Conduction in Bi2O3-based oxide ion conductor under low oxygen pressure. II. Determination of the partial electronic conductivity

In order to investigate the partial electronic conduction in the high oxide ion conductor of the system Bi₂O₃-Y₂O₃ under low oxygen pressure, e.m.f. and polarization methods were employed. Although the electrolyte was decomposed when the \(P_{{\text{O}}_{\text{2}} }\) was lower than the equilibrium \(P_{{\text{O}}_{\text{2}} }\) of Bi, Bi₂O₃ mixture at each temperature, the ionic transport number was found to be close to unity above that \(P_{{\text{O}}_{\text{2}} }\) . The hole conductivity (σ _p) and the electron conductivity (σ _p) could be expressed as follows, $$\begin{gathered} \sigma _p \Omega cm = 5 \cdot 0 \times 10^2 \left( {P_{O_2 } atm^{ - 1} } \right)^{{1 \mathord{\left/ {\vphantom {1 4}} \right. \kern-\nulldelimiterspace} 4}} \exp \left[ { - 106 kJ\left( {RT mol} \right)^{ - 1} } \right] \hfill \\ \sigma _p \Omega cm = 3 \cdot 4 \times 10^5 \left( {P_{O_2 } atm^{ - 1} } \right)^{ - {1 \mathord{\left/ {\vphantom {1 4}} \right. \kern-\nulldelimiterspace} 4}} \exp \left[ { - 213 kJ\left( {RT mol} \right)^{ - 1} } \right] \hfill \\ \end{gathered} $$ These values were much lower than the oxide ion conductivity under ordinary oxygen pressure.     

The Effect of CO2 and H2O on the Kinetics of NO Reduction by CH4 Over Sr-Promoted La2O3

The influence of CO₂ and H₂O on the activity of 4% Sr-La₂O₃ mimics that observed with pure La₂O₃, and a reversible inhibition of the rate is observed. CO₂ causes a greater effect, with decreases in rate of about 65% with O₂ present and 90% in its absence, while with H₂O in the feed, the rate decreased around 35-40% with O₂ present or absent. The influence of these two reaction products on kinetic behavior can be described by assuming competitive adsorption on the surface, incorporating adsorbed CO₂ and H₂O in the site balance, and using rate expressions previously proposed for this reaction over Sr-promoted La₂O₃. In the absence of O₂, the rate expression is $$r_{N_2 } = \frac{{k'P_{{\text{NO}}} P_{{\text{CH}}_{\text{4}} } }}{{{\text{(1 + }}K_{{\text{NO}}} P_{{\text{NO}}} {\text{ + }}K_{{\text{CH}}_{\text{4}} } P_{{\text{CH}}_{\text{4}} } {\text{ + }}K_{{\text{CO}}_{\text{2}} } P_{{\text{CO}}_{\text{2}} } {\text{ + }}K_{{\text{H}}_{\text{2}} {\text{O}}} P_{{\text{H}}_{\text{2}} {\text{O}}} {\text{)}}^{\text{2}} }},$$ which yields a good fit to the experimental data and gives optimized equilibrium adsorption constants that demonstrate thermodynamic consistency. With O₂ in the feed, nondifferential changes in reactant concentrations through the reactor bed were accounted for by assuming integral reactor behavior and simultaneously considering both CH₄ combustion and CH₄ reduction of NO, which provided the following rate law for total CH₄ disappearance: $$(r_{{\text{CH}}_{\text{4}} } )_{\text{T}} = \frac{{k'_{{\text{com}}} P_{{\text{CH}}_{\text{4}} } P_{{\text{O}}_{\text{2}} }^{{\text{0}}{\text{.5}}} + k'_{{\text{NO}}} P_{{\text{NO}}} P_{{\text{CH}}_{\text{4}} } P_{{\text{O}}_{\text{2}} }^{{\text{0}}{\text{.5}}} }}{{{\text{(1 + }}K_{{\text{NO}}} P_{{\text{NO}}} {\text{ + }}K_{{\text{CH}}_{\text{4}} } P_{{\text{CH}}_{\text{4}} } {\text{ + }}K_{{\text{O}}_{\text{2}} }^{{\text{0}}{\text{.5}}} P_{{\text{O}}_{\text{2}} }^{{\text{0}}{\text{.5}}} {\text{ + }}K_{{\text{CO}}_{\text{2}} } P_{{\text{CO}}_{\text{2}} } {\text{ + }}K_{{\text{H}}_{\text{2}} {\text{O}}} P_{{\text{H}}_{\text{2}} {\text{O}}} {\text{)}}^{\text{2}} }}.$$ The second term of this expression represents N₂ formation, and it again fit the experimental data well. The fitting constants in the denominator, which correspond to equilibrium adsorption constants, were not only thermodynamically consistent but also provided entropies and enthalpies of adsorption that were similar to values obtained with other La₂O₃-based catalysts. Apparent activation energies typically ranged from 23 to 28 kcal/mol with O₂ absent and 31-36 kcal/mol with O₂ in the feed. With CO₂ in the feed, but no O₂, the activation energy for the formation of a methyl group via interaction of CH₄ with adsorbed NO was determined to be 35 kcal/mol.     

Polymerization of cyclohexene oxide by methyl-4-[bis(4-bromophenyl)amino]benzoate cation radical salts

Methyl-4-[bis(4-bromophenyl)amino]benzoate cation radical salts having non-nucleophilic anions such as $ {\text{SbF}}^{ - }_{6} $ , $ {\text{PF}}^{ - }_{6} $ and $ {\text{AsF}}^{ - }_{6} $ were newly prepared and found to be very active initiators for the polymerization of cyclohexene oxide at room temperature, in dichloromethane without any external stimulation. The effects of counter ion structure, salt and monomer concentration on the polymerization yield and molecular weight, and the mechanism of initiation are presented.     

Magnetic cobalt-zinc ferrite/PVAc nanocomposite: synthesis and characterization

Metal oxide nanoparticles are the subject of current interest because of their unusual optical, electronic, and magnetic properties. In this work, cobalt zinc ferrite ( $ {\text{Co}}_{0.3} {\text{Zn}}_{0.7} {\text{Fe}}_{2} {\text{O}}_{4} $ ) nanoparticles have been synthesized successfully through redox chemical reaction in aqueous solution. The synthesized $ {\text{Co}}_{0.3} {\text{Zn}}_{0.7} {\text{Fe}}_{2} {\text{O}}_{4} $ nanoparticles have been used for the preparation of homogenous polyvinyl acetate-based nanocomposite ( $ {\text{Co}}_{0.3} {\text{Zn}}_{0.7} {\text{Fe}}_{2} {\text{O}}_{4} /{\text{PVAc}} $ ) via in situ emulsion polymerization method. Structural, morphological and magnetic properties of the products were determined and characterized in detail by X-ray powder diffractometry (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and vibrating sample magnetometer (VSM). The XRD patterns of the $ {\text{Co}}_{0.3} {\text{Zn}}_{0.7} {\text{Fe}}_{2} {\text{O}}_{4} $ confirmed that the formed nanoparticles are single crystalline. According to TEM micrographs, the synthesized $ {\text{Co}}_{0.3} {\text{Zn}}_{0.7} {\text{Fe}}_{2} {\text{O}}_{4} $ nanoparticles had nano-needle morphology with an average particle size of 20 nm. The calculated coefficient of variation (CV) of nanoparticles diameters obtained by TEM micrographs was 16.77. The $ {\text{Co}}_{0.3} {\text{Zn}}_{0.7} {\text{Fe}}_{2} {\text{O}}_{4} $ nanoparticles were dispersed almost uniformly in the polymer matrix as was proved by SEM technique. The magnetic parameters of the samples, such as saturation magnetization (M _s) and coercivity (H _c) were measured, as well. Magnetization measurements indicated that the saturation magnetization of synthesized $ {\text{Co}}_{0.3} {\text{Zn}}_{0.7} {\text{Fe}}_{2} {\text{O}}_{4} /{\text{PVAc}} $ nanocomposites was markedly less than that of $ {\text{Co}}_{0.3} {\text{Zn}}_{0.7} {\text{Fe}}_{2} {\text{O}}_{4} $ magnetic nanoparticles. However, the nanocompoites exhibited super-paramagnetic behavior at room temperature under an applied magnetic field.     

Facile Electrospinning Preparation and Up-Conversion Luminescence Performance of Y3Al5O12:Er3+, Yb3+ Nanobelts

Electrospinning technique was used to prepare $ {\text{PVP}}/\left[ {{\text{Y}}\left( {{\text{NO}}_{ 3} } \right)_{ 3} + {\text{Yb}}\left( {{\text{NO}}_{ 3} } \right)_{ 3} + {\text{Er}}\left( {{\text{NO}}_{ 3} } \right)_{ 3} + {\text{Al}}\left( {{\text{NO}}_{ 3} } \right)_{ 3} } \right] $ composite nanobelts and novel structures of Y₃Al₅O₁₂:Er³⁺, Yb³⁺ (denoted as YAG:Er³⁺, Yb³⁺ for short) nanobelts have been successfully fabricated after calcination of the relevant composite nanobelts at 900 °C for 8 h. YAG:Er³⁺, Yb³⁺ nanobelts were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM) and fluorescence spectroscopy. XRD analysis indicated that YAG:Er³⁺, Yb³⁺ nanobelts were cubic in structure with space group I_a3d. SEM analysis and histograms revealed that the width of YAG:Er³⁺, Yb³⁺ nanobelts was ca. 1.8 ± 0.37 μm under the 95 % confidence level, and the thickness was ca. 81.8 nm. Up-conversion emission spectra analysis manifested that YAG:Er³⁺, Yb³⁺ nanobelts respectively emitted strong green and red emissions centering at 522, 554 and 648 nm under the excitation of a 980-nm diode laser. The green emissions were assigned to the energy levels transitions of $ ^{ 2} {\text{H}}_{ 1 1/ 2} ,^{ 4} {\text{S}}_{ 3/ 2} \to^{ 4} {\text{I}}_{ 1 5/ 2} $ of Er³⁺ ions, and the red emission originated from the energy levels transition of $ ^{ 4} {\text{F}}_{ 9/ 2} \to ^{ 4} {\text{I}}_{{{\text{l5}}/ 2}} $ of Er³⁺ ions. The up-conversion luminescence of YAG:Er³⁺, Yb³⁺ nanobelts doped with various concentrations of Yb³⁺ and Er³⁺ was studied and the optimum molar ratio of Yb³⁺ to Er³⁺ was found to be 15:1. CIE analysis demonstrated that color-tuned luminescence can be obtained by adjusting doping concentrations of Yb³⁺ and Er³⁺ ions, which could be applied in the fields of optical telecommunication and optoelectronic devices. The up-conversion luminescent mechanism and the formation mechanism of YAG:Er³⁺, Yb³⁺ nanobelts were also proposed.     

The mechanism of manganese electrodeposition

The mechanism of manganese electrodeposition from a sulphate bath on to a stainless-steel substrate has been studied by using current efficiency data to resolve the totali-E curves. A simple, two-step electron transfer mechanism: $${\text{Mn}}^{{\text{ + + }}} + {\text{e}}\xrightarrow{{{\text{r}}{\text{.d}}{\text{.s}}}}{\text{Mn}}^{\text{ + }} $$ $${\text{Mn}}^{\text{ + }} + {\text{e}} \to {\text{Mn}}$$ is proposed to explain the following experimentally obtained parameters: cathodic and anodic transfer coefficients, reaction order and stoichiometric number. The mechanism also explains the effect of pH oni _o,Mn and on the corrosion currents.     

Activity and selectivity of a {\text{Pd/}}\gamma {\text{ - Al}}_{\text{2}} {\text{O}}_{\text{3}} catalytic membrane in the partial hydrogenation reactions of acetylene and 1,3-butadiene

A ${\text{Pd/}}\gamma {\text{ - Al}}_{\text{2}} {\text{O}}_{\text{3}}$ membrane supported on a macroporous $\alpha {\text{ - Al}}_{\text{2}} {\text{O}}_{\text{3}}$ tube was prepared by sol–gel processing and used in the partial hydrogenation of acetylene and 1,3-butadiene. The average pore diameter of the ${\text{Pd/}}\gamma {\text{ - Al}}_{\text{2}} {\text{O}}_{\text{3}}$ membrane was 3.6 nm. The gases were separated by Knudsen diffusion. The activity and selectivity of the ${\text{Pd/}}\gamma {\text{ - Al}}_{\text{2}} {\text{O}}_{\text{3}}$ membrane was compared to that of ${\text{Pd/}}\gamma {\text{ - Al}}_{\text{2}} {\text{O}}_{\text{3}}$ catalysts used in a conventional packed bed reactor. The highest selectivity to the partially hydrogenated products occurred when the reactant was premixed with H₂ and was passed through the membrane wall.     

Thermodynamic Properties of Sulfobetaine-Type Surfactants

Sulfobetaine-type surfactants containing a hydroxy group were synthesized by the reaction of long chain monoalkyl dimethyl tertiary amine with 3-chloro-2-hydroxypropanesulfonic acid sodium salt. The structures were characterized by ¹H NMR and ESI-MS. Their critical micelle concentrations (CMC) in aqueous solution were determined by the plate method in the temperature rang from 298.15 to 328.15 K. The thermodynamic parameters of micellization ( $\Delta G_{\text{mic}}^{\theta}$ , $\Delta H_{\text{mic}}^{\theta}$ and $\Delta S_{\text{mic}}^{\theta}$ ) and surface adsorption ( $\Delta G_{\text{ad}}^{\theta}$ , $\Delta H_{\text{ad}}^{\theta}$ and $\Delta S_{\text{ad}}^{\theta}$ ) were calculated from CMC data. The results showed that the micellization and surface adsorption of these surfactants in aqueous solution was a spontaneous and entropy-driven process. The micellization and surface adsorption became easier when the alkyl chain length increased from 12 carbon atoms to 14. The enthalpy–entropy compensation of micellization and adsorption was investigated. The compensation temperature were found to be (311 ± 2) K for both micellization and adsorption. The $\Delta H_{\text{mic}}^{*}$ and $\Delta H_{\text{ad}}^{*}$ decreased, but the $\Delta S_{\text{mic}}^{*}$ and $\Delta S_{\text{ad}}^{*}$ increased with increasing the hydrophobic chain length from 12 to 14.     

Surface and Solution Properties of Amphiphilic Drug-Nonionic Surfactant Systems

A surface tension study was performed on mixed amphiphilic drug-nonionic surfactant systems. The drugs used were adiphenine hydrochloride and nortriptyline hydrochloride whereas surfactants were ethoxylated sorbitan esters and polyethylene oxide?Cpolypropylene oxide?Cpolyethylene oxide triblocks. The critical micelle concentration (CMC) and CMC^id (CMC at ideal mixing condition) values suggest nonideal and attractive interactions among the components. The micellar mole fraction $ (X_{ 1}^{\text{m}} ) $ values calculated using Rubingh??s model indicate predominance of the nonionic surfactant in micelle formation. The mole fraction of surfactant in mixed monolayer $ (X_{1}^{\sigma } ) $ values are greater than $ X_{ 1}^{\text{m}} $ values, indicating a greater contribution of surfactant in monolayer formation. Thermodynamic parameters, viz. Gibbs energy of micellization $ (\Updelta G_{\text{m}}^{\text{o}} ) $ , Gibbs energy of adsorption $ (\Updelta G_{\text{ad}}^{\text{o}} ) $ , and excess free energy of mixed micelles $ (\Updelta G_{\text{ex}}^{\text{m}} ) $ and monolayers $ (\Updelta G_{\text{ex}}^{\sigma } ) $ were also evaluated. All these values suggest stable mixed micelle and mixed monolayer formation.     

Hansen solubility parameters of cellulose acetate butyrate–poly(caprolactone) diol blend by inverse gas chromatography

The specific retention volumes, $ V_{\text{g}}^{0} $ , for adsorption of 21 solute probes on the solid surface of cellulose acetate butyrate (CAB)–poly(caprolactone) diol (PCLD) blend determined in the temperature range by inverse gas chromatography were used to evaluate Hansen solubility parameters (HSP). The effect of plasticizer, PCLD, on the HSP of CAB was investigated. The three components of HSP namely dispersive $ \delta_{2}^{\text{d}} $ , polar $ \delta_{2}^{\text{p}} $ , and hydrogen bonding $ \delta_{2}^{\text{h}} $ of the blend surface were compared with the CAB surface. The $ \delta_{2}^{\text{h}} $ of CAB was increased due to the addition of PCLD, while the change in the dispersive and polar components was found to be insignificant. The three HSP were decreasing linearly with increase of temperature for the blend as well as for pure CAB. The variation of HSP with weight fraction of CAB shown that the $ \delta_{2}^{\text{p}} $ was positively deviating from linearity whereas $ \delta_{2}^{\text{d}} $ and $ \delta_{2}^{\text{h}} $ were negatively deviating from linearity.     

Micellization of Some Bile Salts in Binary Aqueous Solvent Mixtures

The micellization behavior of bile salts—sodium cholate and sodium deoxycholate was studied in aqueous methanol, ethanol and ethylene glycol mixtures (10–20 % v/v) over a temperature range (300–320 K) by surface tension and conductivity methods. Critical micelle concentration, extent of counter ion binding (α), interfacial property (A _min, ζ_max, π-CMC, $ \Updelta G_{\text{ad}}^{ \circ } $ ) and thermodynamic parameters ( $ \Updelta G_{\text{m}}^{ \circ } $ , $ \Updelta H_{\text{m}}^{ \circ } $ , $ \Updelta S_{\text{m}}^{ \circ } $ ) for the micellization process are reported and discussed.     

[CuL(H2O)2]{[CuL][Fe(CN)6]}2·2H2O (L=3,10-Bis(2-hydroxyethyl)-1,3,5,8,10,12-hexaazacyclotetradecane): A Novel Three-Dimensional Coordination Polymer via H-Bonded Linkages of One-Dimensional Zigzag Chain

A complex with the formula [CuL(H₂O)₂]{[CuL][Fe(CN)₆]}₂·2H₂O, where L=3,10-bis(2-hydroxyethyl)-1,3,5,8,10,12-hexaazacyclotetradecane, has been synthesized and crystallographically characterized. The structure is composed of a one-dimensional zigzag chain of $\left\{ {[{\text{CuL}}][{\text{Fe(CN)}}_{\text{6}} ]} \right\}_2^{2 - } $ units, and [CuL(H₂O)₂]²⁺ units. The one-dimensional zigzag chain extents through ${\text{Cu}}{\kern 1pt} - {\kern 1pt} {\text{CN}} - {\kern 1pt} {\text{Fe}}{\kern 1pt} - {\kern 1pt} {\text{CN}} - {\kern 1pt} {\text{Cu}}$ linkages. The adjacent two polymer chains are linked by the ${\text{O}}{\kern 1pt} - {\kern 1pt} {\text{H}}{\kern 1pt} \cdot \cdot \cdot {\kern 1pt} {\text{N}}{\kern 1pt} \equiv {\kern 1pt} {\text{C}}{\kern 1pt} - $ hydrogen bonding between [CuL(H₂O)₂]²⁺ and [Fe(CN)₆]^3?, forming a 3D supramolecular structure with inner hydrophilic channels. Magnetic susceptibility measurements show no exchange interaction between the Cu(II) and Fe(III) ions due to the longer ${\text{Cu}}{\kern 1pt} - {\kern 1pt} {\text{N}}$ (axial) bond length.     

Active Sites of a NiSO4/γ-Al2O3 Catalyst for the Oligomerization of Isobutene

Structural characterization, the mechanism of catalytic activity generation and the nature of active sites of a NiSO₄/γ-Al₂O₃ catalyst for isobutene oligomerization were studied by temperature programmed reduction (TPR), X-ray diffraction (XRD), diffuse reflectance infrared fourier transformed (DRIFTS) and X-ray photoelectron spectroscopy (XPS) techniques. The TPR measurements together with the XRD data indicated that calcination of the catalyst at 500 °C did not form either nickel oxide or nickel aluminate. The presence of only one type of surface nickel species formed by the incorporation of nickel ions into the surface vacant sites of γ-alumina lattice was indicated by XPS with Ar⁺ ions sputtering and TPR measurements. XPS analysis of the calcined catalyst suggested that the oxidation state of nickel ions in the calcined catalyst was (+2) and after calcination the nickel ions were coordinated to relatively more basic ligands. The surface acid centers of the catalyst were found to be only Lewis type. SO₄ ^2? ions were found to be present as a chelating bidentate ligand and enhanced the acidity of metal ( $ {\text{Al}}^{3 + } $ and/or $ {\text{Ni}}^{2 + } $ ) Lewis acid centers. The results suggested that the combined effects of the presence of the bidentate SO₄ ^2? ligand and dehydroxylation generate coordinatively unsaturated $ {\text{Ni}}^{2 + } $ that interact with isobutene during the oligomerization reaction. The formation of lower-valent nickel ions ( $ {\text{Ni}}^{x + } ,x\; \le\; 1 $ ) was demonstrated by in situ DRIFTS using CO as a probe molecule and by XPS measurements. Formation of a binuclear bridging carbonyl complex, $ [{\text{Ni}}({\text{CO}})^{ + } ]_{2} $ suggested that some lower-valent nickel species were formed via in situ reduction by isobutene. Analysis of Ni 2p photolines indicated the appearance of a new lower-valent nickel species ( $ {\text{Ni}}^{x + } ,x \;\le\; 1 $ ) during the course of isobutene oligomerization. Hence it is plausible that lower-valent nickel species might act as the active center for the oligomerization reaction, while the SO₄ ^2? ions enhance the acidity of the Lewis acid sites on the surface and assist in the adsorption of reactant molecules on the surface.     

Structure and Biological Behaviors of Some Metallo Cationic Surfactants

In this study, different cationic surfactants were prepared by esterification with bromoacetic acid of different fatty alcohols, i.e., dodecyl, tetradecyl and hexadecyl species. The products were then reacted with diphenyl amine, and the resulting tertiary amines were quaternized with benzyl chloride to produce a series of quaternary ammonium salts. The metallocationic surfactants were prepared by complexing the cationic surfactants with nickel and copper chlorides. Surface tension of these surfactants were investigated at different temperatures. The surface parameters including critical micelle concentration (CMC), maximum surface excess (Γ _max), minimum surface area (A _min), efficiency (PC₂₀) and effectiveness (π _CMC) were studied. The thermodynamic parameters such as the free energy of micellization ( $\Updelta G_{\text{mic}}^{^\circ }$ ) and adsorption ( $\Updelta G_{\text{ads}}^{^\circ }$ ), enthalpy ( $\Updelta H_{\text{m}}^{^\circ }$ ), ( $\Updelta H_{\text{ads}}^{^\circ }$ ) and entropy ( $\Updelta S_{\text{m}}^{^\circ }$ ), ( $\Updelta S_{\text{ads}}^{^\circ }$ ) were calculated. FTIR spectra and ¹H-NMR spectra were obtained to confirm the compound structures and purity. In addition, the antimicrobial activities were determined via the inhibition zone diameter of the prepared compounds, which were measured against six strains of a representative group of microorganisms. The results indicate that these metallocationic surfactants exhibit good surface properties and good biological activity on a broad spectrum of microorganisms.     

The role of sintering time on reversibility of Ni(s)—NiO(s) electrodes for high temperature solid oxide electrolyte galvanic cells

The reversibility of solid electrolyte galvanic cells such as $${\text{Mo/Ni(s)}}--{\text{NiO(s)/CSZ/Fe(s)}}--{\text{Fe}}_{{\text{1}}--\delta } {\text{O(s)/Mo}}$$ has been studied with respect to the sintering time of the active powders. Pellets from short (7h) and long (14h) sintering times have been prepared and assembled to give the above cells. Each of them has been thermally cycled and only the cells containing Ni(s)-NiO(s) electrodes prepared with a long sintering time give emf versus T curves which are independent of cycle. These values are in close agreement with the literature. For the cell reaction $${\text{NiO(s)}} + (1 - \delta ){\text{Fe(s) = Ni(s)}} + {\text{Fe}}_{1 - \delta } {\text{O(s)}}$$ the free energy change $$\Delta G = - (27.85 \pm 0.06) - (0.02157 \pm 0.00004)T{\text{ kJ mol}}^{ - {\text{1}}} $$ has been found in the temperature range 977–1350 K. To check the electrochemical reversibility, cyclic voltammetry has also been used. On the basis of these results and of SEM analysis of the electrode pellets, a mechanism is proposed whereby only at long sintering time would a triple phase contact at the electrode/electrolyte interface be produced.     

Comportement electrochimique de NbCl5 en milieu NaCl-KCl pur et additionne d'ions fluorure

Dans le domaine de température 700–800°C, les solutions d'ions niobium obtenues par addition de NbCl₅ dans le melange équimolaire NaCl-KCl, sont réduites jusqu'au métal en une seule étape: $${\text{Nb(IV) }} + {\text{ 4e}}^ - \Leftrightarrow {\text{Nb(o)}}$$ Cet échange est réversible, il lui correspond le potentiel standard apparent: $$E_{Nb(IV)/Nb}^{'0} = - 0.64V(Ag - AgCl) \pm 0.01V$$ Les espéces Nb(iv) sont oxydées selon le processus réversible: $${\text{Nb(IV)}} \Leftrightarrow {\text{Nb(v)}} + {\text{e}}^ -$$ Le potentiel standard apparent associé est: $$E_{Nb(IV)/Nb}^{'0} = - 0.74V(Ag - AgCl) \pm 0.05V$$ L'ajout d'ions fluorure déstabilise le complexé NbCl₆ ^2? au profit du complexe NbF₆ ^2? . Ceci se traduit par un déplacement du pie cathodique vers des potentiels plus cathodiques mais le mécanisme de réduction comporte toujours une seule étape mettant en jeu quatre électrons. Dans ces milieux des dépôts de niobium métallique ont eté obtenus caractérisés par rayon X. In the 700–800°C temperature range, NbCl₅ solutions in equimolar NaCl-KCl mixtures are reduced to the metal through a single step: $${\text{Nb(IV)}} + 4{\text{e}}^ - \Leftrightarrow {\text{Nb(o)}}$$ This exchange is reversible and the corresponding apparent standard potential is: $$E_{Nb(IV)/Nb}^{'0} = - 0.64V(Ag - AgCl) \pm 0.01V$$ The Nb(iv) species are oxidized according to the following reversible process: $${\text{Nb(IV)}} \Leftrightarrow {\text{Nb(v)}} + {\text{e}}^ -$$ The associated apparent standard potential is: $$E_{Nb(IV)/Nb}^{'0} = - 0.74V(Ag - AgCl) \pm 0.05V$$ The addition of fluoride ions destabilizes the NbCl₆ ^2? complex and yields the NbF₆ ^2? complex. The cathodic peak potential moves toward more cathodic potentials, but the reduction mechanism still involves a single step with four electrons exchanged. In these media, metallic niobium deposits have been obtained, and characterized through X-ray analysis.     

Reaction in the silver zinc cell

An adiabatic calorimeter was used to measure the thermodynamics of the silver zinc cell. The charge and discharge reactions were shown to take place in two stages involving the production of argentous oxide and argentic oxide respectively. No thermal evidence was found to suggest the existence of a higher oxide of silver. The cell reactions were (1) $$2{\text{Ag + ZnO}} \leftrightharpoons {\text{Ag}}_{\text{2}} {\text{O + Zn, }}\Delta {\text{H = 158}} \cdot {\text{7 kJF}}^{ - {\text{1}}}$$ (2) $${\text{Ag}}_{\text{2}} {\text{O + ZnO}} \leftrightharpoons {\text{Ag}}_{\text{2}} {\text{O}}_{\text{2}} {\text{ + Zn, }}\Delta {\text{H = 176}} \cdot 1{\text{ kJF}}^{ - {\text{1}}}$$ If the cell was left on open circuit for a long period, or the positive electrodes heated, reaction (2) was suppressed and the discharge took place via reaction (1), without any reduction in capacity.     

Surface characterization of cellulose acetate propionate by inverse gas chromatography

The purpose of this paper is to study the surface energetics of the polymer excipient cellulose acetate propionate (CAP) in the solid form. The net retention volumes, V _N, for n-alkanes and polar solutes have been measured in the temperature range 353.15–403.15 K by inverse gas chromatography. The dispersive surface free energy, $ \gamma_{\text{S}}^{\text{d}} $ , and Lewis acid–base parameters $ K_{\text{a}} $ and $ K_{\text{b}} $ , have been determined using V _N values. The $ \gamma_{\text{S}}^{\text{d}} $ values are decreased linearly with increase of temperature. The $ \gamma_{\text{S}}^{\text{d}} $ value at 353.15 K is 24.50 ± 1.54 mJ/m², and the temperature gradient was found to be ?0.287 mJ/m²/K¹. The $ K_{\text{a}} $ and $ K_{\text{b}} $ values are 0.410 ± 0.021 and 1.708 ± 0.388, respectively, which suggest that the CAP solid surface contain relatively more basic sites. The K _a and K _b values of CAP are compared with the similar values obtained on the cellulose acetate butyrate solid surface.     

Thermodynamics of Micellization of Sulfobetaine Surfactants in Aqueous Solution

The thermodynamics of micellization of the sulfobetaine (SB) amphoteric surfactants, that is N-alkyl-N,N-dimethyl-3-ammonio-1-propanesulfonate and N-alkyl-N,N-dimethyl-3-ammonio-1-butanesulfonate (the carbon atom number of the alkyl chain is 12, 14 and 16 respectively) in aqueous solution, have been studied by surface tension measurements with the temperature range from 298.15 to 318.15?K. The critical micelle concentrations (CMC) of SB n-3 and SB n-4 surfactants were determined from the drop-volume methods at different temperatures. The obtained results indicated that the values of critical micelle concentration strongly depended on the surfactants species and temperatures. Thermodynamic parameters ( $ \Updelta G_{\text{mic}}^{ \circ } $ , $ \Updelta H_{\text{mic}}^{ \circ } $ and $ \Updelta S_{\text{mic}}^{ \circ } $ ) of the micelle formation were determined. The micellization was found to be enthalpy-driven at lower temperatures, while this process was entropy-driven at higher temperatures. The enthalpy?Centropy compensation were also investigated. The compensation temperature T _c and $ \Updelta H_{\text{mic}}^{*} $ decreased, while $ \Updelta S_{\text{mic}}^{*} $ increased with the increase in the hydrophobic chain length.     

Reaction kinetics of silicon etching in HF-K2Cr2O7-H2O solution

The reaction kinetics of silicon etching in HF-K₂Cr₂O₇-H₂O solution was studied experimentally. The etch rates were measured with varying HF and K₂Cr₂O₇ concentrations, agitation speed reaction temperature and time. The etch rates of n- and p-Si (100) were both similar. The etchec surfaces consisted mainly of silicon and showed a relatively smooth and planar morphology. At suffi ciently high HF concentration, the etch rate was increased with increasing K₂Cr₂O₇ concentratior due to the increase of hole formation on the silicon surface. However, at low HF concentration the etch rate maintains low value and increases very slowly because of insufficient hole concentratior for etching reaction. The apparent activation energy was about 7.8 kcal/g-mole, and the rate equatior for the silicon etching reaction in HF-K₂Cr₂O₇-H₂O solution was obtained as-r_Si = 600 exp(-3900/T) $$ - r_{Si} = 600{\text{ exp( - 3900/T) C}}_{{\text{K}}_{\text{2}} {\text{Cr}}_{\text{2}} {\text{O}}_{\text{7}} } ^{05} {\text{ C}}_{{\text{HF}}} ^3 $$ C_hk ³ at HF concentrations greater than 8 M.