed that a hydrostatic column is suitable for use with all “green” compositions, with very good phase retention and limited driving pressure at high flow rates. A hydrodynamic column only functioned at limited flow rates with polar compositions of sufficient phase-density difference. The CCC chromatograms obtained with different compositions and columns are shown, and their peak position and sharpness discussed.