Gas chromatography at finite concentrations. Part 2.—A generalised retention theory

Conder, J. R.; Purnell, J. H.

doi:10.1039/tf9686403100

Cited by 111 publications

(41 citation statements)

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“…However, all three are capable of giving consistent KL results for solutes which exhibit multiple sorption mechanisms. The implications of this study and, largely, the earlier studies of 14,16,17) are evident. In particular, bulk solution thermodynamic quantities for testing theories of nonelectrolytic mixtures (15) or for determining hydrogenbond association constants (5, 6 ) can now be obtained with greater confidence for systems which were previously considered to be too troublesome and error prone.…”

Section: Discussionmentioning

confidence: 74%

Concurrent solution and adsorption phenomena in gas-liquid chromatography. Comparative study

Liao¹,

Martire²

1972

Anal. Chem.

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A study is made of three methods for obtaining bulk liquid-gas partition coefficients ( K L ) from GLC retention measurements on solute-liquid phase systems where a multiple sorption mechanism leads to sample size-dependent peak maximum retention times and asymmetric peak shapes. The methods compared all involve retention measurements on several columns differing only in liquid phase weight per cent, followed by extrapolations to give infinite dilution bulk retention volumes. The test solutes studied on four n-octadecane columns at 40.0 O C gave the following average K Z values: n-propanol, 110.3; see-butanol, 55.8; and methylisopropylamine, 106.8. Evidence is found for adsorption of the alcohols on the solid support and at the gas-liquid interface. The relative merits of the three approaches, which yield K L values in excellent agreement with each other, are compared. The implications of this study are discussed. SOLUTE ADSORPTION at the carrier gas-liquid phase interface and/or on the solid support in gas-liquid chromatography (GLC) usually leads to peak asymmetry, to sample size dependent peak maximum retention times, and to retention parameters which depend on the weight per cent of liquid phase in the column packing. This hinders separations, the assignment of meaningful retention parameters, and the determination of bulk solution thermodynamic quantities (1-5).Recently, two methods have been proposed for dealing with chromatographic peaks which are the result of concurrent solution and adsorption partitioning mechanisms (2-6). In these studies the problem of extracting meaningful bulk solution partition coefficients (or retention volumes) was treated. The approaches will be briefly described in the next section. The purpose of the present study is to compare the two methods, and to suggest an alternative approach which involves the production and analysis of solution dominated elution peaks.

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Section: Discussionmentioning

confidence: 74%

Concurrent solution and adsorption phenomena in gas-liquid chromatography. Comparative study

Liao¹,

Martire²

1972

Anal. Chem.

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“…(1) and (2) and the velocity of the discontinuities (Eq. 4), which have been established previously (2)(3)(4). Then we shall show how the general, mathematical theory of the stability of the discontinuities (8) can be applied and combined to the Downloaded by [Columbia University] at 12:30 05 February 2015 …”

Section: Introductionmentioning

confidence: 96%

Propagation of Signals of Finite Concentration in Gas Chromatography. II. Study of the Discontinuities and Their Conditions of Stability

Valentin

Guiochon

1975

Separation Science

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The study of a quasi-ideal chromatography model at finite concentration shows the existence of stable discontinuities, resulting either from sorption or isotherm effects. A set of conditions, illustrated in a diagram, determines the conditions of stability of these discontinuities. Solution thermodynamics shows that there exist three possible modes of peak migration. In all cases a progressive variation of the experimental conditions (pressure or temperature of the column) allows passage from one of these modes to another. One of these three possible modes, the double-shock mode, has not been described previously. It is characterized by front and rear stable discontinuities, and its importance rests on the fact that it corresponds to the minimum band broadening. This mode is observed for a column temperature which is near the boiling point of the solute under the average pressure of the carrier gas. The results also show that the derivation of equilibrium isotherms from the deformation of the peaks obtained with large sample sizes is not valid generally.

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“…The carrier gas is diverted to used by many researchers for thermodynamic meathe saturator and then passes through a diffuser in the surements because this technique does not rely on well-stirred, temperature-controlled liquid bath. It detector calibration and the analysis is very similar to leaves the saturator with its equilibrium vapor presthat of infinitely dilute measurements [6][7][8][9][10][11] . These sure in the carrier gas.…”

Section: Introductionmentioning

confidence: 99%

Application of inverse gas chromatography to the measurement of diffusion and phase equilibria in polyacrylate–solvent systems

Tıhmınlıoğlu

Danner

1999

Journal of Chromatography A

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The inverse gas chromatography technique (IGC) was used to determine the partition and diffusion coefficients of ethyl acetate and 2-ethylhexyl acrylate in polyacrylate for both infinite dilution and finite concentrations of solvent. Experiments were performed over a temperature range of 60 to 1008C, more than 1008C above the glass transition temperature of the polymer. The capillary column IGC model previously developed for determining partition and diffusion coefficients of infinitely dilute solvent has been modified to account for the concentration of the solvent in the polymer phase. Thermodynamic data obtained from retention theory and the modified capillary column IGC model are compared.

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Gas chromatography at finite concentrations. Part 2.—A generalised retention theory

Cited by 111 publications

References 0 publications

Concurrent solution and adsorption phenomena in gas-liquid chromatography. Comparative study

Concurrent solution and adsorption phenomena in gas-liquid chromatography. Comparative study

Propagation of Signals of Finite Concentration in Gas Chromatography. II. Study of the Discontinuities and Their Conditions of Stability

Application of inverse gas chromatography to the measurement of diffusion and phase equilibria in polyacrylate–solvent systems

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