A model of the electrochemical behaviour within a stress corrosion crack

A mathematical model of the electrochemical behaviour within a stress corrosion crack is proposed. Polarization field, crack geometry, surface condition inside the crack, electrochemical kinetics, solution properties and applied stress can be represented by the polarization potential and current, the electrochemical reactive equivalent resistance of the electrode, the change in electrolyte specific resistance and surface film equivalent resistance, respectively. The theoretical calculated results show that (i) when anodic polarization potential is applied, the change in the crack tip potential is small; (ii) when cathodic polarization potential is applied, the crack tip potential changes greatly with the applied potential; (iii) the longer the crack, the smaller the effect of the applied potential on the crack tip potential in both anodic polarization and cathodic polarization conditions. The calculated results are in good agreement with previous experimental results.Notation coordinate, from crack mouth (on the metal surface) to crack tip (cm) - y y = s _L L/(s ₀ – s _L) + L – , function of (cm) - y ₀ y ₀ = s _L L/(s ₀ – s _L) + L (cm) - V polarization potential (V) - galvanic potential of electrode (V) - ₁ galvanic potential of electrolyte (V) - t sample thickness (cm) - w sample width (cm) - S _L crack tip width (cm) - S _o crack mouth width (cm) - L crack length (cm) - s() crack width at position (cm) - _lo specific resistance of electrolyte, as a constant ( cm) - _s specific resistance of metal ( cm) - (, y) specific resistance of electrolyte, varies with potential and crack depth ( cm) - R _b (, y) electrochemical reactive equivalent resistance of electrode, varies with potential and crack depth () - R ₁ electrolyte resistance () - R _s metal resistance () - r(, y) surface film equivalent resistance, varies with potential and crack depth () - r _o surface film equivalent resistance, as a constant () - I _o total polarization current (A) - I net polarization current from integrating 0 to in Fig. 2 (A) - polarization overpotential (V) - _a anodic polarization overpotential (V) - _c cathodic polarization overpotential (V) - Euler's constant     

Mass transport in a weakly stratified electrochemical cell

A study of natural convection in an electrochemical system with a Rayleigh number of the order 10¹⁰ is presented. Theoretical and experimental results for the unsteady behaviour of the concentration and velocity fields during electrolysis of an aqueous solution of a metal salt are given. The cell geometry is a vertical slot and the reaction kinetics is governed by a Butler-Volmer law. To reduce the effects of stratification, the flush mounted electrodes are located (symmetrically) in the middle parts of the vertical walls. It is demonstrated, both theoretically and experimentally, that a weak stratification develops after a short time, regardless of cell geometry, even in the central part of the cell. This stratification has a strong effect on the velocity field, which rapidly attains boundary layer character. Measured profiles of concentration and vertical velocity at and above the cathode are in good agreement with numerical predictions. For a constant cell voltage, numerical computations show that between the initial transient and the time when stronger stratification reaches the electrode area, the distribution of electric current is approximately steady.List of symbols a _i left hand side of equation system - b _i right hand side of equation system - c concentration (mol m^–3) - c dimensionless concentration - c _i concentration of species i' (mol m^–3) - c₀ initial cell concentration (300 mol m^–3) - c ₀ dimensionless initial cell concentration - c_wall concentration at electrode surface (mol m^–3) - dx increment solution vector in Newton's method - D _i diffusion coefficient of species i (m² s^–1) - D ₁ 0.38 × 10^–9 m² s^–1 - D ₂ 0.82 × 10^–9 m² s^–1 - D effective diffusion coefficient of the electrolyte (0.52 × 10^–9 m² s^–1) - _x unit vector in the vertical direction - _y unit vector in the horizontal direction - F Faraday's constant (96 487 A s mol^–1) - g acceleration of gravity (9.81 m s^–2) - i dummy referring to positive (i = 1) or negative (i = 2) ion - f current density (A m^–2) - f dimensionless current density - i₀ exchange current density (0.01 A m^–2) - J _ij Jacobian of system matrix - L length of electrode (0.03 m) - N _i transport flux density of ion i (mol m^–2 s^–1) - n unit normal vector - p pressure (Nm^–2) - p dimensionless pressure - R gas constant molar (8.31 J K^–1 mol^–1) - R _i residual of equation system - Ra Rayleigh number gL ³ c ₀/D (2.54 × 101¹⁰) - S _c Schmidt number /D (1730) - t time (s) - t dimensionless time - T temperature (293 K) - velocity vector (m s^–1) - dimensionless velocity vector - U characteristic velocity in the vertical direction - V _± potential of anode and cathode, respectively - x spatial coordinate in vertical direction (m) - x dimensionless spatial coordinate in vertical direction - x solution vector for c, and - y spatial coordinate in horizontal direction (m) - y dimensionless spatial coordinate in horizontal direction - z _i charge number of ion i Greek symbols symmetry factor of the electrode kinetics, 0.5 - volume expansion coefficient (1.24 × 10^–4 m³ mol^–1) - _s surface overpotential - constant in equation for the electric potential (–5.46) - _s diffusion layer thickness - scale of diffusion layer thickness - constant relating c/y to the Butler-Volmer law (0.00733) - kinematic viscosity (0.9 × 10^–6 m2 s^–1)     

Weak Gel Behaviour of Poly(vinyl alcohol)-Borax Aqueous Solutions

Thermal transition of PVA-borax aqueous gels with a PVA concentration of 60 g/L and a borax concentration of 0.28 M was investigated at temperatures ranging from 15 to 60C using static light scattering (SLS), dynamic light scattering (DLS), and dynamic viscoelasticity measurements. Three relaxation modes, i.e. two fast and one slow relaxation modes, were observed from DLS measurements. Two fast relaxation modes located around 10^–310¹ sec, with one fast mode (_f1) being scattering vector q-dependent and the other fast mode (_f2, with _f2>_f1) being q-independent. The _f1 mode was attributed to the gel mode whilst the _f2 mode could be due to the hydrodynamics of intra-molecular hydrophobic domains formed by uncharged segments of polymer backbones. The slow relaxation mode with relaxation time located around 10¹10³ sec in DLS data was due to the motion of aggregated clusters and was observed only at temperatures above 40C. The amplitude and relaxation time of slow mode decrease as temperature is increased from 40 to 60C. At temperatures below 40C, no slow relaxation mode was observed. The SLS measurements showed PVA-borax-water system had fractal dimensions D _f2.4 and D _f2.0 as temperature was below and above 40C, respectively. The simple tilting test indicated gel behaviour for the PVA-borax aqueous system at temperatures below 40C with a creep flow after a long time exposure in the gravity field. But the dynamic viscoelasticity measurements demonstrated a solution behaviour for PVA/borax/water at temperatures below 40C, the critical gel point behaviour for G() and G() was not observed in this system as those reported for chemical crosslinked gels. These results suggest that the PVA-borax aqueous system is a thermoreversible weak gel.     

Electrochemistry of anodic fluorine gas evolution at carbon electrodes: Part II studies on the ‘CF’ film by the current-interruption,AC impedance,ESCA and auger techniques

The CF films that are formed on the surface of carbon anodes used for the fluorine evolution reaction (FER) in KF·2HF melts at 358 K have been studied by bothin situ electrochemical current-interruption and a.c. impedance methods, and byex situ surface spectroscopy [ESCA (XPS) and Auger] techniques. The surface analysis measurements indicate that a thin CF (CF₂) film, 1.7 nm in thickness is formed on the carbon anodesurface. Results from depth profiling analyses of the film indicate that it is not uniform, higher levels of CF and F components being found towards the carbon anode surface. Thein situ electrochemical measurements demonstrate that an abnormally small interfacial capacitance, (1.6–2.7)×10^–7 F cm^–2, arises in the course of the FER at carbon anodes; this was attributed to the presence of a passive dielectric CF film on the carbon electrodes. The determined interfacial capacitance does not change significantly with potential in the potential range studied, which implies that the thickness of the CF film on the fluorine-evolving carbon anodes may be independent of potential.     

Sex pheromone chemistry of the western spruce budwormChoristoneura occidentalis Free

SCOT capillary Chromatographic and SCOT capillary chromatographic-mass spectrometic analyses of gland washes and effluvia of virgin femaleChoristoneura occidentalis Free, have been conducted with both a diapausing and nondiapausing strain of this insect. The following compounds were identified in gland washes and effluvia in both strains:E andZ11–14Ald,E andZ11–14Ac,E andZ11–14OH and 14Ald, 14Ac, and 14OH. The average aldehyde: acetate: alcohol ratio found by analysis of single glands by virgin females (nondiapausing strain) was 170.73. Analysis of virgin female effluvia gave this ratio as 1038 (diapausing strain: %Z=8, 11, 15, respectively) and 1036 (nondiapausing strain: %Z=8, 11, 12, respectively). The saturated components were generally 1–2% of theE isomer in each case. Comparisons of EAG responses of bothC. occidentalis andC. fumiferana toE11–14Ald,E11–14Ac andE11–14OH were made. Correlations with both laboratory and field data previously published were also made betweenC. fumiferana andC. occidentalis.Lepidoptera: Tortricidae.     

Relationship between preferential adsorption coefficient and intrinsic viscosity in ternary systems

Summary The relation proposed between the preferential adsorption coefficient, , and the intrinsic viscosity, ¦¦ ¦¦=¦¦+AK has been applied in this paper to previously published data. This equation is found to be valid in theta condi tions and far away from them. The obtained results are compared to the ones calculated with the Dondos-Benoit equation.     

Studies on electrical conductivity of gamma irradiated polyaniline

Summary de electrical conductivity at surface of -irradiated polyaniline (PAn) has been studied. EPR spectroscopic results indicate that the variation of spin concentration is consistent with the increase of _de. Electrical conductivity (_de) versus temperature (T) characteristics of unirradiated and irradiated PAn were performed, which demonstrate that the unirradiated curve can fit to ln_deT₁, while the irradiated curve fit to ln_deT_1/4.     

Electrochemical behaviour of viologen-cyclodextrin inclusion complexes. The case of non-alkyl group substituted viologen

The electrochemical behavior of non-alkyl substituted viologen, 4,4-dibenzyl bipyridinium (BzV), 4,4-dicyanophenyl bipyridinium (CyV) and -,-,-cyclodextrin (, , -CD) was studied using cyclic voltammetry and a spectroelectrochemical method. It was found that BzV and Fe(CN) ₆ ^4– formed a charge-transfer (CT) complex with a ratio of 21 and the colour of the solution faded with the addition of an electrolyte. This behaviour is the same as in then-heptyl viologen and ferrocyanide system [1]. BzV, -CD and -CD formed an inclusion complex only in the reduced state, whilst BzV and -CD formed an inclusion complex in both the oxidized and the reduced state. An EC scheme in which a chemical reaction follows an electrochemical reaction was considered to predominate in the BzV and -, -CD systems, while a CE scheme in which a chemical reaction preceded an electrochemical reaction predominated in the BzV and -CD system. On the other hand, CyV was found to form an inclusion complex with -, -, -CD in both the oxidized and the reduced states. therefore a CE scheme was considered to predominate in the CyV--, -, -CD systems.     

Synthesis of new metal-containing side-chain monomers and polymers

New metal-containing vinyl monomers, hexyl-6-oxy-{4-[4-(4-carboxy cyclopentadienyl manganese tricarbonyl phenyl)phenyl]benzoyloxy}methacrylate and hexyl-6-oxy-{4-[4-(4-ferrocenoyl phenyl)phenyl]benzoyloxy}methacrylate, and the corresponding homopolymers and random copolymers with hydroxy monomer hexyl-6-oxy-{4-[4-(4-hydroxyphenyl)phenyl]benzoyloxy}methacrylate were synthesized. The compounds were characterized by¹H NMR; their thermal behavior was investigated by means of differential scanning calorimetry. Monomers and polymers containing the ferrocene unit melt at lower temperatures than those derived from the cyclopentadienyl managanese tricarbonyl moiety. The melting temperatures of the monomers and polymers ranged from 399 to about 515 K, Both monomers and polymers failed to exhibit mesogenic behavior. Values ofM _n,M _w,M _w/M _n, and degree of polymerization were obtained by gel permeation chromatography. TheM _n ranged from 16,500 for the copolymer containing hexyl-6-oxy-{4-[4-(4-ferrocenoyl phenyl)phenyl] benzoyloxy}methacrylate and hydroxy monomer hexyl-6-oxy-{4-[4-(4-hydroxyphenyl)phenyl]benzoyloxy}methacrylate at a 1:3 ratio to 26,000 for the copolymer containing hexyl-6-oxy-{4-[4-(4-carboxy cyclopentadienyl manganese tricarbonyl phenyl)phenyl]benzoyloxy}methacrylate and hydroxy monomer hexyl-6-oxy-{4-[4-(4-hydroxyphenyl)phenyl]benzoyloxy}methacrylate at a 1:3 ratio.M _w/M _n ranged from 1.6 in the case of the copolymer containing hexyl-6-oxy-{4-[4-(4-carboxy cyclopentadienyl manganese tricarbonyl phenyl)phenyl]benzoyloxy}methacrylate and hydroxy monomer hexyl-6-oxy-{4-[4-(4-hydroxyphenyl)phenyl]benzoyloxy}methacrylate at a 1:3 ratio to 2.2 in the case of poly(hexyl-6-oxy{4-[4-(4-carboxy cyclopentadienyl manganese tricarbonyl phenyl)phenyl]benzoyloxy}methacrylate).     

Behavioral responses of maleArgyrotaenia velutinana (Lepidoptera: Tortricidae) to components of its sex pheromone

Males of the redbanded leafroller,Argyrotaenia velutinana (Walker) (Lepidoptera: Tortricidae), were studied for their behavioral responses in laboratory olfactometers and in the field to the 3 components of the female-produced sex pheromone:cis-11-tetradecenyl acetate (c11–14Ac),trans-11-tetradecenyl acetate (t11–14Ac), and dodecyl acetate (12Ac). Dodecyl acetate, when evaporated with c11–14Ac (8%trans) in the field, modified the behavior of feral males nearby the chemical source, causing an increase in the frequency of landing and close approach to the pheromone dispenser. Apparently, an inflight behavioral modification concerning landing or not landing occurs within 60 cm of the source and is mediated by 12Ac. In laboratory olfactometers, c11–14Ac (8%trans) demonstrated a lower threshold for male activation than pure c11- and t11–14Ac and blends of the two isomers. Additionally, over a wide range of dosages, males responded with optimum wing-fanning response to c11–14Ac (8%trans) compared to pure c11–14Ac, c11–14:Ac (30%trans), and pure t11–14Ac, suggesting that thecistrans ratio rather than absolute amounts of either isomer, is a crucial factor in eliciting male response. When presented with c11–14Ac (8%trans) (11), dodecyl acetate caused a significant prolongation of wing-fanning over c11–14Ac (8%trans) alone and resulted in a greater percentage of males moving upwind to the source. Since the increase in wing-fanning and orientation occurred at higher concentrations of the 3-component mixture, the effect of 12Ac in the laboratory may reflect the close-range role of 12Ac in the field.     

Catalytic oxidation of methanol to methyl formate over silver – a new purpose of a traditional catalysis system

Catalytic reaction was performed in the unregarded temperature region over silver catalysts with long catalytic lifetime for the conversion of methanol to methyl formate. O-saturated or O-saturated silver catalysts were studied individually to identify the roles of O, O in the oxidative esterification of methanol over an unsupported polycrystalline silver catalyst. A synergic process is proposed based on the coexistence of -oxygen species and -oxygen species on the surface of polycrystalline silver at about 573 K.     

Sex pheromone ofGrapholita funebrana occurrence ofZ-8- andZ-10-Tetradecenyl acetate as secondary components

Z-8-Dodecenyl acetate (Z8–12Ac),E-8-dodecenyl acetate (E8–12Ac),Z-8-tetradecenyl acetate (Z8–14Ac),Z-10-tetradecenyl acetate (Z10–14Ac), andZ-8-dodecen-1-ol (Z8–12OH) were identified in the proportions 10013052 in female sex gland extracts ofGrapholita funebrana, accompanied by saturated acetates from 12 to 20 carbons with tetradecyl acetate predominating.Z10–14Ac has not previously been described as a lepidopteran sex pheromone component. Best attraction of males is obtained withZ8–12Ac in the presence of a higher proportion ofE8–12Ac than in the female. Inclusion of the 14-carbon acetates did not augmentG. funebrana catches but inhibitedG. molesta. On the other hand, addition ofZ8–12OH at the level optimal forG. molesta reduced attraction ofG. funebrana.     

Effects of gas bubbles on the current and potential profiles within porous flow-through electrodes

This paper presents a mathematical model to calculate the distributions of currenti(x), potentialE(x), gas void fraction (x) and pore electrolyte resistivity (x) within porous flow-through electrodes producing hydrogen. It takes into consideration the following effects: (i) the kinetics of the interfacial charge transfer step, (ii) the effect of the non-uniformly generated gas bubbles on the resistivity of the gas-electrolyte dispersion within the pores of the electrode (x) and (iii) the convective transport of the electrolyte through the pores. These effects appear in the form of three dimensional groups i.e.K=i _o L where i_o is the exchange current density, is the specific surface area of the electrode andL its thickness.= ⁰ L where ⁰ is the pore electrolyte resistivity and =/Q where is a constant, =tortuosity/porosity of the porous electrode andQ is the superficial electrolyte volume flow rate within it. Two more dimensionless groups appear: i.e. the parameter of the ohmic effect =K/b and the kinetic-transport parameterI=K. The model equations were solved fori(x),E(x), (x) and (x) for various values of the above groups.Nomenclature specific surface area of the bed, area per unit volume (cm^–1) - b RT/F in volts, whereR is the gas constant,T is the absolute temperature (K) - B =[1–(I ² Z/4)], Equation 9a - C =(1–B ²), Equation 9b - E(L) potential at the exit face (V) - E(0) potential at the entry face (V) - E(x) potential at distancex within the electrode (V) - E _rev reversible potential of the electrochemical reaction (V) - F Faraday's constant, 96500 C eq^–1 - i _o exchange current density of the electrode reaction (A cm^–2 of true surface area) - i(L) current density at the exit face (A cm^–2 of geometrical cross-sectional area of the packed bed) - I K =i _oL(/Q) (dimensionless group), Equation 7d - K =i _oL, effective exchange current density of the packed bed (A cm^–2) Equation 7a - L bed thickness (cm) - q tortuosity factor (dimensionless) - Q superficial electrolyte volume flow rate (cm³ s^–1) - x =position in the electrode (cm) - Z =exp [(0)], Equation 7f - transfer coefficient, =0.5 - =K/b=(i ₀ L ⁰ L)/b (dimensionless group) Equation 7e - (x) gas void fraction atx (dimensionless) - = ⁰ L, effective resistivity of the bubble-free pore electrolyte for the entire thickness of the electrode ( cm²) - (0) polarization at the entry face (V) - (L) polarization at the exit face (V) - =q/, labyrinth factor - constant (cm³ C^–1), Equation 3a - =/Q (A ^–1) conversion factor, Equation 3b - porosity of the bed - (x) effective resistivity of the gas-electrolyte dispersion within the pores ( cm) - ⁰ effective resistivity of the bubble-free pore electrolyte ( cm)     

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.     

Calorimetric,X-ray and infra-red investigations on poly(hexamethylene adipamide)

Summary In dependence on crystallization conditions three ranges with different crystal structure and heat of fusion were found by DSC,WAXS,and IR for unoriented PA 6.6 samples of densities between 1.10 and 1.17gcm^–3: Range I:_I triclinic, _c ^I =1.225 gcm^–3,H _M ^I = 235 Jg^–1. Range II:_II triclinic, _c ^II =1.165 gcm^–3, H _M ^II =185 Jg^–1. Range III:Continuous variation from _c ^I ,H _M ^I to _c ^II , H _M ^II . _a=1.095 gcm^–3 is independent of crystallization. conditions. The transition between _I and _II is probably due to changes of the chain conformation.     

Studies concerning charged nickel hydroxide electrodes I. Measurement of reversible potentials

Reversible potentials (E _R) have been measured for nickel hydroxide/oxyhydroxide couples over a range of KOH concentrations from 0·01–10 M. It is shown that the couples derived from the parent- and-Ni(OH)₂ systems can be distinguished by the relative change in KOH level on oxidation and reduction. In the case of couples derived from the-class of materials a dependence of 0·470 moles of KOH per 2e change is found compared with 0·102 moles of KOH per 2e change for the-class of materials. Couples derived from the- and-Ni(OH)₂ systems can be encountered in a series of activated and de-activated forms having a range of formal potentialsE ₀ . Activated. and de-activated-Ni(OH)₂/-NiOOH couples are found to lie in the range 0·443–0·470 V whilst-Ni(OH)₂/-NiOOH couples lie in the range 0·392–0·440 V w.r.t. Hg/HgO/KOH. It is demonstrated for de-activated,-Ni(OH)₂/-NiOOH couples thatE _R is independent of the degree of oxidation of the nickel cation between states of charge of 25% and 70%. SimilarlyE _R is constant for states of charge between 12% and 60% for activated-Ni(OH)₂/-NiOOH couples. The constant potential regions are considered to be derived from heterogeneous equilibria between pairs of co-existing phases both containing nickel in upper and lower states of oxidation. Differences inE ₀ between the activated and de-activated couples are considered to be related to the degree of order/disorder in the crystal lattice.     

Overall mass transfer in swirling decaying flow in annular electrochemical cells

Mass transfer coefficients between an electrolyte solution and the inner cylinder of an annulus were determined experimentally, using the electrochemical technique, for both laminar and turbulent swirling flows of a liquid induced by means of a tangential inlet in the annular gap. The average mass transfer coefficients were determined as a function of the axial distance from the entrance, for various diameters of the inlet duct and thicknesses of the annular space, for a Reynolds number range of 100 to 5900. Enhancement of mass transfer up to 400% was achieved in comparison to that obtained in fully developed axial flow. Correlations of the experimental data, taking into account the geometrical and hydrodynamic parameters influencing the overall mass transfer, are presented.Nomenclature A Cathode surface area - C Potassium ferricyanide concentration - D Ferricyanide ion diffusion coefficient - d Tube diameter - e=R ₂–R₁ Thickness of the annular gap - ERR Mean square error between experimental and calculated data - F Faraday's constant - f(N) Function of the geometrical parameters - h Local heat transfer coefficient - l ₁ Limiting diffusional current - k Mass transfer coefficient - L,L ₁,L ₂ Axial distances from the inlet - L/2e Reduced axial coordinate - N=R ₁ /R ₂ Radii ratio of the annular gap - n Number of electrons involved in the electrochemical reaction - Nu _x =hx/ Local Nusselt number - Q Volumic flow rate - R ₁ External radius of the inner cylinder - R ₂ Internal radius of the outer cylinder - Re=2eU/ Reynolds number - Re _x =Ux/ Local Reynolds number - S ₀=U /U Initial swirl intensity - Sc=/D Schmidt number - Sh=2ek/D Sherwood number obtained in swirling flow - Sh_a=2ek/D Sherwood number obtained in fully developed axial flow - Sh _x Local Sherwood number - U Mean axial velocity in the annular gap - U Axial velocity in the inlet duct - x Axial coordinate Greek letters , , , , Correlation parameters - Diameter of the tangential inlet - Thermal conductivity - Kinematic viscosity of the electrolyte - Density of the working solution     

A four-component pheromone blend for optimum attraction of redbacked cutworm males,Euxoa ochrogaster (Guenée)

Four acetates,Z-5-decenyl acetate,Z-5-,Z-7-, andZ-9-dodecenyl acetates, in microgram ratios of 120021 or 120062 were excellent, specific sex pheromone blends for capturing male redbacked cutworm moths in cone traps. Blends in ratios of 120021 and 220021 at 1000 g/ rubber septum dispenser remained highly effective for 6 weeks under field conditions. The essential minor components,Z-5-decenyl,Z-7-, andZ-9-dodecenyl acetates, became inhibitory at concentrations of about 10% in the blends, and this may be an important general phenomenon in lepidopteran pheromones. Blends involving a parapheromone,Z-5-undecenyl acetate, withZ-5-,Z-7-, andZ-9-dodecenyl acetate, in microgram ratios of 820021 or 2020062 were also excellent specific attractants for this species. TheZ-8-dodecenyl acetate had no obvious effect on the attraction of the redbacked cutworm males.     

The impedance of the alkaline zinc-mercuric oxide cell. I. Cell behaviour and interpretation of impedance spectra

The impedances of small (2400 mA h) alkaline Zn-HgO cells have been measured in the range 10 kHz-0.001 Hz at various states of charge from fully charged to fully discharged. The behaviour of the cell conforms to that expected for rate control by charge transfer at the zinc electrode and diffusion in solution. At low frequencies there is a relaxation in the diffusive circuit elements which ultimately results in a complete suppression of the capacitative component of the impedance at zero frequency. The low-frequency behaviour is analogous to convective diffusion and is due to the effective distance between the electrodes being small compared with the characteristic length (D/)^1/2. The magnitude of the charge transfer resistance is the best measure of the state of charge.Nomenclature a effective electrode separation - C _DL double-layer capacitance of cell - C _R capacitative component of cell impedance - C concentration difference - D percentage discharge in Equation 12 - D _i diffusion coefficient of speciesi - R ohmic resistance of cell - R _R resistive component of cell Faradaic impedance - Ui constant defined by Equation 10 - Z total cell impedance - Z _F cell Faradaic impedance - Z _F cell impedance modified for porosity effect - Z _x cell impedance of Faradaic component plus double layer - cell Warburg coefficient (slope ofR _R and 1/C _Rversus su}-1/2) - _C Warburg coefficient calculated fromC _r values - _i cell Warburg coefficient for speciesi - Warburg coefficient calculated fromR _R values - dihedral angle of tail of Sluyters plot (after coming-off high-frequency semicircle) - angular frequency     

Interaction of methane with surfaces of silica,aluminas and HZSM-5 zeolite. A comparative FT-IR study

Infrared investigations on the interaction of methane with silica, aluminas (, and ) and HZSM-5 zeolite have been carried out. At low temperature (173 K), methane adsorption was observed over these oxides and HZSM-5 zeolite. Our findings featured that the infrared inactive ₁ band (2917 cm^–1) of a gaseous methane molecule became active and shifted to lower frequencies (2900 and 2890 cm^–1) when it adsorbed on the surfaces of these adsorbents. Our results also demonstrate that hydroxyl groups played a very important role in methane adsorption over the acidic oxides and the HZSM-5 zeolite. When interaction between the hydroxyl groups and methane took place, the band shift of the hydroxyl groups varied with different oxides. The strength of the interaction decreased according to the following sequence, Si-OH-Al>Al-OH>Si-OH, which is in accordance with the order of their acidities. At higher temperatures, methane interacted quite differently with various oxides and HZSM-5 zeolite. It has been observed that the hydroxyl groups of silica, -alumina and HZSM-5 zeolite could exchange with CD₄ at temperatures higher than 773K, while those on -alumina could exchange at a temperature as low as 573 K. Another interesting observation was the formation of formate species over Al₂O₃ (both and ) at temperatures higher than 473 K. The formate species would decompose to CO₂, or produce carbonate at much higher temperatures. Formation of formate species was not observed over silica and HZSM-5 under similar conditions, -Al₂O₃ did not adsorb or react with methane in any case.