Gas-liquid chromatography of perfluorocarboxylic thioesters

Perfluorocarboxylic thioesters R_FC(O)SR (R_F=CF₃(CF₂)_j, R=CH₃(CH₂)_i, i andj=0–5) were studied for the first time by GLC on packed columns using SE-30, SKTFT-50X, and XE-60 as the stationary phase. The values of thermodynamics functions of sorption were calculated. The correlations between these functions and the molecular structures as well as the conditions of analysis were established. The insertion of the S atom into the molecules of derivatives of perfluorocarboxylic acids causes a decrease in the contribution of the orientation interaction and an increase in the dispersion interaction of thioesters with the stationary phases compared to esters and amides of perfluorocarboxylic acids studied previously. For Part 1, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1165–1168, June, 1997.     

一类椭圆型变分不等式离散问题的迭代算法

根据一类椭圆型变分不等式离散问题所具有的非线性特征，提出了一种简明快速的迭代算法，该方法在解决障碍问题及流体润滑油膜破裂自然边值问题等工程应用问题时具有较高的效率。     

One case of vortex motion in fluid

This text presents an English translation of the significant paper [6] on vortex dynamics published by the outstanding Russian scientist S. A. Chaplygin, which seems to have almost escaped the attention of later investigators in this field. Although it was published more than a century ago, in our opinion it is still interesting and valuable. __________ Originally published in: Trudy otdeleniya fizicheskikh nauk imperatorskogo Moskovskogo obshchestva lyubitelei estestvoznaniya, antropologii i etnografii (Transactions of the Physical Section of Moscow Society of Friends of Natural Sciences, Anthropology and Ethnography), 1903, Vol. 11, No. 2, pp. 11–14. Translated from Russian by S. Ramodanov; edited by D. Blackmore; commented by V. V. Meleshko (Department of Theoretical and Applied Mechanics, Faculty of Machanics and Mathematics, Kiev National Taras Shevchenko University, 01030 Kiev, Ukraine. E-mail: meleshko@univ.kiev.ua) and G.J.F. van Heijst (Fluid Dynamics Laboratory, Faculty of Applied Physics, Eindhoven University of Technology, 5600 MB Eindhoven, The Netherlands. E-mail: g.j.f.v.heijst@tue.nl).     

Automated derivatization for on-line solid-phase extraction-gas chromatography; phenolic compounds

An automated system for derivaatization was coupled on-line with solid-phase extraction-gas-chromatography (SPE-GC). The system was optimized for the determination of phenol and chlorinated phenols in aqueous samples. The test analytes were acetylated with acetic anhydride; proper buffering of the sample was a critical factor. Next, the phenol acetates were enriched on a SPE cartridge and transferred to a GC; two appraoaches were studied. In the first approach, the derivatives were enriched on disposable C18 cartridges (ASPEC type) and desorbed with methylacetate. Aan aliquot of the final eluate was injected on-line the GC by means of a loop-type interface. In the second approach, trace enrichment was performed on 10 × 2 mm i.d. LC-type precolumn packed with polystyrenedivinylbenzene copolymer (PLRP-S) this precolumn was dried with a mitrogen purge and the phenol acetates were desorbed with ethyl acetate which was injectedon-line into the retention gap of the GC under partially concurrent solvent evaporation (PCSE) conditions. The Derivatization-SPE-GC system which was based on the loop-type interface has the advantage of simplicity and easy operation, the main drawback is the impossibility to determine phenol acetates which elute prior to trichlorophenol acetates. With the derivatization-SPE-GC approach using PCSE-based desorption, even the most volatile analyte of the test series, phenol acetate, can be determined successfully. The entire procedure, including the derivatization step, was fully automated and integrated in one set-up. The precision data for the integrated on-line derivatization-SP-FID system were fully satisfactory, with RSD values of 1–12 % at the 1 μg/1 level. When a sample volume of 2.2 ml was analyzed, The detection limits for the chlorinated phenol acetates were in the 0.1–0.3 μg/1 range.     

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.     

Continuous reaction system to investigate the dispersion polymerization of vinyl monomers in supercritical carbon dioxide

A laboratory‐scale continuous reaction system using a stirred tank reactor was assembled in our laboratory to study the dispersion polymerization of vinyl monomers in supercritical carbon dioxide (scCO₂). The apparatus was equipped with a suitable downstream separation section to collect solid particles entrained in the effluent stream from the reactor, whose monomer concentration could be measured online with a gas chromatograph. The dispersion polymerization of methyl methacrylate in scCO₂ was selected as a model process to be investigated in the apparatus. The experiments were performed at 65 °C and 25 MPa with 2,2′‐azobisisobutyronitrile as the initiator and a reactive polysiloxane macromonomer as a surfactant to investigate the effect of the mean residence time of the reaction mixture on the monomer conversion, polymerization rate, polymer molecular weight, and particle size distribution. The results were compared with those obtained in batch polymerizations carried out under similar operative conditions. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4122–4135, 2006     

Practical syntheses of [1,3,5]‐triazine dendritic molecules on solid supports

A practical and divergent synthesis of supported [1,3,5]‐triazine dendritic molecules on Wang resin, PEGA resin, SynPhase? Lanterns, and silica gel is described. The alkylamine linkers used allow derivatization with functionality for both synthetic (e.g., supported reagent and scavenger activity) and chemical biology applications. The use of supported intermediates allows differentiation of symmetric linkers without the need for protecting group chemistry. The synthetic route uses inexpensive, readily available starting materials in a straightforward and scaleable strategy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2248–2259, 2006     

Measurement and prediction of solubilities and diffusion coefficients of carbon dioxide in starch–water mixtures at elevated pressures

The solubility and diffusion coefficient of carbon dioxide in intermediate‐moisture starch–water mixtures were determined both experimentally and theoretically at elevated pressures up to 16 MPa at 50 °C. A high‐pressure decay sorption system was assembled to measure the equilibrium CO₂ mass uptake by the starch–water system. The experimentally measured solubilities accounted for the estimated swollen volume by Sanchez–Lacombe equation of state (S‐L EOS) were found to increase almost linearly with pressure, yielding 4.0 g CO₂/g starch–water system at 16 MPa. Moreover, CO₂ solubilities above 5 MPa displayed a solubility increase, which was not contributed by the water fraction in the starch–water mixture. The solubilities, however, showed no dependence on the degree of gelatinization (DG) of starch. The diffusion coefficient of CO₂ was found to increase with concentration of dissolved CO₂, which is pressure‐dependent, and decrease with increasing DG in the range of 50–100%. A free‐volume‐based diffusion model proposed by Areerat was employed to predict the CO₂ diffusivity in terms of pressure, temperature, and the concentration of dissolved CO₂. S‐L EOS was once more used to determine the specific free volume of the mixture system. The predicted diffusion coefficients showed to correlate well with the measured values for all starch–water mixtures. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 607–621, 2006