Positive polyacetylene electrodes in aqueous electrolytes

Polyacetylene films, contacted with platinum mesh, have been polarized anodically in aqueous H₂SO₄, HClO₄, HBF₄ and H₂F₂ of medium concentrations (30–70 wt%). Two oxidation peaks are observed, the equivalents of which are 1 $${\text{(1) 0}}{\text{.045 F mol}}^{ - {\text{1}}} {\text{ CH (2) 0}}{\text{.23 F mol}}^{ - {\text{1}}} {\text{ CH}}$$ The potential of the Process 1 decreases linearly with increasing acid concentration by 20–40 mV mol^?1 dm^?3, while the potential of Peak 2 exhibits normal Nernst behaviour (about + 60 mV decade^?1. Process 1 is partially reversible, while Process 2 is totally irreversible. From these findings for Process 1 we conclude the reversible insertion of anions into the polyacetylene host lattice, which is primarily oxidized to the polyradical cation, with the co-insertion of acid molecules HA to yield the insertion compound [(CH)⁺·yA^?·vyHA] _x y?4.5% andv=1.5 for H₂SO₄ and HClO₄. In the course of Process 2, the polymer is irreversibly oxidized according to $$( - ^ \cdot {\text{CH}} \cdot \cdot \cdot \cdot \cdot \cdot \cdot \cdot ^ \oplus {\text{ CH}} - )_{x/2} + 2{\text{H}}_{\text{2}} {\text{O}} \to ( - \mathop {\text{C}}\limits_{\mathop \parallel \limits_{\text{O}} } \cdot \cdot \cdot \cdot \cdot \cdot \cdot \cdot \mathop {\text{C}}\limits_{\mathop \parallel \limits_{\text{O}} } - )_{x/2} + 6{\text{H}}^{\text{ + }} + 5e^ - $$ As this process occurs to some extent even in the potential region of Process 1, a continuous degradation of the host lattice occurs upon cycling.     

Solid state ionics—the electrochemical analog memory cell with solid electrolyte

A new type analog memory cell with variable output voltage has been proposed and its performance examined. The cell construction is $$\begin{gathered} {\text{Ag|RbAg}}_{\text{4}} {\text{I}}_{\text{5}} {\text{|(Ag}}_{\text{2}} {\text{Se)}}_{{\text{0}} \cdot {\text{925}}} {\text{(Ag}}_{\text{3}} {\text{PO}}_{\text{4}} {\text{)}}_{{\text{0}} \cdot {\text{075}}} {\text{|RbAg}}_{\text{4}} {\text{I}}_{\text{5}} {\text{|Ag}} \hfill \\ {\text{ }} \uparrow \hfill \\ {\text{ Pt}} \hfill \\ \end{gathered} $$ in which (Ag₂Se)_0.925(Ag₃PO₄)_0.075 is a mixed conductor exhibiting high ionic and electronic conductivity at room temperature. The potential difference between the silver electrode and the platinum electrode depends on the silver activity in the mixed conductor, and it is changed by passing the current between one silver electrode and the platinum electrode. The output voltage of the cell is changed in the range of 150 to 0 mV. At open circuit, the memorized cell voltage decreased by only 1% over several hours.     

Determination of equilibrium silver sulphate concentration in the system Cu-H2SO4-CuSO4-H2O-Ag2SO4-Ag as a function of composition

The value of the ratio \(\gamma _{{\text{Cu}}^{{\text{2 + }}} } /\gamma _{{\text{Ag}}^{\text{ + }} }^2 \) ( \(\gamma _{{\text{Cu}}^{{\text{2 + }}} } ,\gamma _{{\text{Ag}}^{\text{ + }} } \) -are the mean activity coefficients of copper and silver ions, respectively) was calculated from the measured emf of the cell $${\text{Cu(Hg)|H}}_{\text{2}} {\text{SO}}_{\text{4}} {\text{ (}}c_{\text{x}} {\text{)}} - {\text{CuSO}}_{\text{4}} {\text{ (}}c_{\text{y}} {\text{)|Hg}}_{\text{2}} {\text{SO}}_{\text{4}} {\text{, Hg}}$$ and the solubility of Ag₂SO₄ in H₂SO₄ (c _x) and CuSO₄ (c _y) solutions. The concentration of H₂SO₄ in the solution was varied from 0.5 to 2.1 mol dm^?3 that of CuSO₄ from 0.4 mol dm^?3 to saturation. The results were presented as a function: $$\frac{{\gamma _{{\text{Cu}}^{{\text{2 + }}} } }}{{\gamma _{{\text{Ag}}^{\text{ + }} }^2 }} = a_0 + a_1 c_{\text{x}} + a_2 c_{\text{y}} + a_3 c_{\text{x}}^{\text{2}} + a_4 c_{\text{x}} c_{\text{y}} + a_5 c_{\text{y}}^2 .$$ This function allows the estimation of the equilibrium silver ion concentration \(c_{{\text{Ag}}^{\text{ + }} }^{{\text{eq}}} \) in solutions containing both H₂SO₄ and CuSO₄ in the presence of metallic copper. The function is also very useful for the estimation of the \(c_{{\text{Ag}}^{\text{ + }} }^{{\text{eq}}} \) near a working copper electrode.     

The mechanism of manganese electrodeposition

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

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

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

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

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

Packed-bed reactor with continuous recirculation of electrolyte

A comparison of calculated and experimental parameters for the packed-bed reactor working with recirculation of the electrolyte is given. A simple mathematical model was applied and the applicability of the relation $$c = c^0 {\text{ exp(}} - k_1 At/V{\text{) for }}V_c \ll V_R $$ was tested. For the investigated reactor a dimensionless relation has been established from experimentalI-E curves for the single pass mode $$(Sh) = 0 \cdot 5(Re)^{0 \cdot 7} (Sc)^{0 \cdot 33} .$$ For pure practical engineering requirements these two equations together give us a satisfactory way of predicting the concentration-time dependence.     

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

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

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

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

Electrochemical behaviour of CuO-TiO2 catalysts

In order to provide further information on the properties of CuO?TiO₂ catalysts, we have investigated their electrochemical behaviour in 1 M LiClO₄-propylene carbonate electrolyte. It appears that TiO₂ is electrochemically reducible at 1.8 V at room temperature, with a faradaic yield of 0.3–0.4 F per mole of TiO₂ with formation of a TiO₂Li_x phase according to the reaction: $$TiO_2 + xe + xLi^ + \leftrightharpoons TiO_2 Li_x $$ The electrochemical study suggests that TiO₂ enhances Cu(II) electroreduction in titania-supported copper catalysts. This electroreduction of Cu(II) occurs either at 2.2 V according to the path: $$Cu(II) + 2e \xrightarrow{{TiO_{2 } support}} Cu(O), TiO_2 $$ or at 1.8 V through an internal electron transfer between TiO₂Li_x and Cu(II) according to the successive reactions: $$\begin{gathered} TiO_2 + xe + xLi^ + \leftrightharpoons TiO_2 Li_x \hfill \\ Cu(II) \xrightarrow{{TiO_{2 } Li_x }} Cu(O), TiO_2 \hfill \\ \end{gathered} $$ This study shows that electrochemistry may be a novel way of determining and controlling the redox states of metal-supported catalysis.     

Studies concerning charged nickel hydroxide electrodes. VII. Influence of alkali concentration on anodic peak positions

After repetitive potential cycling employing a high positive potential limit (>700 mV wrt Hg/HgO/ KOH) three anodic and one cathodic peak can be observed using aβ-Ni(OH)₂ starting material. Anodic peaks found at 425, 470 and 555 mV in 5 mol dm^?3 KOH shift to less positive potentials as the alkali concentration is increased appearing at 365, 410 and 455 mV respectively in 12.5 mol dm^?3 KOH. Four anodic processes involving various pairs of coexisting phases within both theβ andα-/γ-phase system can be identified as summarized below in order of increasing positive potential: Peak A $$\begin{gathered} Peak A{\text{ }}U_\alpha ^A \to {\text{ }}V_\gamma ^A \hfill \\ Peak B{\text{ }}U_\beta ^B \to {\text{ }}V_\beta ^B \hfill \\ {\text{ }}\mathop C\limits^ + {\text{ }}U_\alpha ^C \to {\text{ }}V_\gamma ^C \hfill \\ Peak E{\text{ }}V_\beta ^B \to {\text{ }}V_\gamma ^E \hfill \\ \end{gathered} $$ Observed shifts in anodic and cathodic peak potentials are consistent with the known influence of alkali and water activity on the reversible potentials for the above processes.     

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

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

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

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

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

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

Behaviour of nitrate impurity in nickelcadmium cells

The oxidation-reduction behaviour of NO₃ ^?, NO₂ ^?, N₂O₂ ^2?, NH₂OH and NH₃ at a platinum electrode in alkaline solution has been investigated using cyclic voltammetry. The results have been compared with the corresponding behaviour of these species at charged, porous cadmium and nickel hydroxide electrodes in order to understand the likely behaviour of NO₃ ^? impurities in nickelcadmium cells. The reactions are shown to be irreversible processes and strongly dependent on the nature of the electrode surfaces. The reactions which are likely to be involved in a charged cell can be represented by the overall scheme: $${\text{NO}}_{\text{3}} ^\_ {\text{NO}}_{\text{2}} ^\_ {\text{NH}}_{\text{3}} \xrightarrow{{{\text{slow}}}}{\text{N}}_2 $$ It is suggested that the self-discharge of cells containing NO₃ ^? is limited by slow kinetic effects rather than by diffusion as previously supposed.     

The effect of position of ester group on critical micelle concentration of ester-linked sulfonates

The critical micelle concentration (CMC) of sodium alkyl sulfoacetates and β-sulfopropionates, and sodium salt of 2-sulfo ethyl ester, 3-sulfo propyl ester and 4-sulfo butyl ester of fatty acids have been determined by the electrical conductance of each aqueous solution. The relation between CMC value and number of total methylene groups (N) for the C_n ^*H_2n ^*+₁COO(CH₂)₃ SO₃Na and C₉H₁₉COO(CH₂)_n ^**SO₃Na (n^*=9, 10 and 11. n^**=2, 3 and 4) can be formulated as follows. $$\begin{gathered} \log {\text{CMC = - 0}}{\text{.293N + 1}}{\text{.778}} \hfill \\ {\text{for C}}_{\text{n}} *{\text{H}}_{{\text{2n}}} *_{ + ^1 } {\text{COO (CH2) 3SO3Na}} \hfill \\ {\text{log CMC = - 0}}{\text{.147 N + 0}}{\text{.011}} \hfill \\ {\text{for C9H19 COO (CH2) n **SO3Na}} \hfill \\ \end{gathered} $$ From these equations it was determined that the methylene unit situated between ester and sulfonate groups is equivalent to 0.5 methylene groups in its effect on CMC. For a given number of carbon atoms in the alkyl chain, the log CMC value increased regularly with a change in the ester group away from the terminal position to more central positions in the hydrocabon chain. The two different types of ester-linkages (RCOO-and ROCO-) have no apparent effect on the CMC value.     

Mass transfer in electrolytic cells with gas stirring

Mass transfer to wall electrodes was investigated in a circular cell agitated by gas bubbles. Perforated and porous plates were used as gas spargers. Electrodes with varying height and electrolytic solutions having different physical properties were tested. It was found that the enhancing effect of gas bubbles on the mass transfer coefficient is a function of the gas hold-up, irrespective of the velocity of the gas flow and the gas distributor employed. The results were correlated for short mass transfer lengths by the relationship $$Sh = 0.231(ScGa)^{\frac{1}{3}} (L/D_c )^{--0.194 _\varepsilon 0.246}$$ and for fully developed mass transfer by $$Sh_\infty = 0.256(ScGa)^{\frac{1}{3}} \varepsilon ^{0.254}$$      

Mécanismes de la réduction electrochimique en milieu non aqueux de materiaux cathodiques utilisés dans les piles au lithium. II. Mécanisme de la réduction electrochimique du chromate d'argent dans le mélange carbonate de propylene-1,2-dimethoxyethane

On the basis of cyclic voltammetric scans of Ag₂CrO₄ membrane electrodes in a mixture of propylene carbonate and 1,2-dimethoxyethane in 1 M LiClO₄, evidence is cited for the formation of an electrooxidizable species after the partial or total reduction of Ag(I) in Ag₂CrO₄. This species can be oxidized more easily than silver in the presence of Li₂CrO₄ and is only stable, with time, when Ag(I) from Ag₂CrO₄ has been completely reduced to Ag(0). We have assumed that this species, produced by the reduction of Ag₂CrO₄, was of chromium with oxidation state + V. According to this hypothesis, the mechanism of the reduction of Ag₂CrO₄ with Ag(0) and Li₂CrO₄ would be the superposition of two steps: electrochemical formation of Cr(V) and reaction of Cr(V) with Ag(I). At high discharge rates, the overall rate of reduction of Ag₂CrO₄ is limited by the rate of reaction between Ag(I) and Cr(V), thus involving a loss of energy corresponding to 0.4 V with respect to the standard potential of the system $${\text{Li}}_{\text{2}} {\text{CrO}}_{{\text{4}}_{{\text{(s)}}} } ,{\text{ Ag}}_{{\text{(s)}}} /{\text{Ag}}_{\text{2}} {\text{CrO}}_{{\text{4}}_{{\text{(s)}}} } /{\text{LiClO}}_{\text{4}} {\text{ 1 M}}{\text{.}}$$ The results obtained account for the good functioning of Ag₂CrO₄ electrodes in batteries.     

Autoxidation of polyunsaturated fatty compounds in mackerel oil: Formation of 2,4,7-decatrienals

The formation of potentially “fishy” off flavor components, especially 2,4,7-decatrienals, in various rancid mackerel oils has been semiquantitatively investigated using preparative thin layer chromatography (TLC) and gas liquid chromatography (GLC) methods. A combination of 2 GLC analyses can be directly employed for free aldehyde analysis. This GLC method is faster and gives a better recovery than the alternative TLC proceeding through the dinitrophenylhydrazone derivatives of the carbonyl compounds. Kinetic relations between decatrienal formation and the degree of autoxidation of polyenoic fatty compounds present in mackerel oil are discussed. The decreases in major polyenoic fatty acids rancid oils, measured by the ratios 1 $$\frac{{18:4\omega 3 + 20:5\omega 3 + 22:6\omega 3}}{{14:0 + 16:0 + 18:0}}$$ or 1 $$\frac{{total polyenoic acid}}{{14:0 + 16:0 + 18:0}}$$ can be related to the formation of 2,4,7-decatrienals and other unsaturated aldehydes.     

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

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