Thermodynamics of Lithium Intercalates in Carbonized Fabric

The method of quasi-equilibrium galvanostatic curves was applied to study the thermodynamics of lithium deintercalation from the system Li _x C₆ (solid phase)/Li⁺ (solution) in the interval 293-323 K and the thermodynamic characteristics (G, S, H) of lithium intercalation compounds in a carbonized fabric in relation to the degree of intercalation x.     

Spin-spin coupling of77Se and31P nuclei in cyclic organophosphorous compounds

We have established that direct phosphorus-selenium spin-spin coupling constants in cyclic compounds with P=Se exocyclic and P-C endocyclic bonds are found in the range¹J_PSe=–708 to –859 Hz; in this case, it is greater for the axial orientation of P=Se than for the equatorial orientation.Deceased.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 776–780, April, 1990.     

Phosphorus-containing podands 7. Complexing properties of ortho-diphenylphosphinyl-substituted diphenyl ethers of oligoethylene glycols with respect to alkali-metal cations

Stability constants of complexes of alkali-metal cations with oligoethylene glycol diethers RO(CH₂CH₂O)_nR (n=1–5), where R=2-Ph₂P(O)C₆H₄ and 2-Ph₂(O)-4-t-BuC₆H₃P, have been determined conductometrically in a tetrahydrofuran-chloroform mixture (41 by volume). The dependence of complexing ability on a number of monopodand donor centers for Li⁺ and Na⁺ has multiple extrema. For K⁺, Rb⁺, and Cs⁺ the complexing abilities steadily increase with the length of the ligand polyether chain. Monopodands based on triethylene glycol and its pyrocatechol analog are highly effective (log K=6.7–7.0) with respect to Li⁺. The synthesis of ligands with a lipophilic tert-butyl substituent in the terminal group is described.For previous communication, see [1]. The number of the communication in [2] is 5, not 4 as printed in error.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 1992–2000, September, 1991.     

Rotational-diffusion anomalies in dye solutions from transient-dichroism experiments

Subnanosecond transient-dichroism experiments have been performed to investigate the rotational diffusion of dyes in solution. Dyes and solvents were chosen in a way to obtain information on the influence of size, shape and hydrogen-bonding abilities either of the solute or the solvent molecules. One finds slow orientational relaxation of di-anionic xanthene dyes in alcohols, while oblate cationic dyes rotate faster in spite of their comparable size. The rotational diffusion times for alcohol solutions exceed the theoretical values predicted by the Debye-Einstein model except for prolate molecules. For a solute molecule with internal mobility the rotational diffusion exhibits a partial slip behaviour. It is shown that the deviations from the Debye-Einstein model are restricted to alcohols since for other solvents either with or without strong hydrogen-bonding abilities the experimental values agree with the hydrodynamic model including the stick-boundary condition. Experiments on erythrosine B reveal the influence of size and shape of the attached solvent molecules.     

Electronic structures and MCD spectra of trigonal Cr(III)S6 systems

MCD, electronic absorption, external heavy atom, and crystal field data are presented for the low energy region (² E _g, ² T _1g, ⁴ T _2g) and high energy region (² T _2g, ⁴ T _1g) of Cr(dtp)₃, Cr(dtc)₃, and Cr(exan)₃. At low energy, MCD intensities of ² E(² E _g) and ² E(² T _g) are as large or larger than ⁴ T _2g, and the MCD technique is advantageous over electronic absorption in this respect. The MCD positions of ² E _g and ² T _1g are nearly the same for these molecules ( 13 kK and 13.6 kK) · ⁴ T _2g of this region appears trigonally split ( 500 cm^–1) in the MCD of dtp but to a smaller extent than in the electronic crystal spectrum of Lebedda and Palmer ( 600 cm^–1). MCD did not resolve such components for exan and dtc. The higher energy region includes ² T _2g and ⁴ T _1g, and the combined MCD and electronic absorption data of the three compounds taken together lead us to conclude the ordering ² A ₁(² T _2g)<² E(² T _2g)<⁴ E(⁴ T _1g). The potentially useful external heavy atom affect on the solution-observed electronic ² E and ⁴ E bands of Cr(dtp)₃ did not shed additional light on this order of E states. Finally, it is concluded that the order of ⁴ T _1g and ² T _2g cannot be decided from O _h crystal field calculations because of experimental uncertainties about choosing centers of gravity. In addition, ⁴ T _1g and ² T _2g are close together so that ordering ² E<⁴ E does not guarantee ² T _2g<⁴ T _1g. However, it can be concluded that the ratio C/B4 is not correct, whereas the larger 7<(C/B)<8 is consistent with the data of all three molecules because of small B parameters ( 0.4). Locating OO transitions may somewhat decrease C/B and Dq.

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Zusammenfassung In der vorliegenden Arbeit werden folgende Meßergebnisse mitgeteilt; MCD, elektronische Absorption, Einfluß eines äußeren schweren Atoms sowie Kristallfelddaten für den Bereich niedriger Energie (² E _g, ² T _1g, ⁴ T _2g) und den Bereich hoher Energie (² T _2g, ⁴ T _1g) von Cr(dtp)₃, Cr(dtc)₃ und Cr(exan). Bei niedriger Energie sind die MCD-Intensitäten von ² E(² E _g) und ² E(² T _1g) genau so groß, oder größer als ⁴ T _2g, und die MCD-Technik bietet Vorteile gegenüber der elektronischen Absorptionsmethode. Die MCD-Werte von ² E _g und ² T _1g sind für die genannten Moleküle etwa gleich ( 13 kK und 13,6 kK). ⁴ T _2g dieses Gebietes erscheint trigonal aufgespalten ( 500 cm^–1) bei MCD von dtp, aber in einem geringeren Maß als im elektronischen Kristallspektrum von Lebedda und Palmer ( 600 cm^–1) MCD löste solche Komponenten bei exan und dtc nicht auf. Der Bereich höherer Energie enthält ² T _2g und ⁴ T _1g, und aus der Kombination von Daten der MCD-Methode sowie der elektronischen Absorption schlossen wir auf die Anordnung ² A _1g(² T _2g)<² E(² T _2g)<⁴ E(⁴ T _1g). Der möglicherweise nützliche Effekt eines äußeren schweren Atoms auf die in Lösung beobachteten elektronischen ² E- und ⁴E-Banden von Cr(dtp)₃ brachte bezüglich dieser Anordnung der E-Zustände nichts Neues. Weiterhin wird gefolgert, daß die Ordnung von ⁴ T _1g und ² T _2g nicht aus O _h-Kristallfeldberechnungen entschieden werden kann, da experimentelle Unsicherheiten bezüglich der Wahl von Schwerpunkten bestehen. Außerdem liegen ⁴ T _1g und ² T _2g nahe zusammen, sodaß aus der Anordnung ² E<⁴ E nicht notwendig ² T _2g<⁴ T _1g folgt. Es kann jedoch gefolgert werden, daß das Verhältnis C/B4 nicht korrekt ist, während 7<(C/B)<8 konsistent mit den Daten aller drei Moleküle ist, da die B-parameter klein sind (0,4). Die Vokalisierung der OO-Übergänge könnten C/B und Dq etwas erniedrigen.

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Presented in part at the 161st American Chemical Society National Meeting, Los Angeles, California, March–April, 1971.

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NDEA Pre-Doctoral Fellow.     

Structure of Charge Transfer Reaction Complexes Formed in Anionic Polymerization of Isoprene

A new mechanism is suggested for the anionic polymerization of isoprene. The key moment of this mechanism is thermal electron excitation of the complex of a living polymer with a monomer to the low lying S₁ (T₁) state involving a charge (electron) and (Li⁺) cation transfer from the terminal unit to the monomer molecule. It is stated that the probability of chemical bonding depends on the spin density on the radical centers of reactant molecules and on the geometry of the reaction complex. The semiempirical AM1 and ab initio 6-31G* quantum-chemical calculations revealed strong interaction for the ground electronic state of the complex (5-10 kcal/mole) and low energies of the excited triplet levels (<10 kcal/mole).     

Identification of raw materials for the production of vodkas based on the results of gas-liquid chromatographic analysis with the use of fuzzy logic

The concepts of fuzzy logic were applied to the analysis of gas-chromatographic data for 12 samples of Russian vodka products. It was found that, with the use of the truth degrees of fuzzy logic propositions on the composition of analytical samples based on a simulation of expert’s reasoning, the grade of raw materials used for the production of the analytical samples can be supposed and the conformity with standards can be established.     

Kinetics of flocculation and thickening of precipitates of bentonitic clay suspension in the presence of acrylamide copolymers in aqueous salt solutions

The kinetics of hindered sedimentation and thickening of the sediments of a real disperse system (bentonitic clay suspension) was studied. The flocculation parameters of acrylamide copolymers in aqueous and aqueous salt solutions were evaluated in relation to the chemical nature and concentration of flocculants and electrolytes.     

Reactivity of Cage-Like Amines toward p-Toluenesulfonyl Chloride and Diphenyl Chlorophosphate in Acetonitrile

The nucleophilic reactivity of amines of the norbornane, norbornene, and adamantane series toward ptoluenesulfonyl chloride and diphenyl chlorophosphate in acetonitrile at 25°C is determined mainly by the steric factor. Parameters characterizing spatial accessibility of the reaction center in the amine molecule have been determined. Cage-like substituents show no appreciable effect on the amine reactivity, as compared to common alkyl groups.