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.     

A novel synthesis of vinyl esters from vinylversatate-10

Vinylversatate-10 (VV10)¹ has successfully been used to synthesise a large number of lower vinyl esters by transvinylation in presence of mercuric acetate and sulfuric acid. The synthesis of vinylhalo esters proceeds with more difficulty. It has been observed that neither Hg(OAc)₂ nor H₂SO₄ alone is capable of initiating the transvinylation. Furthermore, it has been found that a molar ratio 2:1 of VV10 to carboxylic acid is sufficient to drive the reaction to the right by continuous distillation of the vinyl ester formed, and as a result a high yield of vinyl ester is obtained. A mechanism for this reaction and for the formation of side products has been proposed.     

Magnetic properties of MnxMg1-xS solid solutions

The static magnetic properties of the polycrystalline solid solutions Mn_xMg_1-xS(0<x?1) are reported. The experimental data reveal the appearance of a critical concentration x_c=0.13±0.01 for long-range magnetic ordering, which is in good agreement with the result of a series expansion of the mean cluster size for a face-centered cubic lattice with exchange interactions up to 12 nearest neighbours and 6 next-nearest neighbours. At concentrations far below x_c the existence of long-range exchange interactions is demonstrated.     

N-acyl protecting groups for deoxynucleosides : A quantitative and comparative study

A detailed study in search for suitable N-acyldeoxy-nucleosides which could serve as building blocks for the stepwise synthesis of deoxyoligonucleotides was undertaken. Several acyl groups namely 4-t-butylphenylacetyl, 4-t-butylphenoxyacetyl, 4-chlorobenzoyl, 3,4-dichlorobenzoyl, 2-methyl-benzoyl, 2,4-dimethylbenzoyl, nicotinoyl, 4-t-butylbenzoyl and 4-phenylazobenzoyl have been used for the protection of the exocyclic amino groups of deoxynucleosides. Interesting data concering the stability of N-acyl groups towards a potent deacylating system (0.2 N NaOH/MeOH) are presented.     

Copolymerization of ethylene and vinyl acetate at low pressure: Determination of the kinetics by sequential sampling

In behalf of a detailed study on the course of copolymerization reactions, this paper describes an improved and generally applicable experimental method and an efficient computational procedure to match. The experimental method is based on quantitative gas chromatography, and permits frequent measurement of the monomer feed composition throughout (co)polymerization processes at pressures up to 40 kgf/cm² ( = 38.7 atm). The given method is applied to the study of the radical copolymerization of ethylene with vinyl acetate in a series of kinetic experiments, at 62°C and 35 kgf/cm² ( = 33.9 atm) in tert-butyl alcohol, in which 20–40% conversion is reached. Monomer feed composition and degree of conversion are entered into a computational procedure based on nonlinear least-squares methods applied to the integrated version of the copolymer equation. The experimental data, covering a region of ethylene molar feed fractions between 0.24 and 0.74 and copolymer concentrations up to 8 wt-%, are precisely consistent with the usual model. The respective reactivity ratios are r?_e = 0.743 ± 0.005 and r?_v = 1.515 ± 0.007.     

Electrical properties of α-MnS

Electrical data including thermoelectric power, Hall effect and resistivity on iodine-grown crystals of p-type α-MnS are reported. A study of the temperature dependences reveals that the conductivity occurs by holes in a 3d-band (Mn³⁺) and that the mobility of the holes is not thermally activated. Photoelectron spectra confirm the 3d character of the top of the valence band. Accurate analysis of the electrical data gives a satisfactory explanation of the extrinsic and intrinsic behaviour; the simultaneous presence of donors (substitutional iodine) and acceptors (manganese vacancies) is responsible for the observed phenomena.     

HPTLC-Bestimmung von Paracetamol im Serum

Ohne Zusammenfassung

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Determination of paracetamol in serum by HPTLC

     

Magnetic behavior of the oxide spinels: Li0.5Fe2.5−2x Al x Cr x O4

In order to study the effect of substitution of Fe³⁺ by Al³⁺ and Cr³⁺ in Li_0.5Fe_2.5O₄ on its structural and magnetic properties, the spinel system Li_0.5Al _x Cr _x Fe_2.5?2x O₄ (x=0.0, 0.2, 0.4, 0.5, 0.6 and 0.8) has been characterized by X-ray diffraction, high field magnetization, low field ac susceptibility and ⁵⁷Fe Mossbauer spectroscopy. Contrary to the earlier reports, about 50% of Al³⁺ is found to occupy the tetrahedral sites. The system exhibits canted spin structure and a central paramagnetic doublet was found superimposed on magnetic sextet in the Mössbauer spectra (x>0.5).     

联苯胺分光光度法测定食盐中碘含量

基于在盐酸介质中,碘酸钾氧化联苯胺使其显色,提出了光度法测定食盐中微量碘的方法。在40℃的水浴中,当2 mol.L-1盐酸溶液用量为1.00 mL0、.42 g.L-1联苯胺溶液用量为0.80 mL时,方法的线性范围为100~1 400μg.L-1,最大吸收波长在425 nm处,表观摩尔吸光率为1.4×105L.mol-1.cm-1。用于测定加碘食盐中碘含量的测定,回收率在97.5%~101.2%之间,相对标准偏差(n=7)在0.9%~1.9%之间。