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     

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.     

Mass transfer studies at iron felts

Mass transfer has been studied at flow-through iron felts using the reduction of ferricyanide or copper cementation on iron as test reactions. Empirical correlations between a modified Sherwood number and the Reynolds number are proposed. Comparisons of the mass-transfer performance of iron felts with other three-dimensional structures are made.List of symbols a ₃ specific surface area per unit felt volume (m^–1) - A empty cross-section of the reactor (m²) - C concentration (mol m^–3) - C ₀ inlet concentration (mol m^–3) - d _h hydraulic diameter (m) - e fibre thickness (m) - E electrode potential (V) - D diffusion coefficient (m²s^–1) - F Faraday constant (A s mol^–1) - i current density (A m^–2) - I total current (A) - I _L limiting current (A) - J _m mass transfer j-factor=(k/v)Sc ^2/3 - K mass transfer coefficient (m s^–1) - l fibre width (m) - L electrode thickness (m) - Re Reynolds number - vd _h/ - Re modified Reynolds number - vl/ - Sc Schmidt number = /D - Sh modified sherwood number = ka _e l ²/D - t time (s) - T Temperature (K) - superficial liquid flow velocity (m s^–1) Greek characters void fraction - dynamic viscosity (kg m^–1 s^–1) - kinematic viscosity (m² s^–1) - ₃ charge number of the electrode reaction - iron density (kg m^—) - _a apparent density of the felt (kg m^–3) - _m residence time of the reservoir (s)     

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.     

Diffusion-controlled current distributions near cell entries and corners

This paper reports experimental work undertaken to explore diffusion-controlled current distributions immediately downstream of sudden changes in flow cross-sectional area such as may occur at the entry to electrochemical flow cells. Nozzle flows expanding into an axisymmetric circular duct and into a square duct have been investigated using the reduction of ferricyanide ions on nickel micro-electrodes as the electrode process. The spanwise distribution of current has also been studied for the case of the square cell where secondary corner flows are significant.Nomenclature A electrode area (cm²) - c bulk concentration of transferring ions (mol dm^–3) - D cell diameter (cm) - D Diffusion coefficient (cm₂s^–1) - F Faraday number (96 486 C mol^–1) - I limiting electrolysis current (A) - k mass transfer coefficient (cm s^–1) - N nozzle diameter (cm) - u mean fluid velocity (cm s^–1) - x distance downstream from point of entry to cell (cm) - z number of electrons exchanged - electrolyte viscosity (g s^–1 cm^–1) - electrolyte density (g cm^–3) - (Re)_D duct Reynolds number,Du/ - (Re)_N nozzle Reynolds number,Nu/ - (Sc) Schmidt number,/D) - (Sh) Sherwood number,kD/D)     

Mass transfer at the electrodes of the ‘falling-film cell’

In the falling-film cell the electrolyte flows as a thin film in the channel between an inclined plane plate and a sheet of expanded metal which work as electrodes. The present work gives the mass transfer coefficients at both electrodes; the experimental variables are the electrolyte flow-rate, the angle of inclination of the channel and the interelectrode distance. The results allow three different flow regimes to be characterized. At low flow rates, there exists a particular regime where capillary effects are present; in this regime the mass transfer coefficient decreases with increasing flow rate, which is interesting from the point of view of possible industrial electrolytic applications.Nomenclature b width of the inclined channel - D diffusion coefficient - d interelectrode distance - e _m mean film thickness - Grashof number, based ond - Grashof number, based onL - ¯k overall mass transfer coefficient, defined by Equation 9 - L electrode length - Q _v volumetric flow rate - volumetric flow rate per unitQ _vl width of channel - Reynolds number - Schmidt number - Sherwood number, based ond - Sherwood number, based onL - mean velocity of the liquid film - inclination angle of the channel with respect to the horizontal - kinematic viscosity of them electrolyte     

Meniscus shape and lateral wetting at the hanging meniscus rotating disc (HMRD) electrode

The hanging meniscus rotating disc (HMRD) electrode is a configuration in which a cylinder of the electrode material is used without an insulating mantle. We have recently shown that the hydrodynamic behaviour of the HMRD is similar to that of the conventional rotating disc electrode and that this configuration can also be used to study the kinetics of simple charge transfer reactions. In this paper experimental data on the change of meniscus shape upon meniscus height and rotation for different electrode materials are presented and analysed in relation to lateral wetting and stability.List of symbols A electrode area (cm²) - C ₀ ^* bulk concentration (mol cm^–3) - D ₀ diffusion coefficient (cm²s^–1) - f force on a cylinder supporting a hanging meniscus (dyn) - F Faraday (96 500 Cmol^–1) - g gravitational acceleration (cm s^–2) - h height (cm) - h _m meniscus height (cm) - h ₀ critical meniscus height (cm) - i total current (A) - i _L limiting current (A) - i _max kinetic current (A) - k proportionality constant (cm^–1) - K dimensionless constant - n number of electrons exchanged - R _eff effective radius of the electrode (cm) - R ₀ geometric radius of the electrode (cm) - V volume of the meniscus above the general level of the liquid surface (cm³) Greek letters ₀ thickness of hydrodynamic boundary layer (cm) - surface tension (dyn cm^–1) - kinematic viscosity (cm²s^–1) - density difference between the liquid and its surrounding fluid (gcm^–3) - _C normal contact angle - _L local contact angle 0_L + 90° - electrode rotation rate (s^–1)     

Enhanced mass transfer to a rotating cylinder electrode with axial flow

A study of the rotating concentric cylindrical electrode has been made, in which the enhanced mass transfer rate by turbulence promotors to a smooth cylinder has been measured. When a special polypropene cloth was applied in the annulus an increase in the Sherwood number was detected, up to six times the value for a smooth cylinder at low Taylor numbers.Nomenclature A electrode area, dl (m²) - C ₀ bulk concentration (mol m^–3) - D diffusion coefficient (m² s^–1) - e annular gap,R-r (m) - F Faraday's constant, 96487 (As mol^–1) - I _l limiting current (A) - k _l mass transfer coefficient,I _l /nFC ₀ A (m s^–1) - l electrode height (m) - n number of electrons - r, R radius of inner and outer cylinder (m) - u axial liquid velocity (m s^–1) - angular velocity (rad s^–1) - kinematic viscosity (m² s^–1) - liquid density (kg m^–3) Dimensionless numbers Re _a axial Reynolds number 2eu/ - Re rotational Reynolds number 2r ²/ - Sc Schmidt number /D - Sh ^* rotational Sherwood number 2rk _l /D - Sh combined flow Sherwood number 2ek _l /D - St Stanton numberSh/Re /Sc - Ta Taylor number=re/(e/r)^1/2 - a, b, c power indices     

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.     

Synthesis,electrical and optical properties of multifunctional poly[2-(2-ethyl-hexyloxy)-1,4-phenylenevinylene]

Summary Branched monoalkoxy-substituted poly[2-(2-ethylhexyloxy)-1,4-phenylenevinylene] (EH-PPV) was prepared in thin films via the water-soluble precursor technique and solution elimination method. These precursor polymer films could be stretched up to 8 times, and the drawn films of the EH-PPV could be doped with I₂ and FeCl₃ to give conductivities of 5.28x10^-3 and 0.56 S/cm, respectively. The third-order nonlinear optical susceptibility of the polymer was determined by using third harmonic generation (THG) method at 1907 nm, fundamental wavelength. Measured ⁽³⁾(–3; ,,) value was 3.8x10^-12 esu. The maximum emission wavelength of EH-PPV film in photoluminescence spectrum was 560 nm, corresponding to the yellowish red color.     

Investigation of water electrolysis by spectral analysis. I. Influence of the current density

The potential (or current) fluctuations observed under current (or potential) control during gas evolution were analysed by spectral analysis. The power spectral densities (psd) of these fluctuations were measured for hydrogen and oxygen evolution in acid and alkaline solutions at a platinum disk electrode of small diameter. Using a theoretical model, some parameters of the gas evolution were derived from the measured psd of the potential fluctuations, such as the average number of detached bubbles per time unit, the average radius of the detached bubbles and the gas evolution efficiency. The influence of the electrolysis current on these parameters was also investigated. The results of this first attempt at parameter derivation are discussed.Nomenclature b Tafel coefficient (V^–1), Equation 46 - C electrode double layer capacity (F) - e gas evolution efficiency (%) - f frequency (Hz) - f _p frequency of the peak in the psd _v and _i (Hz) - F Faraday constant, 96 487 C mol^–1 - l electrolysis current (A) - J electrolysis current density (mA cm^–2) - k slope of the linear potential increase (V s^–1), see Fig. 1 - n number of electrons involved in the reaction to form one molecule of the dissolved gas - r _b radius of a spherical glass ball (m) - r _e radius of the disk electrode (m) - R _e electrolyte resistance () - R _p polarization resistance () - R _t charge transfer resistance () - u ₁ distribution function of the time intervals between two successive bubble departures (s^–1) - v _g mean volume of gas evolved per unit time (m³ s^–1) - v _t gas equivalent volume produced in molecular form per unit time (m³ s^–1) - V ₀ gas molar volume, 24.5×10^–3 m³ at 298 K - x ₀ time pseudoperiod of bubbles evolution (s) - Z electrode electrochemical impedance () Greek characters _e dimensionless proportional factor (Equation 19) - slope of log /logJ and loge/logJ curves - number of bubbles evolved per unit time (s^–1) - _a activation overpotential (V) - _ci concentration overpotential of reacting ionic species (V) - _cs concentration overpotential of dissolved molecular gas (V) - _ohm ohmic overpotential (V) - _t total overpotential (V) - v parameter characteristic of the gas evolution pseudoperiodicity, Equation 13 (s^–1) - time constant of the double layer capacity change (s) - _v power spectral density (psd) of the potential fluctuations (V² Hz^–1) - _i power spectral density (psd) of the current fluctuations (A² Hz^–1) Special symbols spatial average of the overpotential _j over the electrode surface - time averaged value of - _j fluctuation of around - <> mean value of the total overpotential jump amplitude due to a bubble departure - <I> mean value of the current jump amplitude due to a bubble departure Paper presented at the 2nd International Symposium on Electrolytic Bubbles organized jointly by the Electrochemical Technology Group of the Society of Chemical Industry and the Electrochemistry Group of the Royal Society of Chemistry and held at Imperial College, London, 31st May and 1st June 1988.     

Characteristics of Heterophase Radical Graft Polymerization of Methyl Methacrylate on Polymer Fibres

Graft copolymers with graft PMMA were synthesized using the Cu²⁺—H₂O₂ redox system. The conditions for obtaining graft PCA—PMMA and HC-PMMA of 40–60 composite composition with grafting efficiency at the 85% level are found. The effect of the polymer matrix on the kinetic and thermodynamic properties of graft polymerization of MMA is revealed. Possible schemes of the reactions of graft polymerization of MMA to polycaproamide and hydrated cellulose are proposed based on quantum chemical calculations of the enthalpy of formation of the graft copolymers.The research was conducted under MNTPP Project No. 203 Chemical Engineering (Section 2 General Chemical Engineering) in the scientific-industrial program Higher-Education Research on Priority Directions in Science and Engineering.__________Translated from Khimicheskie Volokna, No. 1) pp. 19–23, January–February, 2005.     

Mass and momentum transfer enhancement due to electrogenerated gas bubbles

The effect of electrogenerated gas bubbles with simultaneous bulk liquid flow on the mass and momentum transfer at a wall of an electrolytic cell is experimentally determined. The local mass transfer coefficient and electrolyte shear stress are obtained using two types of microelectrodes imbedded in the channel wall. The influence of the most important parameters (electrolyte velocity, position along the wall, gas electrogeneration rate) on the transfer enhancement is studied and an analogy between mass and momentum transfer in the presence of bubbles is clearly demonstrated from the experimental results. The comparison with classical correlations, valid for systems involving natural turbulence, shows the higher energetic efficiency of devices where the turbulence is artificially generated by electrolytic gas bubbles.Nomenclature A constant parameter in Equation 3 - ¯C time averaged value of the concentration of a reacting species - c ₀ molar concentration in the bulk of the solution - d microelectrode diameter - d _e hydraulic equivalent diameter - D molecular diffusion coefficient - D _t turbulent diffusivity of mass transfer - f/2 friction factor, =/gr¯v ² - h channel thickness - I _g electrogeneration rate - i _g electrogeneration current density - i _l limiting current density on a microelectrode imbedded in the conducting wall - i_l limiting current density on a microelectrode imbedded in the inert wall - k _d local mass transfer coefficient - k local mass transfer coefficient on a microelectrode in the non-conducting wall - N _M specific mass flux near an interface - Re Reynolds number, = (¯vd _e)/v - s velocity gradient, = (¯v _x/y)y = o - s ⁺ dimensionless velocity gradient, =sd ²/D - Sc Schmidt number, =v/D - Sh Sherwood number, = (k _d x)/D - St Stanton number, =k _d/¯v - ¯v, ¯v _x electrolyte velocity - v ^* friction velocity, = (/)^1/2 - v ⁺ normalized velocity, =¯v _x /v ^* - x axial coordinate - y coordinate perpendicular to the wall - y ⁺ dimensionless length = (yv ^*)/v Greek letters parameter defined in Equation 8 - boundary layer thickness - ⁺ dimensionless form of , = (s/v)^1/2 - , _x electrolyte shear stress - dynamic viscosity - kinematic viscosity - _t momentum transfer diffusivity - specific gravity - ² variance of the fluctuations ofi _L ori _L Paper presented at the International Meeting on Electrolytic Bubbles organized by the Electrochemical Technology Group of the Society of Chemical Industry, and held at Imperial College, London, 13–14 September 1984.     

Electrolytic process optimization by simultaneous-modular flowsheeting

A procedure is described for computer-assisted optimization of an electrolytic process flowsheet. Material, energy, and economic balances for all process units were incorporated in a nonlinear optimization routine for predicting the minimum selling price based on a discounted cash flow rate of return on investment. The optimization utilized a simultaneous-modular approach which was incorporated into the public version of the Aspen flowsheeting package, and used an infeasible path convergence method based on successive quadratic programming procedures. Electrolyte vapour-liquid equilibrium data were estimated by the non-random two-liquid model. The Lagrangian multipliers of the constraint equations were used to determine the sensitivity of the optimum to key process variables. The method was illustrated by evaluation of two process flowsheets for electrosynthesis of methyl ethyl ketone (MEK) from 1-butene based on pilot-plant performance reported in the patent literature.List of symbols A _c cell cost factor ($ cell^–1) - A _H heat exchanger cost factor ($ m^–2) - A _p pump cost factor ($ sl^–1) - A _R rectifier cost factor ($ kVA^–1) - A _T tank cost factor ($l ^–0.5) - A _cm cell maintenance factor ($ A^–1 y^–1) - A _cl cell labour ($ cell^–1 y^–1) - A _cw cooling water cost ($ m^–3) - A _e electricity cost ($ kWh^–) - A _m membrane cost ($ cell^–1 y^–1) - A _om other maintenance factor, fraction of plant capital less cell cost - C _p cooling water heat capacity (kJ kg^–1 °C^–1) - H operating hours per year - I _C current to each cell (A) - I _TOT total current to all cells (A) - L _A Lang factor for auxiliaries - L _C Lang factor for cells - L _R Lang factor for rectifiers - N number of cells in plant - Q heat removal load (kJ h^–1) - R production rate (kgh^–1) - T _cw cooling water temperature rise (°C) - T _LM cooler log mean temperature difference (°C) - U heat transfer coefficient for cooler (kW m^–2 °C^–1) - v _c electrolyte flow to each cell (l ^-1) - v _C cell voltage (V) - _R rectifier efficiency - cooling water density (kg m^–3) - _T surge tank residence time (s)     

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.     

Occurrence and Correlations of Monoterpene Hydrocarbon Enantiomers in Pinus sylvestris and Picea abies

The relative amounts and enantiomeric compositions of monoterpene hydrocarbons in branch and trunk xylem, in needles, and in resin from apical buds in 18 Pinus sylvestris trees have been determined and compared with the terpene content in branch xylem and needles of Picea abies. Besides the high amount of (+)-3-carene, an excess of (+)--pinene has been found in P. sylvestris, whereas in P. abies (–)--pinene dominates over (+)--pinene. In P. sylvestris, clear positive correlations were found between (+)--pinene and (+)-camphene in the four tissues analyzed. Good positive correlations were also observed between (–)--pinene and (–)-camphene in the two types of xylem, between (+)--pinene and (+)--pinene in the resin, and between tricyclene and (–)-camphene in resin and needles. In P. abies, positive correlations were found between (+)--pinene and (+)-camphene in the branch xylem and between tricyclene and (–)-camphene as well as between (–)--pinene and (–)-camphene in the needles. Complex relationships between (–)--pinene and (–)--pinene were found both in the P. abies and in the P. sylvestris tissues. The importance of the enantiomeric composition of -pinene for the host selection of Ips typographus, Tomicus piniperda, and Hylobius abietis is discussed.     

Identification of sex pheromones of two sibling species in dingy cutworm complex,Feltia jaculifera (GN.) (Lepidoptera: Noctuidae)

The sex pheromone components of the two sibling species of the dingy cutworm that occur on the prairies of western Canada were identified in abdomen-tip extracts from calling female moths. Three monounsaturated acetates, (Z)-7-dodecenyl acetate, (Z)-9-tetradecenyl acetate, and (Z)-11-hexadecenyl acetate, are common to both species in ratios of 100133 for species A and 0.30.5100 for species B. The most effective synthetic blends for the attraction of male moths in the field consisted of these three components in ratios of 1010 at 8.8g/lure for species A and 112000 at 500g/lure for species B. The addition of Z5-12Ac to either blend reduced the catches and the addition of Z7-12OH orZ11-16OH to the three-component blend reduced the catches of species B males. The species are morphologically indistinguishable, but the identity of the males attracted to the synthetic blends could be confirmed by their antennal responses to a test blend of the three components using a GC-EAD system. Both synthetic attractant blends are competitive with females and will be useful for studying the distribution, biology, and relative abundances of the two species.Contribution no. 3879005 of the Lethbridge Research Station.     

Mass transfer at rough gas-sparged electrodes

Rates of mass transfer were measured by the limiting current technique at a smooth and rough inner surface of an annular gas sparged cell in the bubbly regime. Roughness was created by cutting 55°V-threads in the electrode normal to the flow. Mass transfer data at the smooth surface were correlated according to the expression j = 0.126(Fr Re)^–0.226 Surface roughness of peak to valley height ranging from 0.25 to 1.5 mm was found to have a negligible effect on the mass transfer coefficient calculated using the true electrode area. The presence of surface active agent (triton) in the solution was found to decrease the mass transfer coefficient by an amount ranging from 5% to 30% depending on triton concentration and superficial air velocity. The reduction in the mass transfer coefficient increased with surfactant concentration and decreased with increasing superficial gas velocity.Nomenclature a constant - A electrode area (cm²) - C _p specific heat capacity Jg^–1 (K^–1) - C ferricyanide concentration (m) - d _c annulus equivalent diameter, (d _o – d _i) (cm) - d _o outer annulus diameter (cm) - d _i inner annulus diameter (cm) - D diffusivity of ferricyanide (cm²s^–1) - e peak-to-valley height of the roughness elements (cm) - e ⁺ dimensionless roughness height (eu ^*/) - f friction coefficient - F Faraday constant (96 500 Cmol^–1) - g acceleration due to gravity (cm s^–2) - h heat transfer coefficient (J cm^–2 s K) - I _L limiting current (A) - K mass transfer coefficient (cm s^–1) - K thermal conductivity (W cm^–1 K^–1) - V _g superficial air velocity (cm s^–1) - Z number of electrons involved in the reaction - Re Reynolds number (_L V _g d _e/) - J mass or heat transfer J factor (St Sc ^0.66) or (St Pr ^0.66), respectively - St Stanton number (K/V _g for mass transfer and h/C _p V _g for heat transfer) - Fr Froude number (V _g ² /d _e g) - Sc Schmidt number (/D) - Pr Prandtl number (C _p/K) - PL solution density (g cm^–3) - kinematic viscosity (cm²s^–1) - gas holdup - u ^* friction velocity = V _L(f/2) - diffusion layer thickness (cm) - solution viscosity (gcm^–1 s^–1)     

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.     

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