On mass transfer effect due to electrolytically evolved gas

Based on the Ibl penetration model mass transfer equations for gas-evolving electrodes were derived and compared to the effect of forced convection. Experimental studies were conducted in a rectangular flow channel with the working electrode facing downward. The variables were linear bubble velocity, linear electrolyte velocity, nature of the gas and electrode position. Up to bubble velocities (U_x) of 2 and 6 cm s⁻¹ for O₂ and H₂ gases respectively, the thickness of the Nernst diffusion layer (δ_av) was described well by the equation δ_av = [Dd_eL/(U_x)_av]^1/3. Intermediate slopes between − 1/3 and − 1 were observed for O₂ bubble velocities between 2 and 6 cm s⁻¹. A theoretical derivation suggests that in the absence of bubble coalescence, the mass transfer effect due to laminar flow induced by electrolytically evolved gas exceeds that due to forced external laminar flow for all practical channel designs.     

Effect of macromolecular length on anisotropic scattering of light in an electric field

Light scattering by monodisperse solutions of rigid rod-like anisotropic macromolecules, with linear dimensions l of the order of incident wavelength λ, oriented in an external d.c. electric field, →E has been analysed. The relative variations δV^E_v, δH^E_v, δV^E_h, δH^E_h of the scattered light components are discussed for the three values [l/λ] = 1, 0·5, 2, and various reorientation parameters, p = [μE/kT] of the permanent dipole moment μ and q = [(₃ − ₁)E²/2kT] of the moment induced by the principal polarizabilities ₁ = ₂ ≠ ₃. The saturation orientation field strength has been calculated for certain macromolecules with the aim of determining their optical anisotropy numerically.     

Effect of electro-chemical properties of sodium salts of various anions on their diffusional parameters in symmetrical cellulose acetate membranes

A relation was obtained between electro-chemical properties of sodium salts (NaCl, NaBr, and Na₂SO₄), and the thermodynamic property of permeability in symmetrical cellulose acetate membranes, the distribution coefficient K and the kinetic property, the overall diffusion coefficients D. K and D were obtained by the method we proposed using measured unsteady- and steady-state dialysis data. The K values increase with the increase of water content and are in the range of 10⁻² for sodium halides and 10⁻³ for Na₂SO₄. D is found to increase with the increase of the solute concentration, and the extrapolated values of D to zero concentration D⁽⁰⁾ are obtained as 0.015–0.03 μm²/s and increase with the increase of water content in the membrane. D can be divided into the concentration independent diffusion coefficients in the dense part of the membrane D_d and in the porous D_p, applying a two-part (perfect or dense and imperfect or porous) model of the membrane. Contrary to D_d, D_p increases with the increase of W_w and can be correlated as D_p,c = _d exp (γ × W_w). It is shown that the averaged D_d, _D increases with the increase of the quantity of the ionic mobility u of the solutes at infinite dilution divided by valence, and that the parameter γ increases with the increase of the ionic mobility u. The value of K increases slightly with the increase of water content and decreases with the increase of the Flory—Huggins parameter χ. The Flory—Huggins parameter χ is calculated from the measured values of distribution coefficients and data obtained from the literature. And it was found that the gradient of linear decrease of χ (λ_cation) depends on equivalent ionic conductivity of anion of salt, λ_an.     

Dynamic mechanical spectra of poly(itaconic acid esters) containing phenyl and cyclohexyl rings

The dynamic mechanical response of a series of poly(itaconic acid esters), in which the ester group, ---COOR, has R = (CH₂)_n ø with n = 0, 1, 2 and ø is either a phenyl or cyclohexyl ring, was studied over the temperature range 90 to 425K. In each case the glass transition temperature T_g, of the cyclohexyl derivative is higher than the corresponding phenyl derivative, and T_g also decreases as n increases. A β-transition, located in both the phenyl and cyclohexyl series, is attributed to motion of the ester groups. In addition the cyclohexyl polymers exhibit a prominant γ-transition caused by cyclohexyl ring movement and there is also a δ-transition in this series which is believed to be a precursor of the γ-transition.     

Reversible electrochemical insertion of anions in poly-p-phenylene from aqueous electrolytes

Poly-p-phenylene (PPP) was synthesized from benzene according to the Kovacic method. Electrodes were made from this electronic insulator by cold- or hot-pressing of the loose, brown powder, under the addition of 7.5 wt. % soot (Corax L^®, Degussa AG). The electrochemical insertion and removal of anions HSO⁻₄, ClO⁻₄ in this material in aqueous solutions of the corresponding acids was investigated by slow cyclic voltammetry.

Initially, only a surface layer of about 0.1 mm thickness takes part in the electrochemical processes, which are reversible. A maximum concentration of anions in the solid of [(−C₆H₄−)⁺₇ A⁻] is attainable. The maximum degree of insertion is equal to 0.14. The insertion potential U_I shifts strongly into the negative direction with increasing concentration c of the acid. A linear U_I/c relationship is observed as in the case of graphite, where the intercalation potential is more positive by 20–200 mV for the same electrolyte. The round trip current efficiency for the insertion/removal cycle increases with increasing acid concentration attaining 100% in 14 M H₂SO₄ or 11.3 M CHlO₄. For a given concentration, increases in the same order as with graphite (H₂SO₄ < HClO₄ < HBF₄), being somewhat lower for a given electrolyte composition. From anodic current limitation (j_lim = 5–10 mA cm⁻²), a diffusion coefficient of about D = 2 × 10⁻⁷ cm² s⁻¹ is derived for the transport of anions in the bulk of PPP. The striking similarity of our results to former findings with graphite is thoroughly discussed. Some general conclusions are derived thereof.     

Walden product, ion-solvent interactions and solvent structure in water-rich mixtures ionic conductances in water-sulfolane, water-acetonitrile and water-dimethylsulfoxide

Conductance measurements are reported for several salts in binary aqueous mixtures containing up to 60 mole % sulfolane, 20 mole % acetonitrile and 20 mole % dimethylsulfoxide. The variations of R = (λ^±₀η₀)_s/(λ^±₀η₀)_w with solvent composition have been compared with those observed in other water-rich mixtures. Alkali cations show R values greater than one with maxima in all the solvent mixtures. This behaviour has been discussed in terms of “sorting”, “averaging” and “steric” effects. Contrary to what happens to alkali cations, halide ions show R values greater or lesser than one according to whether the organic solvent respectively increases or decreases water structure. On these bases we suggest that conductometric behaviour of the halide ions may be indicative of the effect of the cosolvent on the water structure in water-rich mixtures and that DMSO is a water structure breaker.     

Transport numbers and oxygen permeability of SrCe(Y)O3-based ceramics under oxidising conditions

Partial conductivities in the SrCe(Y)O_3−δ system have been studied in oxidising conditions in the temperature range 923–1273 K. Compositions with variable Y content (5 and 10 at.%), Sr deficiency (3 at.%), and with the addition of Fe₂O₃ as sintering aid (2 mol%) were analysed. A modified Faradaic efficiency method and oxygen permeation measurements were employed to appraise the oxide-ionic transport. Oxide-ion transference numbers in air lie in the range 0.19–0.80 and decrease with increasing temperature in the range 973–1223 K. Modelling of total conductivity as a function of oxygen partial pressure (p(O₂)) confirmed that protonic transport is minor under the studied conditions. SrCe_0.95Y_0.05O_3−δ exhibits greater oxide-ion conductivity than SrCe_0.9Y_0.1O_3−δ, indicative of dopant–vacancy association at high dopant contents. Conversely, oxygen permeability is slightly higher for SrCe_0.9Y_0.1O_3−δ as a result of faster surface-exchange kinetics. The oxygen flux through Fe-free membranes is dominated by the bulk in low p(O₂) gradients, when the permeate-side p(O₂) is higher than 0.03 atm, but surface exchange plays an increasing role with increasing p(O₂) gradient. Addition of Fe₂O₃ to SrCe(Y)O_3−δ lowers the sintering temperature by 100 K but results in the formation of intergranular second phases which block oxide-ionic and electronic transport, and thus oxygen permeation. The average thermal expansion coefficients (TECs) are (10.8–11.6) × 10⁻⁶ K⁻¹ in the temperature range 373–1373 K for all studied compositions.     

Kinetics and equilibrium swelling of gelatine gels

The swelling features of gelatine gels in water (good solvent) were studied as a function of thermodynamic conditions of sol—gel transition and ripening. It is shown that the degree of equilibrium swelling Q_e varies with the volume fraction of the polymer in a casting solution φ_o in accordance with the prediction of the classic theory: Q_e φ_o^−0.4. Q_c, as a function of the gelation temperature T_g, the ripening time t_r and φ_o, can be rescaled and described by the single empirical equation: Q_e T_g^−x t_r^−yφ_o^−0.4, where x = 0.1, y = 0.15 for wet gels and X = −0.5, y = 0.04 for dried gels. The kinetics of macroscopic swelling is described by the equation of Peters and Candau, with values of collective diffusion coefficients being in good agreement with values obtained by other workers via photon correlation spectroscopy.     

The static contact angle hysteresis obtained by different experiments for the system PTFE/water

Different experimental methods have been used to determine the static contact angle hysteresis of the system polytetrafluoroethylene/water and the results compared. While the Wilhelmy plate method is not influenced by methodical variations, contact angles determined by the sessile drop and the pendant bubble methods vary with the drop or bubble diameter up to a minimal diameter d_K of the contact area with the solid. This condition seems to be a universal one and should always be checked to ensure that the measured values are comparable. Contact angles calculated from the geometrical parameters of a drop or bubble should be used with care. The surface energetic characters for the PTFE/water are δθ = 19.5°, θ_{a, e} = 108.5° and θ_{r, e} = 89°.     

EPR study of electrochemical lithium intercalation in V2O5 cathodes

The evolution of the cathode material of Li/V₂O₅ cells upon lithium intercalation is studied by Electron Paramagnetic Resonance (EPR) spectroscopy. Below one lithium per V₂O₅(x < 1), where the electrochemical process is completely reversible, V^IV ions of the - and δ-Li_x V₂O₅ phases are detected by EPR. Within this intercalation range, the shape of the EPR signal is dominated by the strong exchange interactions between magnetically concentrated V^IV ions of the Li_x V₂O₅ phases. The intercalation range x > 1 is characterized by a new EPR signal attributed to magnetically diluted vanadyl ions VO²⁺. It is shown that these species do not belong to the Li_x V₂O₅ matrix, but most probably originate from the liberation of surface vanadyl ions during the irreversible transformation of δ-Li_x V₂O₅ into γ-Li_x V₂O₅. On the basis of these results, a mechanism to explain the partial irreversibility of the electrochemical processes is proposed. A third EPR signal is also observed for x 1. This signal is attributed to an electron-hole defect in Li_x V₂O₅, originating from a local charge compensation of the vanadyl vacancies.     

(CH3CH[NH3]CH2NH3)1/2·ZnPO4, a zincophosphate analogue of aluminosilicate zeolite thomsonite

The synthesis and structure of (CH₃CH[NH₃]CH₂NH₃)_1/2·ZnPO₄, an organically templated zincophosphate (ZnPO) analogue of aluminosilicate zeolite thomsonite (THO), are described. The ZnPO framework is built up from an alternating, vertex-sharing, network of ZnO₄ and PO₄ groups (d_av(Zn–O)=1.944 (8) Å, d_av(P–O)=1.535 (9) Å, θ_av(Zn–O–P)=130.5°) involving distinctive 4=1 secondary building units. The 1,2-diammonium propane cations are highly disordered in the [0 0 1] 8-ring channels. Crystal data: (CH₃CH[NH₃]CH₂NH₃)_1/2·ZnPO₄, M_r=198.42, orthorhombic, space group Pncn (no. 52), a=14.119 (6) Å, b=14.136 (5) Å, c=12.985 (5) Å, V=2591 (3) ų, Z=10, R(F)=0.057, R_w(F)=0.061 (for a twinned crystal).     

Aerosol classification by electric mobility: apparatus, theory, and applications

An improved version of the Hewitt (differential) electric mobility analyzer was developed and its classifying characteristics were determined theoretically. The central mobility of the classified aerosol was found to be (q_c + q_m)/4πΛV, where q_c and q_m are the clean air and main outlet flows, respectively, Λ is a geometric factor, and Λ is the center rod voltage. The half-width of the mobility band was found to be (q_a + q_s)/4πΛV, where q_a and q_s are the aerosol and sampling outlet flows, respectively. These expressions were verified by the tests with a monodisperse aerosol of known size and low charge.

A major advantage of this device is that the classified aerosol fraction remains airborne, ready for further use or analysis. Thus, one application of the device is the production of monodisperse test aerosols of known size, charge, and concentration by classification of a polydisperse aerosol. Other current applications include accurate measurement of particle electric mobility moments and high-resolution particle size analysis for polydisperse aerosols in the 0.005–1.0 μm size range.     

AFeO3 (A=La, Nd, Sm) and LaFe1−xMgxO3 perovskites as methane combustion and CO oxidation catalysts: structural, redox and catalytic properties

Catalytic methane combustion and CO oxidation were investigated over AFeO₃ (A=La, Nd, Sm) and LaFe_1−xMg_xO₃ (x=0.1, 0.2, 0.3, 0.4, 0.5) perovskites prepared by citrate method and calcined at 1073 K. The catalysts were characterized by X-ray diffraction (XRD). Redox properties and the content of Fe⁴⁺ were derived from temperature programmed reduction (TPR). Specific surface areas (SA) of perovskites were in 2.3–9.7 m² g⁻¹ range. XRD analysis showed that LaFeO₃, NdFeO₃, SmFeO₃ and LaFe_1−xMg_xO₃ (x·0.3) are single phase perovskite-type oxides. Traces of La₂O₃, in addition to the perovskite phase, were detected in the LaFe_1−xMg_xO₃ catalysts with x=0.4 and 0.5. TPR gave evidence of the presence in AFeO₃ of a very small fraction of Fe⁴⁺ which reduces to Fe³⁺. The fraction of Fe⁴⁺ in the LaFe_1−xMg_xO₃ samples increased with increasing magnesium content up to x=0.2, then it remained nearly constant. Catalytic activity tests showed that all samples gave methane and CO complete conversion with 100% selectivity to CO₂ below 973 and 773 K, respectively. For the AFeO₃ materials the order of activity towards methane combustion is La>Nd>Sm, whereas the activity, per unit SA, of the LaFe_1−xMg_xO₃ catalysts decreases with the amount of Mg at least for the catalysts showing a single perovskite phase (x=0.3). Concerning the CO oxidation, the order of activity for the AFeO₃ materials is Nd>La>Sm, while the activity (per unit SA) of the LaFe_1−xMg_xO₃ catalysts decreases at high magnesium content.     

Direct Measurement of Energy Barriers on Rough and Heterogeneous Solid Surfaces

The “three-liquid” contact angle approach to the surface free energy components of solids was applied to poly (vinyl fluoride), rough and flattened, with and without flame treatment. Lifshitz-van der Waals (LW), γ^LW_SL, and acid-base (AB), γ^LW_SL, components were determined and used to calculate -δG_SL (W^adhesion_SL) for the formation of interfaces of five liquids with polymer. The automated goniometer allowed the determination of the energy barriers, -δ G*_SL as the advancing liquid moved from pinned configuration to a metastable one. The acid-base component of the barriers was much greater than the LW, and the magnitude of the barriers was only slightly reduced by flattening.     

The glass temperature of polymer blends

The entropy theory of glasses is used to derive the glass temperature, T_g, of a binary polymer blend in terms of the glass temperatures of the two substituents. The formula is T_g = B₁T_g1 + B₂T_g2, where B_i is the fraction of flexible bonds of substituent i. A bond is flexible if rotation about it changes the shape of the molecule. Bonds in side groups as well as in the backbone are to be counted. This formula assumes that the free volume, taken here to be the volume fraction of empty lattice sites, is the same for each of the three materials. It has no parameters. The above equation expressed in weight fractions, W_i, is (T_g − T_g1)W₁(γ₁/ω₁) + (T_g − T_g2)W₂(γ₂/ω₂) = 0, where ω_i is the weight of a monomer unit and gg_i is the number of flexible bonds per monomer unit. A more general treatment is given. One variation of the more general treatment which expresses the properties of the blend in purely additive terms gives T_g = B₁T_g1 + B₂T_g2 + KB₁B₂(T_g1 − T_g2)(V₀₁ − V₀₂), where V_0i are the free volume fractions of the homopolymers at their glass temperatures and K is a constant. The added term is usually small. The most general form of the equation requires the energy of interaction between the two unlike molecules, which can be estimated by volume measurements on the blend.     

Electrosorption and inhibition properties of p-norborn2-yl phenolate ions at the mercury/solution interface

The electrosorption properties of p-norborn-2-yl phenolate ions in alkaline solutions were investigated by ac polarographic and electrocapillary measurements.

Two adsorption regions were found. At low bulk surfactant concentrations the adsorption at the positively charged electrode (−0.2 E −0.6 V) is predominant while at higher surfactant concentrations the adsorption at the negatively charged electrode (−0.6 E −1.0 V) is more pronounced. At E = −0.40 V the adsorption parameters were determined (a ≈ 2; ΔG°_A = −32.5 ± 1 kJ mol⁻¹. Between −0.6 E −1.0 V one potential of maximum adsorption for all concentrations does not exist and therefore the adsorption parameters could not be calculated.

At E = −0.40 V progressive two-dimensional nucleation with a nucleation order of 3 was observed which corresponds well with the high attraction constant.

The electrode reaction S₂O²⁻₈ + 2e⁻ → 2 SO²⁻₄ is inhibited by norborn-2-yl phenolate ions in the potential range −0.2 E −0.6 V. In the second potential range of capacity decrease the electrode process is much less retarded. At E = −0.40 V, in a similar manner as described for neutral molecules, a linear dependence of the log k_s (k_s apparent rate constant) on ln c_A and π (π = surface film pressure), respectively, has been found.     

Electrochemical properties of non-stoichiometric V6O13

Non-stoichiometric V₆O_13±0.2 (VO_y) prepared by thermal decomposition of NH₄VO₃ in N₂ atmosphere is investigated cathode material for Li batteries. The maximum lithium composition is found to be Li_2y-3VO_y. The emf vs composition relationship of Li/Li_xVO_2.144 is determined in the interval 0 < x < 1.3, yielding a theoretical energy density of 890 Wh kg⁻¹. The kinetics and reversibility of the VO_y electrode is investigated by cyclic voltammetry and cycling of test cells. The lithium diffusion coefficient and the electronic conductivity of the oxide is found to decrease with increasing lithium content. The cyclability of very thin electrodes is found to be excellent, but inferior results are obtained with practical cells, presumably due to degradation of electrode structure.     

Crystallinity and fusion of ethylene oxide/propylene oxide block copolymers: 2. Type PEP copolymers

Lamella spacings, specific volumes and melting points have been determined for a series of well characterized poly(ethylene oxide)/poly(propylene oxide) type PEP block copolymers with E-block length 48 chain units and P-block lengths 0 to 7 chain units. These properties are interpreted in terms of a stacked lamella model with alternating amorphous and crystalline layers. Both extended-chain and once-folded-chain crystalline lamellae are found, the former with thickness about 32 E chain units and the latter with thickness about 21 E chain units. Compared with the specific volume of supercooled melt of the same composition the specific volume of the polymer in the amorphous lamellae is lower in the extended-chain polycrystals and higher in the once-folded-chain polycrystals. The melting points of the copolymers are low compared to that of perfectly crystalline poly(ethylene oxide), i.e. 37 to 55°C compared with T⁰_m = 76°C. This is due to the large positive free energy of formation from the melt of the crystalline/amorphous end interface (σ_o) and the amorphous layer (σ_a). For extended-chain polycrystals we find σ_o 3 kJ/mol and σ_a 3.5 kJ/mol; for once-folded-chain polycrystals we find σ_o 6 kJ/mol and σ_a 2 kJ/mol. We also find σ_o,x = 2.5 kJ/mol for a completely extended-chain end interface and σ_o,f = 10 kJ/mol for a completely folded-chain end interface.     

Einfluss der säurekonzentration auf die anodische auflosung des indiumamalgams

The effect of HClO₄ concentration on the rate of electrode processes on a stationary indium amalgam electrode in stirred In(ClO₄)₃ solutions at constant ionic strength (3 M NaClO₄) has been investigated. Alongside with the measurement of polarization curves, the exchange current and the true rate of the anodic process of amalgam dissolution (i_a at different potentials (φ) were determined by a radiochemical method. With an increase in the HClO₄ concentration, a sharp decrease in the exchange current is observed; at HClO₄ concentrations below 0.2 M at constant φ, the i_a values are inversely proportional to the HClO₄ concentration. The experimental results are expressed by the equation p] i_a = k[In][H⁺]⁻¹ exp (βφF|RT),

where [In] is the concentration of the indium amalgam. The rate of the cathodic process at constant φ also decreases with a decrease in pH. A hypothesis is advanced according to which partially hydrolysed In(H₂O)₅OH²⁺ ions, rather than In(H₂O)₆³⁺ which are predominant in the solution, participate in the electrode process. The OH⁻ ions, like some other anions, appear to be capable of facilitating the transfer of electrons between the electrode surface and the reacting particle. An analysis of the results obtained (and of data in the literature) shows that partially hydrolysed metal ions play an essential role in electrode processes.