A study of the acidic and catalytic properties of pure and sulfated zirconia–titania and zirconia–silica mixed oxides

Protonated pyridine (PyH⁺) was not found on ZrO₂ (Z) or ZrO₂–TiO₂ (ZT), but was detected on sulfated oxides (ZS, ZTS) by IR spectroscopy. In contrast, ZrO₂–SiO₂ samples containing about 30–80 mol% ZrO₂ showed Brønsted acidity both in nonsulfated (ZS) and sulfated (ZSS) forms. The total acidity was determined by NH₃TPD. Introduction of sulfate ions increased the sitespecific catalytic activity (TOF) in the conversion of cyclopropane or nhexane. The effect of sulfate ions was more significant on samples rich in zirconia. Results suggest that Zr is homogeneously distributed in ZS samples rich in silica. Zirconiabound dimeric sulfate, generating strong acidity, could not be formed in these preparations due to the absence of fairly large ZrO₂ domains.     

Structure of the Reaction Zone of a Steady Detonation Wave in Dinitrodiazapentane

The massvelocity profiles in 2,4dinitro2,4diazapentane samples of different densities were registered by a laser interferometer and the electromagnetic technique. The reaction time was shown to reach 300 nsec and weakly depend on density, while the pressure in the chemical spike can be twice as high as that at the Chapman–Jouguet point. No special features due to diamond formation were observed in the massvelocity profiles registered in the chemical reaction zone.     

Interrelation between the Glass Transition Temperature, Thermal Expansion Coefficient, and Poisson Ratio for Some Glasses in the AV–BVI–CVIISystems

In the framework of the free volume concept, the dependences of _g T _gand T _gon and are considered and the interrelation between the fraction of the fluctuation free volume f _g, Poisson ratio , and Grüneisen lattice parameter for chalcogenide, oxogenide, and oxohalide glasses is discussed. The fluctuation free volume model and the model of soft atomic configurations are compared in terms of anharmonicity of the glasses under investigation.     

Some theoretical considerations on the design of a practical anode in an electrochemical reactor

A theoretical analysis of the membrane current distribution is carried out for a typical three-compartment electrolyser in order to point out the effects of geometry on the design of mesh anodes. The factors considered here include the introduction of an insulated border, the perforation of the anode, the finite conductivity of the substrate, and the introduction of a bus bar connection between the anode and the current lead. It is recommended that no insulated border be introduced, since, while reducing the anode area and consequently its cost, it leads to a nonuniform membrane current distribution and hence decreases membrane efficiency. Also, titanium is found to be a suitable substrate for the anode in spite of its relatively low conductivity.Nomenclature a Dummy variable in Equation 3 - b Border width - b ^* Effective border width - f Fraction of open area in electrode - F _B Parameter defined by Equation 4 - F _p Parameter defined by Equation 8 - F _be Parameter defined by Equation 15 - I Total cell current - i Local current density on the membrane at a point - i Current density along the membrane far from the border - _loc Average value of current density over a small portion of the membrane - _cell Average value of current density over the whole membrane - Average value of current density on membrane far from the border - i _max Maximum value of current density on membrane - _loc,max Maximum value of _loc on membrane due to electrode and bus bar resistance effects - i _p Maximum value of current density over a single electrode perforation - j (–1)^1/2 - l _p Characteristic length of mesh - L Dimension of anode in the direction of bus bar orientation - L Dimension of anode in the direction perpendicular to bus bar - L Width of bus bar - s Interelectrode gap - s ₁ Membrane to anode gap - R Electrolyte and membrane resistance - x _b Coordinate along length of bus bar - x _B Coordinate in border effect analysis - x _e Coordinate along electrode in the analysis of its resistance effect - x _P Coordinate in perforation effect analysis - _b Bus bar thickness - _e Electrode thickness - _b Bus bar resistivity - _e Electrode resistivity - _em Resistivity of metal in electrode - _b Potential at a point on the bus bar - _e Potential at a point on the electrode - ¯ _e Average potential over the electrode - _max Potential at the current source - _cath Potential at the equipotential cathode     

A parameter characterizing the geometry of expanded metal. II. Natural convection mass transfer at expanded metal electrodes

Free convective mass transfer rates at vertical electrodes of expanded metal were measured by the electrochemical method. Electrode height and electrolyte concentration were varied and the dependence of the expanded metal on the geometry and on the mesh orientation with respect to the vertical direction was investigated. A single equation was developed to correlate all the results. Besides the generalized dimensionless groups for natural convection the correlation includes a parameter characterizing the geometry of the expanded metal. The correlation also represents free convective mass transfer results obtained by other investigators with vertical mesh electrodes.Nomenclature a width of narrow space - A mean mesh aperture - c ₀ bulk concentration - d cavity diameter - d _p particle diameter - D diffusivity - g acceleration due to gravity - Gr Grashof number =gh³/v² - h electrode height - H cavity depth - k mass transfer coefficient - LD long dimension of expanded metal - R _h hydraulic radius - Sc Schmidt number=/D - SD small dimension of expanded metal - Sh Sherwood number=kh/D - void fraction - kinematic viscosity - density - electrode area per unit volume - electrode area per unit net area     

Properties ofSrMO 3-δ(M=Fe,Co) as oxygen electrodes in alkaline solution

Strontium ferrates and cobaltates with compositions SrFeO_3- (0.060.40) and SrCoO_3- (0.040.30) were synthesized. The dependence of the oxygen electrode properties on the value was examined in 1 mol dm^–3 KOH solution. In the SrFeO_3- series, the samples with 0.24<<0.29, showed the highest activity in both oxygen evolution and reduction reactions. In contrast, no strong dependence on the value was observed in SrCoO_3-, which also showed a high catalytic activity for oxygen evolution.     

Electrodeposition, composition and structure of Zn—Cr alloys

The effect of polyethylene glycol (PEG 1500) as additive and of deposition conditions on Zn—Cr alloy electrodeposition from an acidic sulfate electrolyte at room temperature, without agitation was investigated. PEG polarizes the overall cathodic reaction and inhibits Zn deposition. Cr codeposition with Zn starts at a cathodic potential of about –1,95 V vs Hg/Hg₂SO₄, which is reached at current density of about 20 A dm^–2 in galvanostatic conditions. Zn—Cr alloy coatings containing up to 28 at % Cr were obtained depending on the plating conditions. SEM observations showed an island-like structure, formed by the local growth of crystals, which covered the surface during further deposition. In the first stages of electrodeposition the powder diffraction spectra contain lines of b.c.c. -(Zn,Cr) phase (a 3.02 Å). After 30 s deposition time weak lines of Zn-based phase (a 2.67 Å, c 4.90 Å) appear, and become clearly visible in coatings deposited for 90 s. The average Cr content in the alloy coatings decreases with advancing deposition. The as-plated surface contains C in organic compounds and Zn(OH)₂. After 50 min sputtering, Zn and a mixture of Cr, Cr₂O₃ and Cr₇C₃ were found. The presence of organic C and O, probably from inclusions of PEG, were also detected.     

Heterogeneous asymmetric reactions. 23. Enantioselective hydrogenation of ethyl pyruvate over cinchonine- and α-isocinchonine-modified platinum catalysts

The enantioselective hydrogenation of ethyl pyruvate to (S)-ethyl lactate over cinchonine- and -isocinchonine-modified Pt/Al₂O₃ catalysts was studied as a function of modifier concentration and reaction temperature. The maximum enantioselectivities obtained under the applied mild conditions were 89% ee using cinchonine (0.014 mmoldm^–3, 1 bar H₂, 23°C, 6% AcOH in toluene), and 76% ee in the case of -isocinchonine (0.14 mmoldm^–3, 1 bar H₂, –10°C, 6% AcOH in toluene). Since -isocinchonine of rigid structure exists only in anti-open conformation these data provide additional experimental evidence to support the former suggestion concerning the dominating role of anti-open conformation in these cinchona-modified enantioselective hydrogenations.     

Specific features of the phase transformations occurring during the sintering process of the beta-alumina based ceramics and their properties

Conclusions During the sintering process of beta-alumina obtained using the method of plasmochemical synthesis, the structural transformation occurs and it is accompanied by the separation of the excess Na₂O and the formation of an intergranular meltlike phase that is saturated with sodium and is characterized by high dielectric properties.The quantity of the meltlike phase and the magnitude of the /( + ) ratio determine the degree of stabilization (stability) and the final resistivity of the material and depend on the initial chemical composition and the heating rate maintained during the sintering process.It was shown that when the duration of residence of the material in the hot zone of the furnace is increased or when the specimens sintered maintaining high heating rates are subjected to additional heat treatment, one observes the occurrance of the reverse structural transformation that is characterized by an increase of the phase ratio /( + ) 1, a reduction in the quantity of the meltlike phase right up to its complete disappearance, and a decrease of the electrical resistivity of the material.In the materials having a large excess quantity of sodium oxide, the process of crystallization of the intergranular NaAlO₂ phase occurs simultaneously with the second phase transformation.The best ceramic and electrophysical parameters were obtained when sintering the material contained 7.9% Na₂O.Translated from Ogneupory, No. 3, pp. 13–18, March, 1990.     

Nucleation and growth kinetics of Ag7NO11 on a platinum single crystal electrode

The process of electrochemical deposition of Ag₇NO₁₁ on a platinum single crystal anode from 5M AgNO₃ is investigated. The nucleation and growth rates are measured at different constant overpotentials. The orientation of the Ag₇NO₁₁ crystals with respect to the substrate surface is determined in the case of deposition on glassy carbon and on the 100, 111 and 110 faces of a platinum single crystal.     

Effect of distortions in the ideal profile of solid phase conductivity on performance efficiency of porouselectrodes

The effect of distortions in the ideal profile of the solid phase conductivity s(x) on porous electrode (PE) performance efficiency has been analysed using a one-dimensional model and an overall polarization curve involving both main and side reactions. Although an ideal electrically equally accessible PE is provided only by a hyperbolic profile s(x) passing through the middle of the electrode (the point s=L), it has been shown that a noticeable improvement in performance can be obtained using a rough approximation with any monotonic function providing a decrease in conductivity in the direction from the back current supply to the front plane of the PE, including functions not necessarily passing through the point s=L in the middle of the electrode. This permits less rigid requirements for the s(x) profile reproduction accuracy and simplification of experimental data acquisition.     

Semiconductor properties of manganese dioxide

Measurements of the d.c. conductivity of different types of-manganese dioxide formed under various conditions and of different thermal history indicate a correlation with the combined water content. The specific conductivity increases exponentially as the water content decreases. The values obtained with anhydrous products which then are transformed to a-manganese dioxide are similar to those obtained with-manganese dioxide prepared by pyrolysis of manganous nitrate. Any effect which might be attributed to the lattice transformation of- into-manganese dioxide could not be observed.A more detailed examination of two specimens of manganese dioxide shows a semilogarithmic relation between thermoelectric voltage and d.c. conductivity. This relationship allows an estimate to be made of the electron concentration at which the electron gas would begin to degenerate. Hence it follows that both for- and- manganese dioxide the concentration of the conducting electrons is far below the degeneration limit.This result is in agreement with the measured activation energies of the conductivity. It is suggested that the water content influences the electronic band structure by successively deforming the rutile structure of-manganese dioxide and hence the manganese-manganese distances within the lattice.     

A chemically regenerative redox fuel cell

A novel chemically regenerative redox fuel cell is described. The electrode reactions are based on the following redox reactions: cathodic reaction: anodic reaction: VO ₂ ⁺ +2H⁺+e VO²⁺+H₂O (E ₀ +1V), SiW₁₂O ₄₀ ^5– SiW₁₂O ₄₀ ^4– +e (E ₀ 0V). Regeneration of the oxidant by direct oxidation with O₂ was achieved by using the soluble heteropoly acid catalysts, H₃PMo₁₂O₄₀ or H₅PMo₁₀V₂O₄₀, whereas regeneration of the tungstosilicic acid, H₃SiW₁₂O₄₀, was accomplished by direct reduction with H₂ utilizing small amounts of Pt, Pd, Rh, Ru or the soluble Pd-4, 4, 4, 4'-tetrasulphophthalocyanine complex as catalysts. Some aspects of the regeneration kinetics and their influence on the overall performance of the redox fuel cell are discussed.     

Electrochemical mass transfer studies in open cavities

Experimental measurements on free convection mass transfer in open cavities are described. The electrochemical deposition of copper at the inner surface of a cathodically polarized copper cylinder, open at one end and immersed in acidified copper sulphate was used to make the measurements. The effects on the rate of mass transfer of the concentration of the copper sulphate, the viscosity of the solution, the angle of orientation, and the dimensions of the cylinder were investigated. The data are presented as an empirical relation between the Sherwood number, the Rayleigh number, the Schmidt number, the angle of orientation and the ratio of the diameter to the depth of the cylinder. Comparison of the results with the available heat transfer data was not entirely satisfactory for a number of reasons that are discussed in the paper.Nomenclature C _b bulk concentration of Cu⁺⁺ (mol cm^–3) - C _b bulk concentration of H₂SO₄ (mol cm^–3) - C _o concentration of Cu⁺⁺ at cathode (mol cm^–3) - C _o concentration of H₂SO₄ at cathode (mol cm^–3) - D cavity diameter (cm) - D diffusivity of CuSO₄ (cm² s^–1) - D diffusivity of H₂SO₄ (cm² s^–1) - Gr Grashof number [dimensionless] (=Ra/Sc) - g acceleration due to gravity (=981 cm s^–2) - H cavity depth (cm) - h coefficient of heat transfer (Wm ^–2 K^–1) - i _L limiting current density (mA cm^–2) - K mass transfer coefficient (cm s^–1) - K ₁,K ₂ parameters in Equation 1 depending on the angle of orientation () of the cavity (see Table 3 for values) [dimensionless] - k thermal conductivity (W m^–1 K^–1) - L ^* characteristic dimension of the system (=D for cylindrical cavity) (cm) - m exponent on the Rayleigh number in Equation 1 (see Table 3 for values) [dimensionless] - Nu Nusselt number (=hL ^* k^–1) [dimensionless] - n exponent on the Schmidt number in Equation 1 (see Table 3 for values) [dimensionless] - Pr Prandtl number (=v/k) [dimensionless] - Ra Rayleigh number (defined in Equation 2) [dimensionless] - Sc Schmidt number (=v/D) [dimensionless] - Sh Sherwood number (=KD/D) [dimensionless] - ^t H⁺ transference number for H⁺ [dimensionless] - ^t Cu⁺⁺ transference number for Cu⁺⁺ [dimensionless] - specific densification coefficient for CuSO₄ [(1/)/C] (cm³ mol^–1) - specific densification coefficient for H₂SO₄ [(1/)/C] (cm³ mol^–1) - k thermal diffusivity (cm² s^–1) - dynamic viscosity of the electrolyte (g cm^–1 s^–1) - kinematic viscosity of the electrolyte (= /)(cm² s^–1) - density of the electrolyte (g cm^–3) - angle of orientation of the cavity measured between the axis of the cavity and gravitational vector (see Fig. 1) [degrees] - parameter of Hasegawaet al. [4] (=(2H/D))5/4 Pr^{– 1/2}) [dimensionless]     

Comportement électrochimique des variétés alpha et beta PbO2 et influence de l'antimoine sur leur reactivité électrochimique en milieu H2SO4, 8N

Résumé L'expérience a montré qu'il est possible d'obtenir par l'oxydation anodique des variétés- et-PbO₂ parfaitement pures au point de vue cristallographique, et que la réduction de-PbO₂ se déroule à un potentiel plus élevé et plus constant que celui observé sur-PbO₂. La réactivité électrochimique de-PbO₂ est plus importante que celle de-PbO₂. L'introduction de Sb dans les réseaux cristallins de ces variétés diminue fortement leur cristallinité et dans le cas de-PbO₂ on obtient toujours simultanément- et-PbO₂. Du point de vue réactivité électrochimique, l'accroissement dû à la présence de Sb est de l'ordre de 33%.

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The results demonstrate the possibility of preparing through anodic oxidation rigorously pure, from the crystallographic point view,- and-PbO₂ phases, and that the reduction of-PbO₂ takes place at a potential which is more positive and more constant than the one obtained with-PbO₂. In a battery, the electrochemical reactivity of-PbO₂ is more important. The introduction of Sb into the lattice of these forms of PbO₂ decreases their crystallinity, and for the case of-PbO₂ we obtained simultaneously- and-PbO₂. Their electrochemical reactivity can increase by about 33%.

     

Kinetics of copper electrodeposition in citrate electrolytes

The kinetics of copper electrocrystallization in citrate electrolytes (0.5M CuSO₄, 0.01 to 2M sodium citrate) and citrate ammonia electrolytes (up to pH 10.5) were investigated. The addition of citrate strongly inhibits the copper reduction. For citrate concentrations ranging from 0.6 to 0.8 M, the impedance plots exhibit two separate capacitive features. The low frequency loop has a characteristic frequency which depends mainly on the electrode rotation speed. Its size increases with increasing current density or citrate concentration and decreases with increasing electrode rotation speed. A reaction path is proposed to account for the main features of the reduction kinetics (polarization curves, current dependence of the current efficiency and impedance plots) observed in the range 0.5 to 0.8 M citrate concentrations. This involves the reduction of cupric complex species into a compound that can be either included as a whole into the deposit or decomplexed to produce the metal deposit. The resulting excess free complexing ions at the interface would adsorb and inhibit the reduction of complexed species. With a charge transfer reaction occurring in two steps coupled by the soluble Cu(I) intermediate which is able to diffuse into the solution, this model can also account for the low current efficiencies observed in citrate ammonia electrolytes and their dependencies upon the current density and electrode rotation speed.Nomenclature b, b ₁, b ₁ ^* Tafel coefficients (V^–1) - bulk concentration of complexed species (mol cm^–3) - (si*) concentration of intermediate C^* atx=0 (mol cm^–3) - C concentration of (Cu Cit H)^2– atx=0 (mol cm^–3) - C C variation due to E - C concentration of complexing agent (Cit)^3- at the distancex (mol cm^–3) - C _o concentrationC atx=0 (mol cm^–3) - C _o C _o variation due to E - Cv _s bulk concentrationC (mol cm^–3) - (Cit H), (Cu), (Compl) molecular weights (g) - C _dl double layer capacitance (F cm^–2) - D diffusion coefficient of (Cit)^3- (cm²s^–1) - D ₁ diffusion coefficient of C^* (cm²s^–1) - E electrode potential (V) - f ₁ frequency in Equation 25 (s^–1) - F Faraday's constant (96 500 A smol^–1) - i, i ₁, i ₁ ^* current densities (A cm^–2) - i i variation due to E - Im(Z) imaginary part ofZ - j - k ₁, k ₁ ^* , K₁, K ₁ ^* , K₂, K rate constants (cms^–1) - K rate constant (s^–1) - K ₃ rate constant (cm³ A^–1s^–1) - R _t transfer resistance (cm²) - R _p polarization resistance (cm²) - Re(Z) real part ofZ - t time (s) - x distance from the electrode (cm) - Z _f faradaic impedance (cm²) - Z electrode impedance (cm²) Greek symbols maximal surface concentration of complexing species (molcm^–2) - thickness of Nernst diffusion layer (cm) - , ₁, ₂ current efficiencies - angular frequency (rads^–1) - electrode rotation speed (revmin^–1) - =K ^–1(s) - _d diffusion time constant (s) - electrode coverage by adsorbed complexing species - (in0) electrode coverage due toC _s - variation due to E     

Local study of wall to liquid mass transfer in fluidized and packed beds. II. Mass transfer in packed beds

Mass and momentum transfer at a wall in liquid-particle systems are studied with a two-dimensional model which consists of fixed spherical turbulence promoters arranged in a simple cubic lattice in a rectangular channel. Local values of the mass transfer coefficient and shear stress at a wall of the channel have been measured at identical locations. The results show that there are large differences between the local values but their distribution along the transfer surface is reproduced identically. The dependence of these local values on each other allows one to obtain a general relationship between overall mass and momentum transfer as well as a correlation of mass transfer results for exchange between a wall and a flowing liquid in a fixed bed of particles.Nomenclature a _g particle specific area - a coefficient in expression s=a ^q (q>0) - a, b coefficients in expressionJ _M=a(Re) ^–b - d _p particle diameter - d microelectrode diameter - D molecular diffusion coefficient - h _K,h _B constants in Ergun equation - J _M=(¯k/u/)(Sc) ^2/3 Colburnj-factor - k local mass transfer coefficient - k local mass transfer coefficient in inert wall - ¯k overall mass transfer coefficient - L length of the transfer surface - q exponent in expressions=a ^q - (Re)=(ud _p)/[v(1-)] modified Reynolds particle number - (Sc)=v/D Schmidt number - s, ¯s velocity gradients at the wall - u superficial liquid velocity - coefficient in Equation 1 - characteristic length - bed porosity - _F fluid density - dynamic viscosity - kinematic viscosity - shear stress at the wall - P/L fluid pressure gradient     

On the Charge Carrier Concentration in Sodium–Calcium Aluminophosphate Glasses

The dc and ac conductivities of the xNa₂O–(35 – x)CaO–7.5Al₂O₃–57.5P₂O₅glasses (mol %) with x= 0–35 are studied in the frequency range from 20 Hz to 1 MHz at different temperatures. It is found that the dc conductivity strongly depends on xonly for glasses with x 10. For glasses with x 5, the dc conductivity is virtually composition independent. The dependence of the ac conductivity plotted on the log(()/_dc) vs. log(/_dc) coordinates is analyzed. The ac conductivity represented in these coordinates depends on xonly for glasses with x 5, in which the dc conductivity does not depend on x. For glasses with xin the range from 10 to 35, all the isotherms of the ac conductivity closely coincide with each other. This result is discussed in the framework of two hypotheses: (1) the conductivity () is determined by the dynamic polarization (of the Maxwell–Wagner type at low frequencies) of the material due to spatial fluctuations of the density of paths providing the migration of sodium ions and (2) the concentration of charge carriers is independent of x.     

Calculation of Temperature Dependences of the Viscosity and Volume Relaxation Time for Oxide Glass-Forming Melts from Chemical Composition and Dilatometric Glass Transition Temperature

The relaxation parameter K _sthat is equal to the ratio of the viscosity to the Kohlrausch volume relaxation time _s is analyzed. It is shown that this parameter can be evaluated from the temperature T ₁₃(corresponding to a viscosity of 10¹³P) and the glass transition temperature T ₈ ⁺determined from the dilatometric heating curve. The maximum error of the estimate with due regard for experimental errors is equal to ±(0.4–0.5)logK _sfor strong glasses and ±(0.6–0.8)logK _sfor fragile glasses, which, in both cases, corresponds to a change in the relaxation times with a change in the temperature by ±(8–10) K. It is revealed that the viscosity, the Kohlrausch volume relaxation time _s , and the shear modulus Gof glass-forming materials in silicate, borate, and germanate systems satisfy the relationship log( _s G/) 1. The procedure for calculating the temperature dependences of the viscosity and the relaxation times in the glass transition range from the chemical composition and the T ₈ ⁺temperature for glass-forming melts in the above systems is proposed. The root-mean-square deviations between the calculated and experimental temperatures T ₁₁and T ₁₃are equal to ±(6–8) K for all the studied (silicate, borate, germanate, and mixed) oxide glass-forming systems. The proposed relationships can be useful for evaluating the boundaries of the annealing range and changes in the properties and their temperature coefficients upon cooling of glass-forming melts.     

Physicochemical properties of electrodepositedβ-lead dioxide: Effect of deposition current density

The influence of current density on the coulometric efficiency of -PbO₂ deposition in 0.5 M cM lead nitrate, the nonstoichiometry, impurity of -PbO₂ and voltammetric double layer capacitance have been studied. While the coulometric efficiency is about 95% at current densities less than 30 mA cm^–2, it decreases at higher current densities. The oxygen deficiency, , in -PbO_2- has been found to be invariant with the current density. X-ray diffraction studies provide a linear decrease in the weight percent of -PbO₂ as an impurity in the -PbO₂ with increase in current density, and the -PbO₂ is found to be absent at 100mA cm^–2 or higher. The estimated double layer capacitance from the cyclic voltammograms recorded in the potential range 0.70–1.10V, increases with deposition current density, indicating enhanced surface area.