Reaction graphs and a construction of reaction networks

Summary A general definition of reaction graphs is presented. For a pair of isomeric molecular graphs and , related by a chemical transformation , the reaction graph is determined using a maximal common subgraph defined for vertex mapping . A binary operation defined for graphs constructed over the same vertex set enables us to decompose the reaction graph into the sum of prototype reaction graphs. A decomposition of an overall reaction graph can be advantageously used for the construction of a reaction network. An oriented path in this network beginning at and ending at corresponds to a breakdown of the transformation into a sequence of intermediates.     

Iodine sorption,porosity, and wettability of carboxymethylcellulose of low degree of substitution

Cellulosic fabric was carboxymethylated by single-bath method for different durations. arrived at a maximum when plotted against the time of reaction. This might be interpreted by the dissolution of the highly substituted fractions. The fibrous character of the carboxymethylated samples remained unchanged, but the accessibility of the cellulose characterized by iodine sorption, porosity, and wettability changed significantly. The carboxymethylation had a complex effect on the investigated parameters: the values of accessibility were increasing initially, caused by opening the fibrillar structure, but decreasing later as the swollen structure was collapsing during air-drying. The studied properties were depending not only on the changes in but also on the reaction parameters.     

Effect of solvent on the partial molal volumes and heat capacities of nonelectrolytes

Group contributions to in seven solvents and to in three solvents have been tabulated. The variation of group parameters is discussed in terms of the solvent compressibility coefficient, _T. The scaled particle theory (SPT) is used to calculate cavity contributions to and C _p2 ^o . Interaction contributions are obtained from the cavity terms and and values estimated through the additivity schemes. values are more sensitive to solute-solvent interactions than in water and less sensitive in methanol. The SPT results for heat capacities support the concept of structural promotion by hydrophobic solutes in water.     

Effect of charge on the standard partial molar volumes and heat capacities of organic electrolytes in methanol and water

Previously developed additivity schemes for nonelectrolytes have been used to estimate and for tetraalkyl and tetraphenyl methanes in methanol and water. Corrections have been applied to the thermodynamic values of these model compounds to account for a variation in size of the central atom, and these were used to ascertain the effect of charge on and of alkyl and phenyl quaternary ions having N, P and B as central atoms. Investigations of R₄NBr, (R=methyl to heptyl) salts show that the charge effect on and of R₄N⁺ ions is large and relatively independent of ion size suggesting that the solvent molecules penetrate the ions. The ability to estimate and of the quaternary ions in the bromide salt solutions has made it possible to make ionic assignments with some confidence; (Br^–) has been evaluated as 19.7±2 and 30.2±7 cm³-mol^–1 and (Br^–) as –83±7 and –68±30 J-K^–1-mol^–1 in methanol and water, respectively. The use of organic ions for making ionic assignments of and is critically examined and comparisons with other assignments are made. The scaled particle theory is employed to divide the heat capacities of electrolytes into cavity and interaction contributions.     

Perturbative solution of the RPA equation. An application to the calculation of rotational strengths

The RPA equation is solved by perturbation in Møller-Plesset (MP) and Epstein-Nesbet (EN) partitions, which are first compared on a specific example. To still accelerate the faster one (EN), a third scheme is proposed, which involves preliminary diagonalization within a limited subset , followed by usual EN perturbation between and the rest of the whole configuration space. Criteria for the choice of are given.     

Interpolation of parameters of solutions expressed as functions of composition

The number of parameters in the polynomial is discussed for N components and a polynomial extending up to power n. This number is found to be but may be N less for relative thermodynamic functions. The equation of degree n for an N-component system requires the use of data for each of the i-component systems. Data on the n-component systems suffice if n相似文献   

Einflu? der Herstellungsbedingungen auf die Eigenschaften eines Celluloseaustauschers mit Salicyls?ure als funktioneller Gruppe

Zusammenfassung Die Darstellung eines Celluloseaustauschers mit Salicylsäure als funktioneller Gruppe wurde variiert, um die optimalen Bedingungen sowohl hinsichtlich eines raschen Austausches als auch im Hinblick auf eine hohe Kapazität zu finden. Zwei Arten von Cellulose (vernetzt und mikrokristallin) und verschiedene Reaktionszeiten wurden verwendet. Die Eigenschaften der Reaktionsprodukte wurden mit Hilfe von Titrationskurven zur Bestimmung der Kapazität und durch Messung des nicht-isotopen Austauschs und des Isotopenaustausches als Funktion der Zeit untersucht. Optimale Bedingungen wurden mit mikrokristalliner Cellulose und einer Reaktionszeit von 15 min erhalten.

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Effect of the conditions of preparation on the properties of a cellulose exchanger containing salicylic acid as a functional group

The preparation of a cellulose derivative containing salicylic acid as functional group was varied in order to find optimal conditions with respect to fast exchange as well as high capacity. Two kinds of cellulose (cross-linked and microcrystalline) and different reaction times were used. The properties of the products were investigated by titration curves to determine the capacity and by measuring the non-isotopic exchange and the isotopic exchange as a function of time. Microcrystalline cellulose and a reaction time of 15 min gave optimal results.

     

Preferential solvation in three component systems: Evaluation of Kirkwood-Buff parameters

The extent of local excess or deficiency of a component solvent near the solute in a mixed binary solvent has been calculated using the Hall formalism for the Kirkwood-Buff equation. The possibility of calculation of the two solute-solvent Kirkwood-Buff parameters using the values is discussed. A model calculation using literature data for preferential solvation in mixed binary solvents is presented. The solute-solvent and solvent-solvent interactions and the relative size of the solvents are also shown to be relevant factors in determining the values.     

Reactions of alkoxy and hydroxy radicals generated photochemically from hydroperoxide molecules

In the present work as well as HRO^. radicals were generated in the photochemical interaction of 1,2-benzanthracene with -ethyl phenyl hydroperoxide /HROOH/ in C₆H₆ and CCl₄ at 304 K. radicals were trapped by C₆H₆. The main reaction of HRO^. radicals is hydrogen abstraction from the hydroperoxide group of HROOH. Although OH radicals are less selective, the hydrogen abstraction is the main process during their interaction with aromatics in contrast to reactions in aqueous solutions, where addition to the benzene ring is the rate-determining process in CCl₄:

Kettenverzweigung bei der Polymerisation von Vinylchloracetat und Vinylacetat

Zusammenfassung Bei niedrigen Umsätzen und einer Polymerisationstemperatur von 50°C erhaltene Polyvinylacetate sind unverzweigt; das gleiche gilt für Polyvinylchoracetate. Bei diesen wurde die bei höheren Umsätzen auftretende Verzweigung durch Verseifung und Acetylierung der Polymeren sowie durch Messung von []-, und Werten an den Polymeren bestimmt. Eine Selbstverzweigung der wachsenden Kette konnte nicht gefunden werden. *** DIRECT SUPPORT *** A3615144 00012

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Chain branching in vinyl chloroacetate and vinyl acetate polymerization

Polymerization of vinyl acetate and vinyl chloroacetate to low conversions at 50°C gave unbranced polymers. The branching of polyvinyl chloroacetates at higher conversions was determined by hydrolysis and acetylation of the polymers and by measuring [], and . No self-branching of the growing chains could be found.

     

Pseudo-point groups and chronality in enumeration of reaction pairs

Summary The pseudo-point group is constructed to characterize the symmetry of a basic pair of hexagonal reaction graphs having no par-bonds on its edges. Any pairs of reaction graphs (reaction pairs) are considered to be obtained by adding par-bonds to the edges of the basic pair; they are counted by the USCI (unit-subduced-cycle-index) approach. Thus, the six edges of the basic pair are assigned to the coset representation (/C _2v ). After the subduction of the is calculated, the partial-cycle-index method of the USCI approach is applied to the combinatorial enumeration of reactions pairs.Reaction pairs are classified to two categories, i.e. isoenergetic and anisoenergetic. An isoenergetic pair is concluded to be a self-reaction pair, while an anisoenergetic pair corresponds to a non-self-reaction pair. The concept of chronality is also discussed to clarify the symmetrical nature of the resulting orbits.     

The thermodynamics of dilution ofn-dodecyltrimethylammonium bromide micelles in aqueous solutions

Summary The relative partial molal thermodynamic functions ₁ and have been derived from reported experimental light scattering and calorimetric measurements on micellar solutions ofn-dodecyltrimethylammonium bromide. It is shown that the magnitudes of the thermodynamic functions are considerably larger than can be accounted for by the interaction of the electrical double layers surrounding the micelles. Possible enthalpy changes arising from a change in micelle shape, size and degree of dissociation on dilution are discussed.

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Zusammenfassung Die relativen molaren thermodynamischen Partialfunktionen , andS ₁wurden abgeleitet aus Literaturwerten von Lichtstreuungsmessungen und kalorimetrischen Untersuchungen an mizellaren Lösungen vonn-Dodecyltrimethylammoniumbromid. Es wird gezeigt, daß die Zahlenwerte der thermodynamischen Funktionen erheblich größer sind als von der Wechselwirkung der elektrischen Doppelschichten zu erwarten ist, die die Mizellen umgeben. Mögliche Enthalpieänderungen, die sich aus Änderungen von Größe, Gestalt und Dissoziationsgrad bei Verdünnung herleiten, werden diskutiert.

     

Kinetics of the reaction of superoxide anion-radical with olefins

Kinetic investigation of the reaction of electrochemically generated with perfluorooctene, styrene, and cyclohexene in acetonitrile, in the presence of tetraethylammonium perchlorate used as a background electrolyte, revealed that reacts with styrene and perfluorooctene at the double bond, and the reactivity of the olefins with respect to decreases with decrease in the electrophilicity of the substituents at the double bond: perfluorooctene > styrene > cyclohexene. The main transformation products of styrene are phthalic and benzoic acid esters.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 733–737, April, 1990.The authors thank V. B. Bol'evoi for his contribution to the discussion of the results obtained.     

Über ein Verfahren zur Erzeugung zweiseitig eingespannter,kurzer Polyethylen-Modellketten

Zusammenfassung Ein Algorithmus zur Erzeugung zweiseitig eingespannter Polyethylen-Modellketten im Diamantgitter wird vorgestellt, dessen Grundidee folgendermaßen angegeben werden kann: Die Gesamtheit der Modellketten bestimmter Kettenlängen zu einem vorgegebenen Anfang-End-Vektor erhält man, indem man zunächst die Grundverteilung zu diesem Anfang-End-Vektor bestimmt, durch Hinzufügen von geeigneten Paaren einander entgegengesetzter Gittervektoren die für die gegebene Kettenlänge möglichen Vektorverteilungen ermittelt und schließlich zu diesen alle möglichen Anordnungsmöglichkeiten der Gittervektoren sucht. Der Algorithmus wird im Abschnitt 2.1. am Beispiel des ebenen Wabengitters erläutert und dann im Abschnitt 2.2. auf das dreidimensionale Diamantgitter angewendet. Das Flußschema des entsprechenden Computerprogramms ist im Anhang angegeben.

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An instruction is given for generating polyethylene model chains fixed at their two ends in the diamond lattice. The fundamental thought is as follows: The ensemble of model chains of given length and end-to-end vector is obtained in three steps. First of all the basic distributions of chain vectors belonging to is determined. Secondly, all the possible distribution of chain vectors consistent with given chain length are found by addition of suitable pairs of opposite chain vectors to the basic distribution. Thirdly, all the allowed sequences of chain vectors are arranged.In section 2.1. this method is demonstrated for the plane honeycomb lattice. In section 2.2. it is applied to the tridimensional diamond lattice.The flow diagram of the computer programme is given in the appendix.

     

Structure of products of the addition of methane- and ethane-sulfenyl chlorides to acrylic acid derivatives

Conclusions When alkanesulfenyl chlorides are added to acrylic derivatives CH₂=CHR (R=COOH, COOCH₃, COOCH₃ CN, CONH₂ a mixture of the isomers and is formed and the proportions of these depend on the nature of the substituent R.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1069–1075, June, 1966.     

Configuration and conformation of substituted 1,3,2-dioxaarsenanes

The configuration and conformations often 2-, 4-, and 5-substituted 1,3,2-dioxaarsenanes were studied from their PMR spectra. Inversion of the shielding constants of protons in the 4, 6, and 5 positions and of methyl groups in the 5 position was established, and the axial orientation of the As-Cl and As-OR bonds, the equatorial orientation of the 4-CH₃ group, and the chair conformation of the six-membered heteroring were proved. The anisotropies of the diamagnetic susceptibility were estimated for the first time: and (dipole approximation); and (nondipole approximation). The cyclic torsion angle (= 58°) as found for 2-chloro-1,3,2-dioxaarsenane by the R-factor method. Conclusions regardiwng the conformation of the ring and substituents were confirmed by a study of the specific effect of an aromatic solvent on the position of the resonance lines.Communication I from the series Investigation of the Stereochemistry of Organic Arsenic Compounds by NMR Spectroscopy.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 457–463, April, 1973.     

Vibrational spectra and structure of sulfonium nitroimides

Vibrational spectroscopy and x-ray structure analysis have been used to investigate three new types of sulfonium nitroimides: N-nitrosulfylimides, N-nitrosulfoximides, and N,N-dinitrosulfodiimides. Structural parameters have been determined for the molecules , , and .Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2489–2496, November, 1991.     

Hyperpolarizability of polyene chains in Hückel model with an accounting for real geometry

It has been found that in the transconfiguration, the Hückel hyperpolarizability of -shells ( ) vanishes at a bond angle of 125. The cis configuration is characterized by alternation of the sign of , depending on whether N/2 is odd or even (N is the number of carbon atoms). Approximate relationships have been established: for the trans form, and for the cis form.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 28, No. 1, pp. 25–28, January–February, 1992.The authors wish to express their sincere appreciation to A. V. Luzanov for steady interest in the work and for detailed discussion of the entire set of problems that are involved.     

Light-scattering studies on solutions of potassium-polyphosphate

Summary Light scattering measurements on a number of samples of potassium polyphosphate dissolved in 0.1 M NaBr solution in water were made. With fair approximation, the second virial coefficient was found to be inversely proportional toM _w ^0.5 (M _w = Weight-average Molecular Weight). In conjunction with intrinsic viscosities, the values ofM _w were used in calculating the radius of gyration, . The ratio was found to be constant indicating that potassium Kurrol Salt exists as random coils in solutions. The average value of Flory constant calculated with the help of the available data was found to be 1.96 × 10²¹ which is quite close to that predicted by Flory.Post Doctoral fellow.