Prediction of gas chromatographic retention time via an additive thermodynamic model

A straightforward group contribution model based on thermodynamic parameters was developed to predict retention times for a series of alcohols and ketones on three different stationary phases. Thermodynamic parameters determined from gas chromatographic retention data for structurally similar compounds via a three-parameter model were used to predict the retention times of test molecules consisting of ketones and alcohols. The model worked well for the compounds tested with a root mean square error of prediction of 5.50 s across all compounds, phases, and temperature ranges studied. Considering just the alcohols, the error of prediction was 2.79 s across all phases and temperatures.     

Extrapolation and interpolation of gas chromatographic retention times

Summary An empirical method of extrapolating and interpolating gas chromatographic retention times obtained at three equally spaced isothermal temperatures is described. The accuracy of the method was evaluated from retention time data obtained using packed glass columns. A procedure for constructing retention time tables for homologous series and the derivation of an equation for calculating retention times as a function of temperature is also presented.     

Considerations for the automated collection of thermodynamic data in gas chromatography

Thermodynamic modeling of retention times in gas chromatography depends on the accurate estimation of thermodynamic parameters. Previous research has used manual injections of samples with coinjection of a dead time marker to obtain accurate measurements of the retention factor of analytes. Ideally this process would be automated. Herein an approach is presented by which thermodynamic parameters can be estimated both autonomously and accurately. This method also allows for a consistent estimation of thermodynamic parameters regardless of factors such as data system delays and the nature of the void time marker employed. Ignoring these factors can lead to significant errors in the prediction of retention times when using thermodynamic models.     

Monte-carlo simulation of gas chromatographic separation for the prediction of retention times and peak half widths

Summary A new method for prediction of gas chromatographic retention times and peak half widths is based on the renewal theory. The only requirements are the heats of vaporization of the compounds to be separated and one calibration measurement. With this data, retention times and peak half widths can be predicted for isothermal as well as temperature-programmed gas chromatography. For the separation of non-polar substances on non-polar stationary phases the prediction error for retention times is approx. 1–2%. First simulations of polar molecules and polar stationary phases indicate that this method is also applicable in these cases but some extension will be required.     

The variation of carrier gas viscosities with temperature

After describing simplified equations exspressing the temparature dependency of the viscosity of carrier gases (helium, nitrogen and hydrogen ) relative to a base value, absolute relationships based on the kinetic theory of gases are discussed. Comparative data obtained using various calculation methods are given and are compared to measured values. Based on the kinetic relationshipsm, of viscosity. Finally, the influence of pressure on the viscosity is also briefly discussed. As a supplement, Viscosity data are tabulated for the three gases in the range of 0°C to 400°C in increments of 2 K, calculated using the kinetic relationships.     

Possible amounts of oxygen in the carrier gas as compared to sample amounts

Summary The amount of oxygen which may be present in the gas volume corresponding to a peak is investigated and compared to the sample amounts. It is shown that even with high purity carrier gases one may have a significant excess of oxygen present at low sample amounts. Attention is drawn to the possibility of impurity build-up by diffusion e.g. through the septum.     

Application of thermodynamic‐based retention time prediction to ionic liquid stationary phases

First‐ and second‐dimension retention times for a series of alkyl phosphates were predicted for multiple column combinations in GC×GC. This was accomplished through the use of a three‐parameter thermodynamic model where the analytes’ interactions with the stationary phases in both dimensions are known. Ionic liquid columns were employed to impart unique selectivity for alkyl phosphates, and it was determined that for alkyl phosphate compounds, ionic liquid columns are best used in the primary dimension. Retention coordinates for unknown phosphates are predicted from the thermodynamic parameters of a set standard alkyl phosphates. Additionally, we present changing retention properties of alkyl phosphates on some ionic liquid columns, due to suspected reaction between the analyte and column. This makes it difficult to accurately predict their retention properties, and in general poses a problem for ionic liquid columns with these types of analytes.     

New stationary phase polarity parameters considering the electric intermolecular interactions in gas chromatographic column

Summary The possibility of evaluation of the parameters representing the dispersive solute-solvent interactions is presented. B_N and B_s values can be used to describe the liquid phase polarity and to predict the retention indices of alcohols when the model polyxyethylene glycol dialkyl ethers and their sulphur analogs are used as stationary phases. The possibility of the first ionization potentials estimation is also presented.     

A new gas chromatographic retention index for pesticides and related compounds

A new gas chromatographic (GC) retention index based on a homologous series of tri-n-alkylamines is proposed for use in the detection of pesticides and related compounds because the standard n-paraffin hydrocarbons used for the Kovats index do not show up well on the nitrogen-phosphorus detectors commonly used in pesticide analysis. Using fused silica bonded phase capillary columns (DB-1 or DB-5), the trialkylamine indices of 106 selected pesticides and related compounds were measured and their relationship to the Kovats index determined.     

Prediction of gas chromatographic retention indices of linear,branched, and cyclic alkanes from their physicochemical properties

Kováts retention indices for a series of linear, branched, and cyclic alkanes on squalane at any temperature, and on other stationary phases of different polarity at a given temperature, are related to physicochemical properties of the solutes, such as boiling point and molar refraction, by multiple regression analysis. The equations found permit calculation of the Kováts retention index for all alkanes, with standard deviations close to experimental error. The same equations can also be used for calculating the physicochemical parameters they contain.     

Viscosities of carrier gases at gas chromatograph temperatures and pressures

Summary Equations are derived for viscosities of H₂, He, N₂ and Ar for use at chromatographic temperatures which are accurate to within 0.3% for H₂, and 0.1% for the other gases. The effect of pressure is usually negligible but may increase the viscosity of N₂ or Ar by as much as 0.5% at 25°C or lower and 5 atm or higher.     

Influence of the carrier gas on retention factors of gaseous hydrocarbons on polytrimethylsilylpropyne using capillary gas chromatography

The retention factor and height equivalent of a theoretical plate for gaseous hydrocarbons C₁—C₄ were studied on capillary columns with the layer of the new polymeric adsorbent polytrimethylsilylpropyne (PTMSP) as functions of the nature and pressure of the carrier gas. The retention factor k increases in the series helium < nitrogen < carbon dioxide. The k values depend linearly on the average pressure of the carrier gas in a capillary column with the adsorption PTMSP layer.     

Phenomenon of dual‐ and single‐retention behaviors of solutes and its validation by computational simulation in linear programmed temperature gas chromatography

The current theory of programmed temperature gas chromatography considers that solutes are focused by the stationary phase at the column head completely and does not explicitly recognize the different effects of initial temperature (T_o) and heating rate (r_T) on the retention time or temperature of a homologue series. In the present study, n‐alkanes, 1‐alkenes, 1‐alkyl alcohols, alkyl benzenes, and fatty acid methyl esters standards were used as model chemicals and were separated on two nonpolar columns, one moderately polar column and one polar column. Effects of T_o and r_T on the retention of nonstationary phase focusing solutes can be explicitly described with isothermal and cubic equation models, respectively. When the solutes were in the stationary phase focusing status, the single‐retention behavior of solutes was observed. It is simple, dependent upon r_T only and can be well described by the cubic equation model that was visualized through four sequential slope analyses. These observed dual‐ and single‐retention behaviors of solutes were validated by various experimental data, physical properties, and computational simulation.     

Application of histograms in evaluation of large collections of gas chromatographic retention indices

The effective use of gas chromatographic retention data presented in the form of retention indices (RI) requires the development of a comprehensive structure-based digital archive of retention parameters. Development of such an archive includes the collection of all available RI values for a variety of compounds including replicates measured under slightly different conditions. Review of retention data often shows a relatively wide range of RI values for certain well studied compounds that is larger than expected on the basis of the simple reproducibility of experimental measurements. The finding of unusual RI data distributions and their examination presents a possible way to detect and correct errors during the development of comprehensive RI libraries.     

Relationship between thermodynamic characteristics and isothermal retention indices

Summary Thermodynamic characteristics determined from retention data measured under isothermal conditions were used for the calculation of retention indices of a number of model compound. The minimum retention index difference required for the identification of two adijacent compounds as well the temperature dependency of retention index are discussed. The possibility of alculating thermodynamic characteristics from retention indices published in the literature was also investigated.Dedicated to Professro J. F. K. Huber on the occasion of his 60th birthday.     

Comparing columns for gas chromatography with the two-parameter model for retention prediction

The retention times of selected compounds in temperature programmed gas chromatography were predicted using a two-parameter model, on the basis of thermodynamic data obtained from isothermal runs on seven capillary columns, primarily substituted with 5% diphenylsiloxane. The scope for using thermodynamic data obtained from isothermal runs on one column to optimize separation on a different column or a different instrument setup was investigated. Additionally, the predictive utility of thermodynamic data obtained using a DB-5 column that had been in use for three years was compared to that of a new column of the same model. It was found that satisfactory separation could be achieved on one capillary column or instrument setup on the basis of thermodynamic data obtained using a different column or instrument set-up.     

Selection of carrier gas velocity in the analysis of a multicomponent sample

Summary The selection of the average linear carrier gas velocity in the analysis of a multicomponent mixture under isothermal and programmed-temperature conditions is discussed. It is shown that one shouls always select a velocity which is at least equal but preferably higher than the optimum average gas velocity of the earliest peak at the initial column temperature.These symbols essentially correspond to those specified by the British Standard [6], ASTM [7] and IUPAC [8] GC nomenclastures.     

The temperature dependence of retention indices in gas chromatography

Summary A linear dependence of (T–T₁)/[1(T)–1(T₁)] on temperature (considering the retention index 1(T₁) at temperature T₁ as a standard value) is derived. Both ther retention index at an assigned temperature and the temperature dependence of the retention index can be calculated from retention data measured at two temperature-programing rates.