The nonlinear shear gradient effect on the shear viscosity of a ternary system near a plait point

We have studied the shear viscosity of a ternary liquid mixture (water-ethanol-chloroform) near a plait point by the capillary method and found an apparently strong levelling-off as we approach the critical point. This levelling-off cannot be explained simply in terms of a strong cusp. It is found that the nonlinear shear gradient effect suggested by Oxtoby can be used to explain this behavior.     

Effect of temperature on the basicity of certain aliphatic-aromatic amino alcohols

Conclusions Ionization constants were obtained of 14 amino alcohols and one tertiary amine in 50% ethanol in the range of 10–25° and thermodynamic characteristics of the ionization process of the investigated ammonium ions were calculated.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 669–671, March, 1976.The authors express their gratitude to S. V. Bogatkov for participation in discussion of the obtained results.     

Calculations of electric dipole hyperpolarizability of polyatomic molecules

Coupled Hartree-Fock perturbation theory is employed to compute electric dipole hyperpolarizabilities of water, ammonia and methane with three different GTO basis sets. The results were extremely sensitive to the form of zero-order HF wave-functions. In some cases large discrepancies between computed and experimental values suggest that the latter ones must be reviewed. A comparison with other computations is also made.     

Exchange of deuterium with OH groups of HY zeolites

The exchange reaction of D₂ with OH groups of HY zeolites was followed both in the solid and gas phase by IR and MS. The rates of D₂–OH and D₂–H₂ exchange increase considerably with dehydroxylation of the sample. The active centers are probably vacancies formed by removal of oxygen from the lattice, they catalyze the dissociation of D₂. Dehydroxylation of the sample is accompanied by the formation of 3 740 cm^–1 hydroxyls, whose exchange with D₂ is slower than that with other OH groups and which affect the kinetics in the gas phase.

---

D₂ OH HY - O₂–OH O₂–H₂ . , , , O₂. OH, 3740 ^–1, , OH .

     

Chromatographic analysis of hydrocarbons in marine sediments and seawater.

The low concentration of hydrocarbons anticipated in pollution baseline studies necessitates the development of analytical techniques sensitive at the sub-microgram per kilogram concentration level. The method of analysis developed in this laboratory involves dynamic headspace sampling for volatile hydrocarbon components of the sample, followed by coupled-column liquid chromatography for the non-volatile components. These techniques require minimal sample handling, reducing the risk of sample component loss and/or sample contamination. Volatile sample components are separated from the matrix in a closed system and concentrated on a TENAX-GC packed pre-column, free from large amounts of solvent and ready for GC/GC-MS analysis. Non-volatile compounds, such as the benzpyrenes, may be extracted from large volumes of water and concentrated on a Bondapak C18 packed pre-column for coupled-column liquid chromatographic separation and analysis. Results of the application of these techniques to the analysis of samples from sites of known low level hydrocarbon contamination are presented and discussed.     

Functionalization of substituted 2-(1H)pyridones. II. Synthetic pathways to c-6 modified 3-cyano- and 3-carboxy-2-(1H)pyridones from a common precursor

Starting from readily available 1,2-dihydro-6-methyl-2-oxo-3-pyridinecarbonitrile, 1, viable synthetic pathways to a number of C-6 functionalized 1,2-dihydro-2-oxo-3-pyridinecarbonitriles and corresponding acids are presented. Through the utilization of dianion chemistry, the C-6 methyl substituent is selectively functionalized to three different oxidation levels.     

Electrochemical investigations of amino acids at solid electrodes: Part I. Sulfur components: Cystine,cysteine, methionine

The electrochemical oxidation of sulfur amino acids has been investigated by ac measurements and cyclic voltammetry at solid electrodes (Au, vitreous carbon). Electrochemical oxidation proceeds first in the adsorbed state and second by diffusion at metal electrodes. Electrochemical oxidation is catalyzed by a labile metal oxide. At vitreous carbon electrode oxidation in the adsorbed state is only present in the case of methionine. XPS studies have shown the presence of

1. Download full-size image

as intermediate species. To explain the experimental results a reaction path is proposed.     

Photoinduced activation of molecular oxygen by various porphyrins,bis-porphyrins,phthalocyanines, pyridinoporphyrazins,and their metal derivatives

Aerobic irradiation of tetraphenylporphyrins, phthalocyanines, tetra-t-butylphthalocyanines, tetracarboxylphthalocyanines, tetrapyridinoporphyrazins and some of their metal derivatives with visible light (λ > 420 nm) give singlet oxygen by energy transfer and oxygen superoxide by electron transfer, but some of their Cu, Zn of Pt derivatives are efficient quenchers for superoxide formation.     

Distribution de la densite des electrons de valence dans Cu2As

The distribution of valency electron density in Cu₂As (C38) has been determined by Fourier synthesis using as coefficients the values ΔF = F_obs ? F_core (F_core corresponds to the structure factors of the inner orbitals). The bonding between the pyramidal-site copper atoms and the arsenic atoms is exposed, as well as the bonding between tetrahedral-site and pyramidal-site copper atoms.The structural evolution of the unit cell from the Cu₂Sb-type (C38) to the Fe₂P-type (C22) and Co₂P-type (C23) can be related to the metal-metalloid interaction. This interaction mainly involves the pyramidal-site metal atoms in the Cu₂Sb-type, and the tetrahedral-site metal atoms in the Fe₂P- and Co₂P-types.     

On-line sorbent extraction, preconcentration and determination of lead by atomic absorption spectrometry

A method for the quantitative preconcentration of lead based on an existing batch process was developed for implementation in a flow system including a flame AAS detector. Lead can be quantitatively preconcentrated as pyrrolidinedithiocarbamate or dithizonate on an activated carbon minicolumn. The chelates are eluted in methyl isobutyl ketone and introduced directly into the nebuliser-burner. An enrichment factor of 50 is typically obtained for a preconcentration time of 2 min (lead can be determined at concentrations between 15 and 400 ng/ml), which results in a throughput of ca. 25 samples per hr. The sensitivity achieved with the two reagents is similar, but the selectivity provided by APDC exceeds that of dithizone. Based on the results obtained in the determination of lead in reference materials (minerals and skim milk), the proposed APDC method is applicable to real samples.