A relationship between the retention indices on nematic and isotropic phases and the shape of polycyclic aromatic hydrocarbons

Summary An equation has been derived allowing to predict retention index values on nematic phases from computable parameters and sizes of the molecules of polycyclic aromatic hydrocarbons. Another equation, which has also been derived, allows to determine the shape parameter of a molecule from chromatographic data.     

Correlation of unified retention indices for OV-101 and squalane

Summary Gas chromatographic unified retention indices for 43 hydrocarbons (alkanes and cycloalkanes) are given for squalane and OV-101. Comparison of these values and unified retention index increments are presented as linear regression equations with high correlation coefficients and acceptable standard deviations.     

Retention index values of hydrocarbons on open-tubular columns coated with methylsilicone liquid phases

Summary The influence of temperature and liquid phase film thickness of open-tubular (capillary) columns on the retention index values of hydrocarbons on methylsilicone liquid phases is discussed. Data obtained on methylsilicones and squalane are compared. Retention index values of 43 hydrocarbons between 40 and 70 °C on OV-101 liquid phase are listed.     

Relationship between the average molecular polarizabilities of polycyclic aromatic hydrocarbons and their retention indices determined on various stationary phases

The Kováts retention indices of 10 polycyclic aromatic hydrocarbons were determined on SE-30, OV-101, SE-52, OV-7 and OV-17 stationary phases. A significant correlation has been found between the retention indices and the average molecular polarizabilities of the analyzed substances. Equations were derived for the direct determination of the average molecular polarizabilities from the retention index values. The influence of the temperature on this relationship is also indicated.     

Unified retention index of hydrocarbons separated on dimethylsilicone OV-101

Summary Gas chromatographic retention indices of 51 hydrocarbons were determined on OV-101 dimethylsilicone between 40 and 70°C. From the measured data the unified retention indices were calculated.     

Unified retention indices of hydrocarbons on BP-1 dimethylsiloxane stationary phase

Summary Gas chromatographic retention indices for 23 hydrocarbons were determined on BP-1 dimethylsiloxane between 45 and 65°C. From the data measured unified retention indices were calculated. These values agree well with the corresponding experimental values. The values of unified retention indices obtained on BP-1 are compared with those determined on OV-101 and on squalane. The differences between the unified and the experimental retention indices on BP-1, OV-101 and squalane columns are shown.     

Gas chromatographic retention indices for alkenes on OV-101 and squalane capillary columns

Summary Gas chromatographic retention indices for 47 C₅ to C₈ alkenes on OV-101 dimethylsilicone at 50 and 70 °C were determined within a standard deviation of 0.3i.u. Data obtained on OV-101 are compared with those measured on squalane. The comparison of the retention index and dl/dT values from both columns is presented as linear regression equations with correlation coefficients greater than 0.98.     

Factors affecting the retention of polycyclic aromatic hydrocarbons in gas chromatography

Summary The retention index of a planar polynuclear aromatic hydrocarbon on the GC phases OV-101, SE-52, and OV-17 is strictly related only to the boiling point, and less closely to the relative molecular mass. The very approximates relation with connectivity index ins only a consequence of the latter. On a nematic lqiuid crystal phase, a variation of activity coefficient, expressed in terms of a shape factor, also influences the retention of PAH.     

Determination of average molecular polarizabilities of polycyclic aromatic hydrocarbons directly from retention indices

Summary A significant correlation has been found between the retention indices of polycyclic aromatic hydrocarbons on non-polar stationary phases and the average molecular polarizabilities of the molecules separated on these phases. Equations have been derived for the determination of the average molecular polarizabilities, directly from the retention indices.     

Correlation equations for prediction of gas chromatographic separation of hydrocarbons on squalane

Summary The retention index of several hydrocarbon classes on squalane was found to be predictable (within two index units) with help of a physico-chemical index and a correction-structural number. A large number of structural elements were examined by means of correlation analysis and regression equations were obtained for calculation of the structural number. The multinomial regression equations were simplified by combining in one factor the important structural elements. A set of a limited number of selected representatives for every hydrocarbon class was found to give reliable estimations for the regression coefficient equations.     

Calculation of retention indices at an assigned temperature from temperature-programmed data

Summary A method is presented for the calculation of retention indices at an assigned temperature from temperature-programmed data. If the retention times at two different program rates for the solutes and the n-alkanes are known, the retention indices at an assigned temperature can be calculated directly.     

Gas chromatographic retention of alkyl phosphates on ionic liquid stationary phases

Retention behaviors of alkyl phosophates were studied on a series of ionic liquid gas chromatography columns. The selectivity of the IL columns for alkyl phosphates were compared with a 5% phenyl column as a route to evaluating the potential use of IL columns in the analysis of alkyl phosphates in petroleum samples in both one- and multi-dimensional GC. Most interestingly, we demonstrate for the first time the dependence of elution order on separation temperature for members of a homologous series of compounds. At low temperatures it was found that trihexyl phosphate eluted before trioctyl phosphate, while at higher temperatures this pattern was reversed.     

Influence of Van der Waals' volume of ethers,esters, carbonyls and alcohols on retention in gas chromatography stationary phases of different polyrity

Summary Equations for Retention Index (I) versus Van der Waals, volume (V_w) on squalane are studied for alcohols, carbonyls, esters and ethers. Each equation includes linear and branching substances with different positions of the functional group in the carbon chain. The study is extended to stationary phases with polarities from 4.29 to 91.54 on the Tarjan et al. scale. Variations of the slope and origin ordinate values with the polarity of the stationary phase are discussed.     

The true physical meaning of the corrected retention volumes in GC

Summary Through a straightforward mathematical derivation it is shown that the compressibility correction factor equals the ratio of gas pressure at the column outlet to the average pressure in the column, . Therefore, by multiplying by this factor, the experimentally measured retention volumes can be recalculated to the average pressure in the column. Corrected retention volumes thus represent the volume of the mobile phase under real conditions of chromatography in the column. Appropriate definitions for corrected retention volumes and factorj are formulated.     

Theoretical interpretation of the retention indices of alkylbenzenes

Summary The correlation between retention data of alkylbenzenes in GLC (measured on the stationary phase OV-101) and contribution of the Gibbs solvation energy are investigated in order to determine the dominant factor controlling retention. The retention in GLC can be predicted with help of our thermodynamic retention model.     

Calculation of retention indices of isoparaffins on different phases

Summry The changes in the retention indices of isoparaffins on phases with different polarities (according to the Rohrschneider-McReynolds system) are examined. It is established that the values of the retention index do not depend on the polarity of the following phases: squalane, normal C₂₄, C₂₈, C₃₀, C₃₂, C₃₄ and C₃₆ paraffins, C₈₇H₁₇₆, the silicones SE-30, OV-1, OV-101, as well as dinonyl phthalate and acetyl tributyl citrate. An empirical equation established peremits the prediction of retention indices of C₆–C₁₀ isoparaffins at different temperatures on all these phases.     

The chromatographic behaviour of cycloolefins on stationary phases of different polarity. Prediction of their retention indices and boiling points

Summary The retention indices of mono and polycycloolefins with endo or exo double bonds, on squalane or polypropylenglycol 425 are related to their physico-chemical properties such as boiling point, molar volume, molar refraction, and refractive index. Equations have been empirically obtained, from which accurate retention indices of these compounds can be predicted. Unknown boiling points of some of these compounds can also be calculated from their lineal relation with the retention index on squalane.     

Porous polymers coated with stationary phases. Contribution of the support to retention behaviour in gas chromatography

Summary The gas chromatographic behaviour of a series of compounds of different polarity on columns of Ethofat 60/25 on Chromosorb P HMDS (an inactive support) and Chromosorb 101 (an active support) was investigated. To observe how the support influences the chromatographic process, we separated the contribution to the retention volume of the interaction phenomena associated with the stationary phase, the solid support and the corresponding interfaces. In some cases the Chromosorb 101 exerts an influence on the process even with high percentages (>10%) of stationary phase. The values of the experimental partition constants of a series of compounds and the factors that contribute to adsorption on these columns are calculated.