Intrinsic and extrinsic factors in anion electron-stimulated desorption: D- from deuterated hydrocarbons condensed on Kr and water ice films

The results of D(-) ion desorption induced by 3-20 eV electrons incident on condensed CD(4), C(2)D(6), C(3)D(8), C(2)D(4), and C(2)D(2) are presented. These compounds were deposited in submonolayer amounts on the surfaces of multilayer solid films of Kr and nonporous and porous amorphous ice. While desorption of the D(-) anions proceeds via well-known processes, i.e., dissociative electron attachment (DEA) and dipolar dissociation, significant perturbations of these processes due to presence of the different film substrates are observed. We have shown that it is possible to distinguish between the character and nature of these perturbations. The presence of the nonporous ice perturbs the D(-) desorption intensity by affecting the intrinsic properties of the intermediate anion states through which dissociation proceeds. On the other hand, the presence of the porous ice introduces extrinsic effects, which can affect electron energy losses prior to their interaction with the hydrocarbon molecule and/or the energies and intensities of the fragment species after dissociation. Simple mechanisms responsible for the observed variations in the intensities of desorbed anionic signals are proposed and discussed. Electron transfer from transient anion states to electron states of the substrate film or nearby hydrocarbon molecules appear as the most efficient mechanism to reduce the magnitude of the DEA process.     

Application of kinetic investigations for interpretation ofn-hexane and benzene adsorption on active carbon

Differencies between the mechanism ofn-hexane and benzene adsorption on active carbon were investigated on the ground of kinetic measurements. As it has been stated, the kinetic measurements show fundamental differencies between the mechanism of adsorption in spite of analogy existing in the state of adsorption equilibrium. Within the range investigated, only the adsorption ofn-hexane follows the model of volume filling of micropores. Existence of those differencies is also confirmed by measurements of effective diffusion coefficient values as well as changes of activation energy of the diffusion—adsorption process.

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Anwendung kinetischer Untersuchungen zur Interpretation des Adsorptionsverhaltens vonn-Hexan und Benzol an Aktivkohle

Zusammenfassung Mittels kinetischer Messungen untersuchte man die Unterschiede im Mechanismus des Adsorptionsverlaufes vonn-Hexan und Benzol an Aktivkohle. Man stellte fest, daß trotz der Analogie im Adsorptionsgleichgewichtszustand die kinetischen Messungen auf prinzipielle Unterschiede im Adsorptionsmechanismus hinweisen. Im untersuchten Bereich verläuft nur die Adsorption vonn-Hexane nach dem Modell der Mikroporenvolumenausfüllung. Die auftretenden Unterschiede wurden auch durch die Berechnungen der Werte der effektiven Diffusionskoeffizienten sowie Änderungen der Aktivierungsenergie des Diffusions-Adsorptionsprozesses bestätigt.

     

Bond energy, aromatic stabilization energy and strain in IPR fullerenes

Various models applied to DFT structures and energies of 2-D and 3-D aromatic molecules shed new light on the effects of strain and aromaticity in these systems. The cyclic pi electron delocalisation does not stabilize the fullerene C60 formation; and 5-6 and 6-6 CC bonds have near-identical bond stretch potentials.     

Kinetics and mechanism of base hydrolysis of Reinecke's salt revisited – specific salt effects

The kinetics of base hydrolysis of the trans-[Cr(NH₃)₂(NCS)₄]^– anion follows the rate law: -d[complex]/dt = k ₀ + k ₁[OH^–] (50–70 °C, [OH^–] = 0.1–1.9 M and = 2.0 M). The specific salt effect has been investigated for eight aqueous media: NaCl, NaBr, NaI, NaClO₄, KCl, KBr, CsCl and CsBr. The alkali-independent path (k ₀) does not show any specific effect of inert electrolyte ions, the activation parameters: H = 113.5 ± 0.4 kJ mol^–1 and S = 24.1 ± 1.3 J mol^–1 K^–1 are interpreted in the frame of a dissociative interchange mechanism (I _d). For the alkali-dependent path (k ₁) the specific salt effect is observed for cations of the inert electrolyte, showing an important role for ion-pair formation between the cations and reagent complex anion in the activation process. A linear correlation between lnk ₁ and lnK ₀ (K ₀ – ion-pair formation constant) has been found for the cations studied. The dissociative, via conjugate base, mechanism (D _CB) has been proposed for the alkali-dependent path.     

Stereochemistry of organophosphorus cyclic compounds—II : Stereospecific synthesis of cis- and trans 2-halogeno-2-oxo-4-methyl-1,3,2-dioxaphosphorinans and their chemical transformations

cis- and trans-2-Chloro-2-oxo-4-methyl-1,3,2-dioxaphosphorinans have been obtained by stereospecific reactions of diastereomerically pure 2-methoxy-4-methyl-1,3,2-dioxaphosphorinans or 2-hydrogen-2-oxo-4-methyl-1,3,2-dioxaphosphorinans with chlorine and sulphuryl chloride, respectively. Similarly, the action of the corresponding brominating agents on isomeric phosphites and phosphonates afforded pure cis- and trans-2-bromo-2-oxo-4-methyl-1,3,2-dioxaphosphorinans. It has been shown that halogenolysis proceeds with retention of configuration at the P atom. On the basis of the ¹H- and ³¹P-NMR spectra conformation of the halogenoanhydrides obtained has been discussed briefly.It has been also found that model nucleophilic substitution reactions occur with inversion of configuration at the P atom in the cyclic halogenoanhydrides.     

Infrared study of adsorption of methanol,deuterated methanol and ethylene on the surface of ZSM-5 type zeolite

The surface species resulting in exposing of the ZSM-5 zeolite at elevated temperatures to methanol, deuterated methanol or ethylene have been studied by IR method.The three-step adsorption at 150°, 300°, 420° C or one-step adsorption at 420° C have been carried out in order to prepare the samples for IR. In all cases the most prominent band appeared in the range 1495–1515 cm^?1; besides two bands at about 1470 and 1370 cm^?1 have been observed. On the basis of Greenler's results and of the shift values of the bands in our spectrum of adsorbed deuterated methanol it was supposed that the band 1495–1515 cm^?1 is due to the OCO group from the surface species. Moreover these species would involve both oxygen atoms from the surface of zeolite but not from OH groups of methanol.     

Small-angle x-ray scattering studies on epoxidized butadiene-styrene block copolymers

Small-angle x-ray scattering (SAXS) and scanning electron microscopy (SEM) investigations for epoxidized butadiene-styrene (BS) block copolymers were performed. For unepoxidized copolymers, the SAXS curve exhibits a maximum which indicates that the copolymer has heterogeneity domain morphology. Using the standard theory for a two-phase system, mean distances between domains, the correlation length l _p , and the thickness of the phase boundary were calculated from the SAXS data. It was found that the epoxidation of BS copolymers decreases the ability of the copolymer to separate the individual components. As the content of the epoxide groups increases, the dimensions of the domains decrease until they disappear, the boundary between domains and the matrix becomes less and less definite, and the copolymer composes a homogeneous system. The disappearance of the two-phase structure of the BS copolymers indicates an increase in the compatibility of polystyrene and epoxidized polybutadiene. According to the method of Van Krevelen, the solubility parameters of polystyrene and epoxypolybutadiene were calculated. Small differences between these parameters support the conclusions drawn from the SAXS investigations     

Intermittency and the central limit theorem

Central limit theorem estimates of anomalous fractal dimensions of self-similar random cascades are studied. It is found that, in general, the normal approximation fails badly. A systematic series of approximations which converges to the exact result (both for the fractal dimensions and for the distribution itself) is derived for the -model. Consequences for the empty bin effect are indicated.Supported by the World Laboratory/HED and the CERN/LAA Projects     

Thermal analysis of binary and ternary systems of salicylic acid,sodium salicylate and sodium hydrogen carbonate

The thermal decompositions of binary and ternary systems of salicylic acid, monosodium salicylate, disodium salicylate and sodium hydrogen carbonate were studied by thermogravimetry and differential thermal analysis. The possibility was shown of analyzing systems involving components which react with each other upon heat treatment. Use can be made of results of this work to follow the course and extent of the reaction employed in the commercial method of manufacturing sodium salicylate and to check declared compositions of salicylate mixtures.

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Zusammenfassung Die thermische Zersetzung binärer und ternärer Systeme, die Salicylsäure, Mononatriumsalicylat, Dinatriumsalicylat und Natriumhydrocarbonat enthalten, wurde untersucht. Die Möglichkeit der Analyse von Systemen, deren Komponenten bei Hitzebehandlung miteinander reagieren, wurde gezeigt. Die Ergebnisse dieser Arbeit gestatten den Verlauf und das Ausmaß der Reaktionen zu untersuchen, welche bei dem Herstellungsverfahren von handelsüblichen Natriumsalicylat ablaufen und die deklarierte Zusammensetzung von Salicylatmischungen zu prüfen.

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Résumé Etude par thermogravimétrie et analyse thermique différentielle de la décomposition thermique de systèmes binaires et ternaires constitués d' acide salicylique salicylate monosodique, de salicylate disodique et d'hydrogénocarbonate de sodium. On montre la possibilité d'analyser des systèmes dont les composants réagissent entre eux lors du traitement thermique. Les résultats de cette étude permettent de suivre le déroulement et le degré d'avancement de la réaction utilisée dans le procédé commercial de fabrication du salicylate de sodium et de contrôler la composition déclarée des mélanges de salicylates.

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Kinetics of particle deposition in the oblique impinging jet cell

A new oblique impinging-jet (OBIJ) cell was developed, suitable for colloid deposition studies at various interfaces. In contrast to previously used orthogonal cells, the OBIJ construction makes possible direct microscope observations of particle deposition on nontransparent substrates. The cell performance was tested by studying kinetics of polystyrene latex particle deposition on mica. Two limiting cell configuration were used in the experiments: (i) the lower position (inverted microscope observation of substrate surface through air) and (ii) the upper position (observation of the substrate surface with adsorbed particles through the suspension layer). The dependence of local mass transfer rate (particle flux) on the position over the substrate surface was studied for various flow Reynolds numbers. It was demonstrated that deposition rate attained maximum at the flow stagnation point whose position was dependent on Re number. Moreover, it was shown that the local flux decreased at much slower rate when moving in the downstream direction, than for previously used impinging-jet cells. Consequently, the area of uniform transport conditions was larger, enabling more precise determination of the limiting particle flux at the stagnation-point. The dependence of the flux on Re number was systematically studied for various ionic strength of the suspension. It was demonstrated, in accordance with previous results for the ordinary impinging-jet, that the flux increased significantly for low ionic strength and high Re number. This phenomenon, referred to as the inverse salt effect, was interpreted in terms of the convective diffusion theory. The governing transport equation originating from this theory was solved numerically, for the region near the stagnation point, using the finite-difference method. These numerical solutions were used for nonlinear fitting of the flow intensity parameter dependence on the Re number. In this way the flow field in the vicinity of the stagnation point was fully characterized. It was concluded that the new cell can be exploited as an effective experimental tool for colloid deposition studies on various substrates.