Electrochemical studies of the reaction between titanium metal and titanium ions in the KCl-NaCl molten salt system at 973 K

The reaction between titanium metal and titanium ions in the KCl?NaCl molten salt system was investigated by means of electrochemical and physical methods at 973 K in an inert gas atmosphere (argon). It was found that the reaction between titanium metal and Ti³⁺ in the molten salts with TiCl₃ followed a simple reaction (I). However, in the case of the concentration of K₂ TiF₆ being higher than 2.7 mol % the reaction was (II); in the case of it being less than 0.8 mol %, reactions (III) and (III′) were followed. $$\begin{gathered} 2Ti^{3 + } + Ti = 3Ti^{2 + } (I) \hfill \\ 3Ti^{4 + } + Ti = 4Ti^{3 + } (II) \hfill \\ Ti^{4 + } + Ti = 2Ti^{2 + } (III) \hfill \\ 3Ti^{2 + } = Ti + 2Ti^{3 + } (III')(on cooling) \hfill \\ \end{gathered} $$ It was also found that these reactions were controlled by charge transfer and diffusion simultaneously.     

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.     

The thermoelectric power in Bi2O3

The thermo electric power, ΔE/ΔT, of the cell $$\begin{gathered} O_2 + N_{2, } Pt/Bi_2 O_3 (\delta phase)/Pt, O_2 + N_2 \hfill \\ (T + \Delta T) (T) \hfill \\ \end{gathered}$$ has been measured as a function of oxygen pressure (10^?4 atm ? p(O₂) ? 1 atm) in the temperature range 650–800° C. The experimental result can be described by: $$[ \in ({\rm O}_2 /{\rm O}^{2 - } ) - \in (e, Pt)] = [45.6 \pm 5.6 log p(O_2 ) - 261](\mu VK^{ - 1} )$$ within experimental error, where ε(O₂/O²), the Seebeck coefficient ofδ-Bi₂O₃, stands for \(\mathop {\lim }\limits_{\Delta T \to 0} \Delta E/\Delta T\) The change of ΔE/ΔT with oxygen pressure corresponds to the change of the partial molar entropy of O₂. The heat of transport of O^2? ions is calculated to be 0.13 eV ± 0.01 whereas the activation enthalpy for ionic conduction is 0.30 eV. From this discrepancy it is concluded that the free ion model of Rice and Roth cannot be applied, while the extended lattice gas model of Girvin might explain the results when strong polaron coupling is assumed.     

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.     

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.     

Experimental determination of the factors affecting zinc electrowinning efficiency

A series of experiments were conducted to investigate the factors affecting the efficiency of zinc electrowinning. The experiments were conducted in 10-1 cells using a high purity industrial zinc sulphate solution. The lowest specific energy consumption achieved in the cells was 2637 kWh t^?1 Zn under the following conditions: $$\begin{gathered} 70 g1^{ - 1} Zn in cell solution \hfill \\ 180 g1^{ - 1} H_2 SO_4 in cell solution \hfill \\ 45^\circ C cell temperature \hfill \\ 400A m^{ - 2} current density \hfill \\ \end{gathered} $$ Further energy savings can be achieved by reducing the current density but this would also reduce the cellroom production capacity. Increasing the electrolyte temperature to 50° C also reduced the energy consumption, however additives capable of controlling deposit morphology at these high temperatures were required. The effects of zinc concentration, acid concentration, deposition time and additive levels are also reported.     

Characteristic velocity and mass transfer in rotating impeller column

The effects of system variables on flow characteristics and mass transfer rate were studied in a rotating impeller column using a ternary system of water (continuous phase)-acetone (solute)-cyclohexane (dispersed phase). The characteristic velocity, Peclet numbers in both phases and mass transfer coefficient between phases were correlated as; $$\begin{gathered} \bar U_o = 6.3(10^2 )(Nd_I )^{ - 2.1} Z_C^{0.83} \hfill \\ \frac{{\bar U_C L}}{{D_C }} = 1.26N^{ - 1.11} d_I ^{ - 2.17} Z_C^{0.59} \bar F_C^{1.9} \hfill \\ \frac{{\bar U_d L}}{{D_d }} = 20.5N^{ - 0.78} d_I ^{ - 1.36} Z_C^{0.25} \bar F_C^{0.09} \hfill \\ \frac{{k_{OC} aL}}{{\bar U_d }} = 13.2N^{ - 1.33} d_I ^{0.74} Z_C^{0.93} \bar F_C^{0.78} \hfill \\ \end{gathered} $$      

Electrochemical study of aluminium ion reduction in acidic AlCl3-n-butyl-pyridinium chloride melts

Electrochemical reduction of AlCl₃ dissolved in acidic AlCl₃-n-butyl-pyridinium chloride melt was studied by linear sweep voltammetry and chronopotentiometry at tungsten and platinum electrodes, in the Al₂Cl ₇ ^? concentration range 0.3 to 0.5 M between 30 and 60°C. Al₂Cl ₇ ^? bulk reduction was preceded by a nucleation (tungsten) or alloy formation phenomenon (platinum). The overall results agree rather well with the mechanism: $$\begin{gathered} 2AlCl_4^ - \rightleftarrows Al_2 Cl_7^ - + Cl^ - \hfill \\ 4Al_2 Cl_7^ - + 3e \rightleftarrows Al + 7AlCl_4^ - \hfill \\ \end{gathered} $$ The electrochemical reaction appeared quasi-reversible. Calculated values of the product of the transfer coefficient by the number of the electron exchanged in the rate determining step were in the range 0.45 to 0.7. Diffusion coefficients for Al₂Cl ₇ ^? were calculated.     

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.     

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.     

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.     

Comparative e.m.f. study of CaF2 and β-alumina cells with Ni/NiF2 and Fe/FeF2 or Cr/CrF2 electrodes

The reliability of employing beta-alumina as electrolyte for fluorine potential measurement is examined by measuring the e.m.f.s of the galvanic cells with metal/metal fluoride electrodes and comparing with those obtained by using CaF₂ as electrolyte under identical conditions. The results from both types of galvanic cell can be superimposed to give the following standard Gibbs energy of formation, ΔG _f ⁰ , of FeF₂ and CrF₂ over extended ranges of temperature: $$\begin{gathered} \Delta G_f^0 (FeF_2 ) = - 702.0 + 0.125 20T (K) ( \pm 0.70) kJ mol^{ - 1} (506 - 1063K) \hfill \\ \Delta G_f^0 (CrF_2 ) = - 732.8 + 0.087 90T (K) ( \pm 0.64) kJ mol^{ - 1} (497 - 1063K) \hfill \\ \end{gathered} $$ The absence of significant temperature-dependent errors in both these measurements are verified by a third law treatment of the data yielding values of ?716.8 and ?777.4 kJ mol^?1 for ΔH _f.298 ⁰ of FeF₂ and CrF₂, respectively. The feasibility of using beta-alumina electrolyte cells for e.m.f. measurements on other metal/metal fluoride systems is discussed in the light of the existence of a useful potential domain of beta-alumina. High sodium potential in the electrode system can lead to sodium depletion. Likewise, low sodium potential may result in oxidation of the metals in the electrodes. Both these limiting factors are also examined.     

The corrosion of copper in ethylene glycol-water mixtures containing chloride ions

The anodic oxidation of copper at 25°C in 50% (w/w) ethylene glycol-water and in aqueous solutions has been studied by linear sweep voltammetry. The effect of chloride concentration at pH 0 and 3 has been explored. The results in both solvents follow a similar pattern. At pH 0 and in the absence of chloride, only one anodic peak is observed corresponding to the dissolution of copper metal as copper(II) ions. At intermediate chloride concentrations (0.01–0.03 M), two additional peaks are detected which have been attributed to the following reactions: $$\begin{gathered} Cu + Cl^ - \to CuCl + e^ - \hfill \\ CuCl \to Cu^{2 + } + Cl^ - + e^ - \hfill \\ \end{gathered} $$ When the chloride concentration is increased further, the three peaks gradually collapse back into one, corresponding to the dissolution of copper as a copper(I) chloro-complex. An additional peak appears at pH 3 which has been ascribed to the formation of copper(I) oxide. The results have been interpreted usingE-pCl diagrams determined for the copper-chloride system in both 50% ethylene glycol-water and aqueous solutions. Further information has been obtained from rotating disc measurements and from microscopy. The relevance of these results to corrosion in automotive cooling systems is discussed.     

Thermodynamic Properties of Sulfobetaine-Type Surfactants

Sulfobetaine-type surfactants containing a hydroxy group were synthesized by the reaction of long chain monoalkyl dimethyl tertiary amine with 3-chloro-2-hydroxypropanesulfonic acid sodium salt. The structures were characterized by ¹H NMR and ESI-MS. Their critical micelle concentrations (CMC) in aqueous solution were determined by the plate method in the temperature rang from 298.15 to 328.15 K. The thermodynamic parameters of micellization ( $\Delta G_{\text{mic}}^{\theta}$ , $\Delta H_{\text{mic}}^{\theta}$ and $\Delta S_{\text{mic}}^{\theta}$ ) and surface adsorption ( $\Delta G_{\text{ad}}^{\theta}$ , $\Delta H_{\text{ad}}^{\theta}$ and $\Delta S_{\text{ad}}^{\theta}$ ) were calculated from CMC data. The results showed that the micellization and surface adsorption of these surfactants in aqueous solution was a spontaneous and entropy-driven process. The micellization and surface adsorption became easier when the alkyl chain length increased from 12 carbon atoms to 14. The enthalpy–entropy compensation of micellization and adsorption was investigated. The compensation temperature were found to be (311 ± 2) K for both micellization and adsorption. The $\Delta H_{\text{mic}}^{*}$ and $\Delta H_{\text{ad}}^{*}$ decreased, but the $\Delta S_{\text{mic}}^{*}$ and $\Delta S_{\text{ad}}^{*}$ increased with increasing the hydrophobic chain length from 12 to 14.     

Calciumβ″-alumina and Nasicon electrolytes in galvanic cells with solid reference electrodes for detection of sulphur oxides in gases

Calcium-β″-alumina and Nasicon were applied as solid electrolytes for SO _x (x=2 or 3) gas detection. The following two galvanic cells with solid reference electrodes were assembled $$\begin{gathered} Pt|O_2 ,CaO||Ca - \beta '' - Al_2 O_3 ||CaSO_4 |SO_3 ,SO_2 ,O_2 |Pt \hfill \\ Pt|O_2 ,Na_2 O||Nasicon||Na_2 SO_4 |SO_3 ,SO_2 ,O_2 |Pt \hfill \\ \end{gathered} $$ Calcium and sodium sulphates were used as auxiliary electrolytes to provide protection of β″-Al₂O₃ or Nasicon electrolytes from chemical reaction with SO₂. The e.m.f. was measured in the temperature range 850–1070 K for five various test gases. The measured e.m.f.s had values a little lower than the calculated ones. The results show clearly that both the cells can act as SO _x electrochemical sensors for temperatures not exceeding 1070 K.     

Mass transfer characteristics of electrochemical reactors employing gas evolving mesh electrodes

Mass transfer rates were measured at a single screen and a fixed bed of closely packed screens for the simultaneous cathodic reduction of K₃Fe(CN)₆ and anodic oxidation of K₄Fe(CN)₆ in alkaline solution with H₂ and O₂ evolution, respectively. Variables studied were gas discharge rate, number of screens per bed and position of the electrode (vertical and horizontal). For single screen electrodes, the mass transfer coefficient was related to the gas discharge rate by the equations: $$\begin{gathered} K = aV^{0.190} , for H_2 evolving electrodes, \hfill \\ K = aV^{0.469} , for O_2 evolving electrodes \hfill \\ \end{gathered} $$ . Electrode position was found to have no effect on the rate of mass transfer for single and multiscreen electrodes in the case of H₂ and O₂ evolution. Mass transfer coefficients were found to increase with an increasing number of screens per bed in the case of H₂ evolution, while in the case of O₂ evolution the mass transfer coefficient decreased with an increasing number of screens per bed. A mathematical model was formulated to account for the behaviour of the H₂ evolving electrode which, unlike the O₂ evolving electrode, did not obey the penetration model. Power consumption calculations have shown that the beneficial effect of mass transfer enhancement is outweighed by the increase in the voltage drop due to gas evolution in the bed electrode.     

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.     

Electrochemical preparation of cuprous oxide powder: Part I. Basic electrochemistry

The preferred process for the production of cuprous oxide powder is via the anodic dissolution of copper in alkaline solution of sodium chloride. The principal reactions are as follows: $$\begin{gathered} Cu + nCl^ - = CuCl_n^{1 - n} (n = 2, 3) \hfill \\ 2H_2 O + 2e = H_2 \uparrow + 2OH^ - \hfill \\ 2CuCl_n^{1 - n} + 2OH^ - = Cu_2 O \downarrow + 2nCl^ - + H_2 O \hfill \\ \end{gathered} $$ In the present investigation the basic electrode processes were studied systematically under a broad range of conditions using linear sweep voltammetry. Variables studied include the concentration of sodium chloride and sodium hydroxide (i.e., alkalinity), temperature of the solution, two categories of additives (an inhibitor for preventing the deposition of spongy metallic copper powder on the cathodes, and a chemical reducing agent for reducing the cupric ions to the cuprous state), and the effect of carbonate ions (resulting from the spontaneous absorption of carbon dioxide from the air by sodium hydroxide). Useful guidelines concerning the electrolysis conditions, additives, and the concentration limit of carbonate ions have been established. The proper operating conditions can be considered to be as follows: 80–85°C, NaCl 240–260 gl^?1, NaOH below 1 gl^?1. Conditions pertaining to the use of additives are the following: calcium gluconate 0–5 gl^?1, Na₂CrO₄ below 0.5 gl^?1, Na₂Cr₂O₇ below 0.25 gl^?1, NH₂OH·HCl below 2.5 gl^?1, N₂H₄·H₂O below 2.5 gl^?1, sucrose 0–5 gl^?1. Special attention must be given to eliminate or reduce the presence of carbonate ions in the electrolyte below 0.25 gl^?1 Na₂CO₃.     

Mass transfer in annular electrolytic cells with gas stirring

Mass transfer towards the inner electrode and the wall electrode was studied in an annular cell stirred with an inert gas bubble flow. Experimental data obtained for the wall electrode follow the relationship found previously for circular cells; namely $$Sh = 0.231(ScGa)^{1/3} (L/D_e )^{ - 0.194_\varepsilon0.246}$$ Study of the influence of gas hold-up on the mass transfer rate towards the inner wall electrode has yielded the following relationship: $$Sh_\infty= 0.315(ScGa)^{1/3_\varepsilon0.231}$$      

Mass transfer characteristics of gas-sparged fixed-bed electrodes composed of stacks of vertical screens

Mass transfer rates at a gas-sparged fixed-bed electrode made of stacks of vertical screens were studied by measuring the limiting current for the cathodic reduction of potassium ferricyanide. Variables studied were air flow rate, physical properties of the solution and bed thickness. The mass transfer coefficient was found to increase with increasing air flow rate up to a certain point and then remain almost constant with further increase in air flow rate. Increasing bed thickness was found to decrease the mass transfer coefficient. Mass transfer data were correlated by the equation $$J = 0.2(ReFr)^{ - 0.28} ({L \mathord{\left/ {\vphantom {L d}} \right. \kern-\nulldelimiterspace} d})^{ - 0.28} $$ For a single vertical screen electrode the data were correlated by the equation $$J = 0.187(ReFr)^{ - 0.26} $$