Preparative synthesis of the stable α-fluorosulfatotetrafluoro-ethylbis(perfluoroisopropyl)methyl radical

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2450–2451, October, 1990.     

Fluoroaliphatic esters of fluorosulfonic acid. 4. Reactions of α-fluorosulfatoperfluoro ketones with nucleophilic reagents

-Fluorosulfatoperfluoroethyl isopropyl ketone I and fluorosulfatopentafluoroacetone II react with alkali metal chlorides and bromides to form the corresponding -haloperfluoro ketones as a result of direct nucleophilic substitution.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2066–2069, September, 1990.     

Effect of pressure on free-radical copolymerization kinetics. I. A concept of additivity of partial molar volumes of activation

A short review of the effect of pressure on copolymerization kinetics shows the necessity of simple models for a better understanding of activation volumes. Therefore, a simple concept, possibly generally valid for free-radical polymerization, is proposed, based on the assumption that molar volumes of activation can be expressed as an addition of a characteristic radical and a monomer contribution, regardless of the combination involved. The scheme may facilitate the visualization of the transition state and contribute to the understanding of reaction mechanisms of radical polymerizations. Ethylene–vinyl acetate copolymerization at 62°C with tert-butyl alcohol as solvent agrees with the proposed scheme, appearing from the pressure independence of the product of reactivity ratios at the different levels (35,600, and 1200 kg/cm²). Implicitly it can be shown that an ethylene monomer contributes about 2 cm³/mole more to the activation volumes of the propagation reactions than does the vinyl acetate monomer, whereas for the radicals the difference of the respective contributions to the activation volumes is opposite in sign.     

Estimation scheme for level-dependent uncertainty of analytical result: application for determination of 1-hydroxypyrene in urine

The estimation scheme of uncertainty of determination of 1-hydroxypyrene (1-OHP) in urine was developed analysing the main stages of the analytical procedure: (1) preparation of 1-OHP standards, (2) creation of the calibration curve for the high performance liquid chromatography (HPLC) analysis method with the evaluation of recovery, (3) measuring procedure of aliquot of urine, (4) adjusting the pH of aliquot and hydrolysis with enzyme, (5) solid phase extraction, (6) concentration of the extract, (7) injection of the extract to chromatograph and analysing by the HPLC method, (8) calculation of 1-OHP mass from the calibration curve, (9) calculation of 1-OHP concentration in urine. The evaluation of the uncertainty is based on quantification of individual components. Combined uncertainty was calculated using the law of propagation of uncertainties according to the EURACHEM/CITAC guidelines. Level dependence of the uncertainty arises from the calibration curve. The limits of detection and quantification were found to be equal to 0.03 and 0.1 ng/mL, respectively. The calculated expanded level-dependent uncertainty covers 47–27–25% within the concentration range 0.03–0.1–0.4 ng/mL with the materials and equipment used. These parameters could easily be recalculated according to the proposed scheme if there are some changes in the analysis procedure.     

Study on the retention behaviour of low-molar-mass polystyrenes and polyesters in reversed-phase liquid chromatography by evaluation of thermodynamic parameters

Polymers can be characterized under sorption conditions, to obtain information on molar mass and chemical composition. In order to get a better understanding of their retention behaviour under such conditions, the evaluation of thermodynamic parameters obtained from van't Hoff analyses on low-molar-mass polystyrenes (PS) and polyesters (PE) in various THF–water mixtures on a C₁₈ column is described in this study. Linear van't Hoff behaviour was observed in almost all cases. Negative values for both ΔH and ΔS were found for both PS and PE oligomers, which increase with increasing %THF. For ΔS this is explained from multi-site attachment effects. For PS, the non-linear relations between ΔH and ΔS, and degree of polymerization (p) could be properly described by the Stockmayer–Fixman equation. Although less clear, similar trends were found for PE. For PS, evidence for penetration effects of oligomer chains into the bonded chains was obtained. Martin plots for both PS and PE were shown to be non-linear in all investigated eluent compositions. The extent of non-linearity is suggested to depend on the conformation of a polymer in solution. No distinct enthalpy–entropy-compensation temperature (EECT) independent of p was found for PS, thus confirming the findings of an earlier study in which no exact molar mass independence was found under critical conditions. Further evaluation of EECT for PS oligomers revealed a retention mechanism independent of the binary eluent composition. This indicates that conclusions from this study can also be used for a qualitative understanding of sorption mechanisms in the gradient elution mode. Finally, for PS it was shown that ΔG equals zero under critical conditions, thus confirming theoretical predictions.     

Substitutive sulfotrioxidation of unsaturated and araliphatic organofluorine compounds

Conclusions Reaction of SO₂ or SO₃/[B₂O₃] with terminal fluoroolefins or fluoroalkylbenzenes gives the corresponding fluoroalken-2-yl fluorosulfates and fluorobenzyl fluorosulfates.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2791–2795, December, 1982.     

Effect of molar mass ratio of monomers on the mass distribution of chain lengths and compositions in copolymers: Extension of the stockmayer theory

In statistical copolymers, there exists a distribution according to molar mass as well as according to chemical composition. Stockmayer derived distribution functions, describing the relative weight of a particular molar mass and composition interval, assuming equal molar masses of the monomer units. In this article we present an extension of the distribution functions, suited for those cases where the aforementioned assumption is not valid. The final mathematical results is a product of the original Stockmayer distribution function and a correction function, due to the unequality of molar masses. It appears the correction function is dependent on the average composition, the composition deviation, and the ratio of molar masses of the monomers. Furthermore, a three-dimensional representation of distributions has been developed to get insight in the shape of the distributions.