Determination of gas-liquid partition coefficients by gas chromatography

This review covers theoretical principles and experimental procedures for the determination of gas-liquid partition coefficients, KL, by gas chromatography. In order to precisely define the relationship between KL, retention time and experimental parameters, the retention theory, both for ideal and for imperfect gas phase, is expounded. The most important sources of systematic error, as peak asymmetry, mixed retention mechanisms, column hold-up time and stationary phase mass determination, are discussed. Although the review is focussed on packed columns, comparison to capillary columns is discussed in those aspects in which these last show advantages.     

Determination of partition coefficients by automatic equilibrium headspace gas chromatography by vapor phase calibration

Summary Equilibrium headspace gas chromatography has been applied to the determination of the partition coefficients of volatile compounds in water-air systems. Only techniques that are suited to a fully automatic headspace procedure using the pneumatic headspace sampling-technique have been considered. Particularly simple is the technique of vapor phase calibration —VPC where an external vapor standard is used to calibrate the concentration of the volatile analyte in the headspace, while the concentration in the sample is found from the difference in the total amount in the vial. This technique is described in detail for 2-butanone in water. Finally, the water-air partition coefficients of several selected volatile compounds at different temperatures are listed together with their temperature functions.Dedicated to Professor Leslie S. Ettre on the occasion of his 70th birthday.     

Determination of siloxane-water partition coefficients by capillary extraction-high-resolution gas chromatography study of aromatic solvents

Partition coefficients of benzene, toluene, ethylbenzene and xylenes (BTEX), between crosslinked polydimethylsiloxane and water, were determined at room temperature by capillary extraction (a form of in-tube solid-phase microextraction, SPME) coupled to open tubular gas chromatography (in-tube SPME-high-resolution GC). A series of 7-9 repetitive extractions, performed on a 1-ml volume of diluted aqueous BTEX sample by the double-syringe squeeze method, gave exponential regression curves which fit very well with those predicted by partition theory. From the equations of the curves of relative FID response vs. extraction number, experimental Kd were easily calculated and the results compared with literature values. The whole measurement requires about 1 h from the start of the experiment to the final calculation of all BTEX partition coefficients. In-tube SPME resulted in a fast, clean, efficient, and cheaper alternative than the classic 1-cm, externally coated, SPME fiber-holder technique.     

Simultaneous determination of endocrine-disrupting phenols and steroid estrogens in sediment by gas chromatography-mass spectrometry

A simple and effective method has been developed to simultaneously determine endocrine-disrupting phenolic xenoestrogens and steroid estrogens in sediment by using ultra-sonicated extraction in combination with silica gel fractionation, derivatization with pentafluropropionic anhydride, and gas chromatography-mass spectrometry (GC-MS) in selected ion monitoring mode (SIM). Satisfactory recoveries have been obtained for phenolic xenoestrogens and steroid estrogens. The method enables the determination of targets at concentrations of lower nanogram-per-gram in sediments. The method has been successfully applied to the sediments collected from Pearl River Estuary (PRE), South China Sea, China. Nonylphenol and bisphenol-A (BPA) were detected in the range from 204.2 to 664.5 ng/g and 0.6 to 4.0 ng/g, respectively. None of the estrogens were found in the sediment samples.     

毛细管柱气相色谱法测定土壤中的有机氯农药

研究了使用毛细管柱气相色谱法测定土壤中有机氯农药的分离条件、萃取方法、净化方法以及用替代品进行全程质量控制的方法。有机氯农药检出限在 1 .1～ 4.0 μg L之间 ,各化合物保留时间的RSD <0 .1 % ,所测定化合物的质量浓度在 0 .0 0 6～ 0 .2 0mg L范围内 ,各物质校正曲线 (浓度与峰面积 )的相关系数在 0 .992 6～ 0 .9971之间。用正己烷 丙酮 ( 1 1 ) 1 0 0mL超声波萃取 ,有机氯农药的萃取回收率在 96.3%～ 1 1 4% ,RSD为 0～ 1 1 %。用国产硅镁吸附剂净化 ,有机氯农药的回收率在 1 0 0 %～ 1 40 %之间 ,弗罗里硅土的回收率在 1 0 4 %～ 1 33%之间 ,硅镁吸附剂可以替代弗罗里硅土用于样品的净化。     

Rapid headspace gas chromatographic method for the determination of liquid/gas partition coefficients

A rapid, efficient and low-cost headspace technique useful for the determination of liquid/gas partition coefficients of gases and volatile substances of low and intermediate solubility is described. The equilibration step is carried out at constant pressure using glass syringes, with a ratio of liquid/gas phase volumes of ca. 1:3; after 30 min at the desired temperature, the headspace is recovered by transfer into another syringe and analyzed by gas chromatography. A study of the partition coefficients in water at 37 degrees C of 27 volatile compounds demonstrated that the method is fully applicable for all gases, with exception of those with a partition coefficient higher than 300.     

气相色谱-质谱法同时测定化妆品中18种氯代烃类有机溶剂

建立了同时测定化妆品中18种氯代烃类有机溶剂的气相色谱-质谱(GC-MS)检测方法.样品在饱和氯化钠溶液中由正十四烷振荡提取后,以Agilent J&W DB-624超高惰性毛细管柱(30m×0.25 mm×1.4μm)为分离色谱柱进行分析,以电子轰击(EI)源、SIM模式进行质谱监测,外标法定量.结果 表明,18种化...     

用于气相色谱和气相色谱-质谱测定植物样品中含氯有机污染物残留的样品前处理方法

根据植物样品中的主要干扰物质,建立了用于气相色谱(GC)和气相色谱-质谱联用(GC-MS)测定植物样品中含氯有机污染物残留的样品前处理方法,有效提高了对植物样品中有机氯农药及多氯联苯检测的灵敏度。采用均质提取法对样品进行提取,考察了凝胶渗透色谱(GPC)和固相萃取(SPE)对提取液的净化效果。结果发现,采用GC测定目标物时,提取液需经GPC和SPE两次净化;而采用GC-MS测定目标物时,仅用SPE一次净化即可。该方法快速、经济、灵敏,适合多种植物样品中有机污染物残留分析的样品前处理要求。     

Wrong gas/liquid partition data by gas chromatography

In a paper published in 1992 [K.S. Reddy, J.-Cl. Dutoit, E.sz. Kováts, Pair-wise interactions by gas chromatography. I. Interaction free enthalpies of solutes with non-associated primary alcohol groups, J. Chromatogr. 609 (1992) 229] retention indices and standard chemical potential differences (SPOT-s) are given for about 160 solutes on a liquid branched paraffin hydrocarbon of the carbon number, z = 78. For the temperature dependence of the SPOT-s the proposal of Kirchhoff was accepted i.e. that at higher temperatures the molar heat capacity difference of the solute between the gas phase and the solution is nearly constant in a broad temperature range. The data were determined under conditions where the effect of adsorption could be neglected. By comparing the published data with those determined on another branched paraffin of the carbon number, z = 87 [F. Riedo, D. Fritz, G. Tarján, E.sz. Kováts, A tailor-made C87 hydrocarbon as a possible non-polar standard stationary phase for gas chromatography, J. Chromatogr. 126 (1976) 63] it is shown that the reported thermodynamic constants of solutes determined experimentally at higher temperatures (the group "H") are wrong on C78. In the present paper, the method of correction and the resulting corrected data are given. In later papers retention data are given on eight polar derivatives of the hydrocarbon C78 relative to those measured on the nonpolar standard [R. Cloux, G. Défayes, K. Fóti, J.-Cl. Dutoit, E.sz. Kováts, Pair-wise interactions by gas chromatography. III. Synthesis of isosteric stationary phases for gas chromatography, Synthesis (1993) 909; G. Défayes, K.S. Reddy, A. Dallos, E.sz. Kováts, Pair-wise interactions by gas chromatography. V. Interaction free enthalpies of solutes with primary chloro- and bromo-alkanes, J. Chromatogr. A 699 (1995) 131; K.S. Reddy, E.sz. Kováts, Pair-wise interactions by gas chromatography. II. Sociation free enthalpies of some hydrogen bonding solutes with non-associated primary alcohol groups, Chromatographia 34 (1992) 249; K.S. Reddy, R. Cloux, E.sz. Kováts, Pair-wise interactions by gas chromatography. IV. Interaction free enthalpies of solutes with trifluoromethyl-substituted alkanes, J. Chromatogr. A 673 (1994) 181; K.S. Reddy, R. Cloux, E.sz. Kováts, Pair-wise interactions by gas chromatography. VI. Interaction free enthalpies of solutes with primary methoxyalkane, cyanoalkane and alkanethiol groups, J. Chromatogr. A 704 (1995) 387; A. Dallos, A. Sisak, Z. Kulcsár, E.sz. Kováts, Pair-wise interactions by gas chromatography. VII. Interaction free enthalpies of solutes with secondary alcohol groups, J. Chromatogr. A 904 (2000) 211]. Obviously, the same data which are wrong in the nonpolar standard are also wrong in these solvents. The corrected data in the polar solvents are given in supplementary tables.     

Simplified method for the determination of chlorinated fungicides and insecticides in fruits by gas chromatography

A fast, reliable method for the determination of more than twenty chlorinated fungicides and insecticides in a variety of fruit samples is presented. The pesticides are extracted from chopped samples with magnetic stirring, after adding 13 ml of acetone-phosphate buffer-brine solution (12:1, v/v) with 5 ml of n-hexane. The continuous module employed allows sequential decolourization of the organic phase, solvent changeover and solid-phase extraction for clean-up and preconcentration purposes. A 1-microl aliquot of the pesticides in ethyl acetate (eluent) is finally injected into the gas chromatograph for separation and identification. The method provides excellent clean-up despite the complexity of the matrices involved. Fruit samples (5-20 g) containing 0.1-1250 ng/g pesticides were analysed with a high precision (4-6%). After contamination of the fruit samples for 12 h, average recoveries >90% at fortification levels of 5-25 ng/g were obtained for most of the pesticides. Positive findings of these pesticides in fruits purchased at local markets were confirmed by GC-MS.     

Spectrophotometric determination of acidity constants by two-rank annihilation factor analysis

Annihilation of the contribution of one chemical component from the original data matrix is a general method in rank annihilation factor analysis (RAFA). However, RAFA is not applicable for studying the protonation equilibria of multiprotic acids. In this work, a two-rank annihilation factor analysis (TRAFA) method was proposed for determination of the acidity constants of diprotic acids. After recording the electronic absorbance spectra of the acids at different pH, the contributions of both H₂A and A²⁻ were annihilated from the absorbance data, which made feasible the determination of two successive acidity constants. The method was validated by analysis of simulated data and its application to the determination of the acidity constants of calmagite, as a reference compound. A close agreement was obtained between the resulted values by TRAFA and the declared values. Indeed, the method was used for determination of the acidity constants of two new chromenone derivatives in binary solvents mixtures of methanol and water. The effects of changing solvent composition on acidity constant data were explained by linear solvation free energy relationships (LSFER) utilizing solvatochromic parameters.     

Simultaneous determination of griseofulvin and 6-desmethylgriseofulvin in plasma by electron-capture gas chromatography

Two methods have been developed for the simultaneous determination of griseofulvin and its major metabolite 6-desmethylgriseofulvin in plasma using electron-capture gas chromatography. The first method was based on the quantitative reversion of the 6-desmethyl metabolite to griseofulvin by diazomethane. Plasma extract was chromatographed both before and after treatment with diazomethane, the former being the measure of griseofulvin and the latter representing the sum of the two compounds. In the second method, plasma extract was treated with diazobutane and griseofulvin and the butylated metabolite were separated by gas chromatography. The sensitivity for griseofulvin was 20 ng/ml by both methods and that for the metabolite was 20 ng/ml and 40 ng/ml by the first and the second method, respectively. The concentrations of the metabolite as well as griseofulvin were determined in dog and human plasma after oral administration of griseofulvin.