Prediction of the retention in reversed-phase liquid chromatography using solute–mobile phase–stationary phase polarity parameters

• Published in: Journal of Chromatography A Vol. 955; no. 1; pp. 19 - 34
• Main Authors: Torres-Lapasió, J.R., Garcı́a-Alvarez-Coque, M.C., Rosés, M., Bosch, E.
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 26-04-2002; Elsevier
• Subjects: Algorithms; Analytical chemistry; Chemistry; Chromatographic methods and physical methods associated with chromatography; Chromatography, Liquid - methods; Exact sciences and technology; Other chromatographic methods; Retention prediction; Polarity measurements; Phase composition; Hydrocarbon; Chromatographic retention; Benzene derivatives; Prediction; HPLC chromatography; Theoretical study; Iterative method; Polycyclic aromatic compound; Mobile phase; Reversed phase chromatography; Functional group; Stationary phase
• ISSN: 0021-9673
• DOI: 10.1016/S0021-9673(02)00205-4

A previously reported algorithm, based on the equation:
log
k=(
log
k)
0+p(P
N
m
−P
N
s
)
, that relates the retention in reversed-phase liquid chromatography with solute (
p), mobile phase (
P
m
N
) and stationary phase (
P
s
N
) relative polarity parameters, is improved. The retention data reported by several authors for different sets of compounds, eluted with acetonitrile–water and methanol–water mixtures, are used to test the algorithm and elaborate a database of
p values. The methodology is successfully applied to predict the retention using
P
m
N
values calculated as
P
m
N
=1.00−(2.13
ϕ)/(1+1.42
ϕ) for acetonitrile–water and
P
m
N
=1.00−(1.33
ϕ)/(1+0.47
ϕ) for methanol–water,
ϕ being the organic solvent volumetric fraction. The polarity parameters are demonstrated to be useful to transfer retention data between solvent systems and between columns. Accordingly, the retention in a solvent system is predicted by characterising the working column with a small training set of compounds having diverse polarities, and using the
p values known for another solvent system or column. The
p polarity parameter is found to be a good descriptor of the retention, allowing the prediction of the expected elution order and peak overlaps.