Indirect determination of low vapour pressures using solid-phase microextraction--application to tetrachlorobenzenes and tetrachlorobenzyltoluenes

There is still a gap of reliable vapour pressure data at ambient temperature for low volatile organic substances due to the difficult and time-consuming determination using the classical methods. Static headspace extraction with a solid-phase microextraction (SPME) fibre in combination with gas chromatographic analysis provides an inexpensive tool for the indirect determination of low vapour pressures down to 10(-5) Pa. The procedure consists of two steps: (a) exposure of SPME fibre in the headspace above the test chemical over minutes to hours and (b) desorption and quantification of extracted amount. The calibration was performed using low volatile reference substances with well-known vapour pressures. A good correlation was found between substance uptakes of SPME fibre and vapour pressures. The method was applied, e.g. to tetrachlorobenzenes and to selected tetrachlorobenzyltoluenes with questionable vapour pressures. We obtained values between 0.98 and 13.5 Pa for the former and results between 0.13 and 0.68 mPa for the latter group of congeners. The scope of the method can be extended to substances with even lower vapour pressures, provided that reliable reference data are available.     

Study and prediction of alkylbenzenes’ vapour pressures

Vapour pressures of 1,4-di-tert-butylbenzene (379–1647 Pa), 1,3,5-tri-tert-butylbenzene (203.9–241 Pa), 1-methyl-3,5-di-tert-butylbenzene (16.7–435.8 and 1318–103,880 Pa), and 1,2,2-trimethylpropybenzene (36.3–287.4 Pa) have been measured using a transpiration method and an ebuliometric method. Based on the literature and obtained by the authors experimental data a comparative study of prediction capabilities of the following methods has been carried out: Ambrose–Walton's, Lee–Kesler's, Riedel's and the modification of Riedel's method made by Vetere.     

Development and test of a new Knudsen effusion apparatus for the measurement of low vapour pressures

A new Knudsen effusion apparatus based on the mass-loss technique was developed. The apparatus was designed for the measurement of vapour pressures below 1 Pa, at temperatures between 250 K and 470 K, using simultaneously up to seven effusion cells. The quality of the results obtained with this new apparatus was verified through the study of two reference compounds, anthracene and phenanthrene. Both the measured vapour pressures and the derived standard molar enthalpies of sublimation are in excellent agreement with values available in the literature for these compounds.     

High-temperature liquid chromatography. Part I. Determination of the vapour pressures of binary solvent mixtures—Implications for liquid chromatographic separations

This paper is the first in a series of consecutive publications, explaining the concept of high-temperature liquid chromatography under various important aspects. The first publication deals with the determination of the vapour pressure of binary solvent mixtures used in reversed-phase liquid chromatography. Also, the practical implications regarding the use of elevated temperatures in liquid chromatography and towards commercially available HPLC systems are explained.     

Vapour pressures and osmotic coefficients of binary mixtures of 1-ethyl-3-methylimidazolium ethylsulfate and 1-ethyl-3-methylpyridinium ethylsulfate with alcohols at T = 323.15 K

Osmotic coefficients of binary mixtures containing alcohols (ethanol, 1-propanol, and 2-propanol) and the ionic liquids 1-ethyl-3-methylimidazolium ethylsulfate and 1-ethyl-3-methylpyridinium ethylsulfate were determined at T = 323.15 K. Vapour pressure and activity coefficients of the studied systems were calculated from experimental data. The extended Pitzer model modified by Archer, and the modified NRTL model (MNRTL) were used to correlate the experimental data, obtaining standard deviations lower than 0.012 and 0.031, respectively. The mean molal activity coefficients and the excess Gibbs free energy of the studied binary mixtures were calculated from the parameters obtained with the extended Pitzer model of Archer.     

Thermal analysis and vapour pressure of a new series of tungsten(VI) oxo-alkoxide-β-ketoesterate complex precursors for the chemical vapour deposition of tungsten oxide

A new series of tungsten complexes, tungsten(VI) oxo-alkoxide-β-ketoesterate complexes have been synthesized and characterized by infrared and NMR spectroscopy. Thermogravimetric analysis has been carried out on the complexes as a function of temperature, and isothermally as a function of time. Based on the thermal analysis data, these complexes are evaluated for their suitability as precursors for the chemical vapour deposition of tungsten oxide thin films. The vapour pressure of these precursors is estimated using the Langmuir equation.     

Vapour pressures of selected organic compounds down to 1 mPa,using mass-loss Knudsen effusion method

A recently developed Knudsen effusion apparatus was improved and used for measurements of vapour pressures of selected organic compounds. Calorimetric studies were conducted using a Calvet-type calorimeter, complementing the information obtained for the vapour pressures and facilitating the modelling and analysis of the data.Vapour pressures of benzoic acid, a reference substance, were determined at temperatures between 269 K and 317 K, corresponding to a pressure range from 2 mPa to 1 Pa, extending the range of results available in the literature to lower pressures. Benzanthrone was studied between temperatures 360 K and 410 K (5 mPa–1 Pa) in order to test the apparatus at higher temperatures.Values presented in the literature for the vapour pressure of solid n-octadecane, one of the most promising compounds to be used as “phase change material” for textile applications, were found inconsistent with the triple point of the substance. Sublimation pressures were measured for this compound between T = 286 K and 298 K (2–20 mPa) allowing the correction of the existing values. Finally, vapour pressures of diphenyl carbonate, a compound of high industrial relevance for its use in the production of polycarbonates, were determined from T = 302 K to 332 K (0.02–1 Pa).     

The Dynamic Impact Experiments Under Active Confining Pressure and the Constitutive Equation of PP/PA Blends at Multi-Axial Compressive Stress State

Summary : A special active hydraulic confining pressure installation matched with Φ14.5 mm SHPB apparatus was developed. A series of active confining pressure impact experiments for PP/PA blends are performed in this special SHPB system under two kinds of axial strain rate: 8.0*10², 1.4*10³ s⁻¹ and the active confining pressure of 0 MPa, 4 MPa, 8 MPa, 12 MPa, 15 MPa, 20 MPa. The axial strain-time profile, the axial stress-time profile and the hoop strain-time profile of the specimen are recorded online respectively. According to the equilibrium equation, the complete state of principal stress and principal strain of PP/PA blends under multi-axial stress state is analyzed. The experimental results reveal that the axial stress-strain curves all are related to the confining pressure and the strain rate. It can also be seen that under a constant effective strain rate the effective stress- effective strain curves at different confining pressures are coincident basically. This manifests that under a certain effective strain rate there is only one unique effective stress- effective strain curve. The multi-axial constitutive equation for PP/PA blends is suggested finally as: where σ_conf is the confining pressure value. For 113 PP/PA blends, E = 2.98 GPa, α = −31.15 GPa, β = 93.31 GPa, θ₂ = 8.54 µS, E₂ = 0.82 GPa.     

The influence of cytosine methylation on the chemoselectivity of benzo[a]pyrene diol epoxide‐oligonucleotide adducts determined using nanoLC/MS/MS

Benzo[a]pyrene is a major carcinogen implicated in human lung cancer. Almost 60% of human lung cancers have a mutation in the p53 tumor suppressor gene at several specific codons. An on‐line nanoLC/MS/MS method using a monolithic nanocolumn was applied to investigate the chemoselectivity of the carcinogenic diol epoxide metabolite, ( ± )‐(7R,8S,9S,10R)‐benzo[a]pyrene 7,8‐diol 9,10‐epoxide [( ± )‐anti‐benzo[a]pyrene diol epoxide (BPDE)], which was reacted in vitro with a synthesized 14‐mer double stranded oligonucleotide (5′‐ACCCG₅CG₇TCCG₁₁CG₁₃C‐3′/5′‐GCGCGGGCGCGGGT‐3′) derived from the p53 gene. This sequence contained codons 157 and 158, which are considered mutational ‘hot spots’ and have also been reported as chemical ‘hot spots’ for the formation of BPDE‐DNA adducts. In evaluating the effect of cytosine methylation on BPDE‐DNA adduct binding, it was found that codon 156, containing the nucleobase G₅ instead of the mutational hot spot codons 157 (G₇) and 158 (G₁₁), was the preferential chemoselective binding site for BPDE. In all permethylated cases studied, the relative ratio for adduction was found to be G₅? G₁₁ > G₁₃ > G₇. Permethylation of CpG dinucleotide sites on either the nontranscribed or complementary strand did not change the order of sequence preference but did enhance the relative adduction level of the G₁₁ CpG site (codon 158) approximately two‐fold versus the unmethylated oligomer. Permethylation of all CpG dinucleotide sites on the duplex changed the order of relative adduction to G₅? G₇ > G₁₁ > G₁₃. The three‐ to four‐fold increase in adduction at the mutational hot spot codon 157 (G₇) relative to the unmethylated or single‐stranded permethylated cases suggests a possible relationship between the state of methylation and adduct formation for a particular mutation site in the p53 gene. Using this method, only 125 ng (30 pmol) of adducted oligonucleotide was analyzed with minimal sample cleanup and high chromatographic resolution of positional isomers in a single chromatographic run. Copyright © 2009 John Wiley & Sons, Ltd.