Factor analysis of some chemical and physical influences in gas-liquid chromatography

Abstract

Some fundamental factors influencing retention indices in gas-liquid chromato raphy are studied by the mathematical technique offactor analysis. Eight abstract eigenvectors are required to span the factor space and to reproduce the data matrix within experimental error. A scaling-test vector termed the uniqueness test is used to compare compounds in the scheme. A procedure is presented for accurately predicting a solute retention index on any stationary phase in the system if the retention indices of that solute on eight carefully chosen stationary phases are known. The procedure can also be used to predict retention indices of any solute in the system on a given stationary phase if the retention indices of eight chosen solutes on that column are known. The usefulness of this procedure for predicting retention indices is illustrated for four solutes which were purposely left out of the analysis. Using the rotation part of the factor analysis, the following solute physical parameters tested successfully as factors of the space: molar polarization and dipole moment squared.A solvent property which tested successfully was the uniqueness of etherlike linkages.

Predicting solvation energies for kinetic modeling

“…Initial work in this area, focused on establishing a selectivity ranking of solvents 78 using the ideas of characteristic phase constants and on obtaining solute descriptors, was performed by Rohrschneider. [93][94][95] His preliminary work was followed by several others including McReynolds, 96 Snyder, 97,98 Weiner and Howery, 99,100 Hawkes, 101 and Wilson et al [102][103][104] It was subsequently realized that the approach for solvent characterization using phase constants was inadequate, 78,[105][106][107][108][109] and the use of the partial molal Gibbs free energy as a quantitative measure of stationary phase ranking was proposed. 78 An excellent review of this topic is available by Cramer and Truhlar.…”

Teaching chemometrics: A course on application of mathematical techniques to chemistry

“…Chemists have found several forms of factor analysis to be useful for solving chemical problems. Principal component analysis has been used for the deconvolution of overlapped chromatographic peaks (35), for the analysis of the mass spectra of mixtures (36), and for studying retention in gas chromatography (37). Target, transformation factor analysis has been applied to the qualitative and quantitative determination of the components of mixtures, via mass spectral analysis (38).…”

Multicolor Chemical Imaging by Sum Frequency Generation Imaging Microscopy of Monolayers on Metal Surfaces

“…The application of FA in chemistry has been pioneered by Malinowski in the 1980s . The FA method has been applied in Raman spectroscopy, infrared spectroscopy, nuclear magnetic resonance, mass spectrometry, and so on to determine reaction mechanics, kinetics, and the number and identities of components in a series of related multicomponent mixtures. − ,− …”