Analysis of products of the industrial synthesis of ethylene oxide by two-dimensional gas chromatography using packed capillary columns

Procedures for separating products of the synthesis of ethylene oxide by two-column gas chromatography using both conventional capillary PLOT columns and packed capillary columns of a new type bearing microparticulated adsorbents are proposed. A combination of packed capillary columns with a microthermostat reduces both separation time and the size of the chromatographic system, which becomes compatible with microreactors. The short time of analysis enables the control over the work of a series of microreactors in a cyclic mode using one chromatographic system.     

Quantum dynamics of H2 formation on a graphite surface through the Langmuir Hinshelwood mechanism

We have studied the formation of the H2 molecule on a graphite surface, when both H atoms are initially physisorbed. The graphite surface is assumed to be planar, and a model potential is obtained in a semiempirical way to reproduce the experimental properties of H physisorption on graphite. The reaction probability has been computed in the case when the angular momentum of the relative H-H motion lies parallel to the surface plane. Three-dimensional wave packet calculations have been performed for collision energies ranging from 2 to 50 meV. It is shown that the reaction occurs with a significant probability and produces the H2 molecule with a considerable amount of vibrationnal energy. A simple mechanical model is presented, where desorption of the nascent H2 molecule results from two successive binary elastic collisions.     

3, 3, 3-Trifluoropropyl(methyl)cyclosiloxanes

The influence of the number of 3, 3, 3-trifluoropropyl(methyl)siloxane links (/) in the cyclotetrasiloxanes _mD_4-m, where D represents the dimethylsiloxane link and m=0–4, on the rearrangement of these compounds in acetone solution under the action of sodium siloxanolate has been studied. The rearrangement takes place with the formation of a linear polysiloxane the degradation of which yields, in addition to the initial ring, cyclosiloxanes with a different structure. The rate of rearrangement of _mD_4-m and of the formation of a linear polysiloxane rises with an increase in m from 0 to 3. The equilibrium concentration of the linear polysiloxane formed from _mD_4-m is inversely proportional to m. Results have been obtained on the kinetics of the formation of the cyclosiloxanes _mD_n, where m=0–5, n=0–5, and m+n=3–6, in the rearrangement of the rings D₃, ₂D₂, ₃D, and ₄. The reactivity of the siloxane links rises in the sequence (CH₃)₂Si-O-Si(CH₃)₂ < (CF₃CH₂CH₂)-(CH₃) Si-O-Si(CH₃)₂ <(CF₃CH₂CH₂) (CH₃)Si-O-Si(CH₃) (CH₂CH₂CF₃) . Because of the negative inductive effect transferred through the siloxane links, the 3, 3, 3-trifluoropropyl groups strongly activate the siloxane ring with respect to nucleophiiic reagents.For part I, see [3].     

A chemical study of 2-butyne-1,4-diol

Commercial grade 2-butyne-1,4-diol has been used in electroplating for several years. In laboratory experiments, its presence in the electrolyte increases the current efficiency of zinc electro-winning. Its chemical behaviour in solution is not well known. The present paper indicates that the brownish technical grade 2-butyne-1,4-diol contains the monomer, the dimer and some trimer. Pure monomeric 2-butyne-1,4-diol is a white solid obtained by evaporation of the technical grade product. The monomer is slowly transformed into dimer and possibly into a trimer when dissolved in water. Various analytical techniques were used in the study of this system. Factor analysis with column cross-validation was applied to chromatographic data to help in the resolution of the system.     

Oxidative Deprotection of Cyclic Acetals and Trimethylsilyl Ethers by γγ-Picolinium Chlorochromate Under Nonaqueous Conditions

Deprotection of cyclic acetals and oxidative desilylation of trimethylsilyl ethers into the corresponding carbonyl compounds with -picolinium chlorochromate (-PCC) under nonaqueous conditions at room temperature is described. Oxidation of aldehydes to carboxylic acids was not observed in any case.     

Arylation of 2,5-dimethyl-4-phenylpyridine

The position of the pyridine ring is arylated by reaction of 2,5-dimethyl-4-phenylpyridine with phenyllithium and p-tolyllithium. Destructive oxidation of the diaryl-substituted pyridines primarily affects the pyridine ring.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1359–1361, October, 1970.     

The catalytic reactions of triethyl- and triethoxy-silane with unsaturated sulphides

The hydrosilylation of mono- and di-alkenyl sulphides of the type RS(CH₂)_nCH=CH₂ (R = C₂H₅, CH₂=CH, CH₂=CHCH₂, C₃H₇, n = 0, 1 and 4) by triethyl- and triethoxy-silane, catalyzed by H₂PtCl₆·6 H₂O, (Ph₃P)₃RhCl and (PhCN)₂PdCl₂·Ph₃P, has been studied. The addition of hydrosilane to the double bond of alkenyl sulphide leads to a mixture of two isomeric monoadducts. The hydrosilane can cleave the C---S bond of the initial sulphides giving the corresponding derivatives of thiosilanes, X₃SiS(CH₂)_nCH=CH₂ (X = C₂H₅, C₂H₅O). Hydrosilylation of alkenyl sulphides is accompanied by some side reactions such as dehydrocondensation, reduction and polymerization. The effect of the catalyst nature, the structure of hydrosilane and alkenyl sulphide on the reaction route has been investigated.     

Partial molal heat capacities of aqueous tetraalkylammonium bromides as functions of temperature

Enthalpies of solution have been measured from 5 to 85°C for aqueous tetraethyl- and tetrapropylammonium bromides, and the integral heat method is employed to evaluate for these electrolytes over a wide temperature range. Data taken from the literature have been used to evaluate for aqueous Bu₄NBr over a similar temperature range. These data, along with similar data for Me₄NBr, previously reported, have been used to evaluate absolute ionic heat capacities. While the absolute values agree only qualitatively with two other methods of division, the temperature dependences of the three methods essentially agree up to 65°C. Heat capacities due to structural effects on the solvent, obtained by subtracting the inherent heat capacities of the ions, are extraordinarily positive for all four tetraalkylammonium ions and have negative temperature coefficients, indicating that all four ions, including the tetramethylammonium ion, are structure-making ions.     

Copper precipitation from sulfate solutions with calcium carbonates

Mechanism of interaction of copper sulfate with natural calcium carbonates, responsible for low residual copper concentrations in solutions and for the behavior of open and closed systems in storage is considered.