Kinetics of the cathodic decomposition of silver iodide in molten alkaline nitrates

The cathodic decomposition of AgI was studied using a single pulse galvanostatic technique. The working electrode was an AgI-rotating disc immersed in the molten KNO₃-NaNO₃ eutectic. Linear overpotential-log (current density) plots were obtained for varying concentrations of I⁻. Evidence was found for the existence of two different control steps, depending on the iodide concentration. At lower I⁻ concentrations a chemical reaction forming an adsorbed AgI⁻₂ complex ion is postulated as the rate-determining step. At higher I⁻ concentrations the rds is related to the electrochemical reaction AgI + e = Ag° + I⁻. An alternative charge transfer process is suggested corresponding to the transfer of an I⁻ ion between the two ionic media.     

Voltammetric study of halide ion adsorption on platinum in perchloric acid solutions

Periodic current/potential curves were taken potentiostatically at 30 mV/sec on smooth platinum in 1 N HClO₄ with different additions of HCl, HBr, and HI, in the potential range between hydrogen evolution and deposition of oxygen or of the respective halide ion. The effect of increasing halide ion concentration, starting at 10⁻⁶ M, on hydrogen adsorption and oxygen adsorption was studied systematically. Impedance measurements were made at 1000 c/s under the same conditions as the measurements of the current/potential curves. It is concluded from the dependence of the double layer capacitance upon the bulk concentration of halide ions in the double layer region that nearly a monolayer of adsorbed ions is present there for ₀c_Cl⁻ ≈ 10⁻² M, ₀c_Br ≈ 10⁻⁴ M, and ₀c_HI ≈ 10⁻⁵ M. The measurements at larger concentrations, especially for I⁻, show additional effects which are due to the deposition of halides and to the reverse reaction.     

Redox behavior and selective oxidation properties of mesoporous titano- and zirconosilicate MCM-41 molecular sieves

Mesoporous titano- and zirconosilicate molecular sieves, Ti-MCM-41 and Zr-MCM-41, respectively, with Si/M ratios in the range from 11 to 96 (M=Ti or Zr), have been synthesized by the hydrothermal method and characterized by XRD, XRF, N₂ adsorption and diffusive reflectance UV–Vis (DRUV–Vis), FT-IR and electron spin resonance (ESR) spectroscopic techniques. The redox behavior and selective oxidation properties of these materials have been investigated. ESR of samples reduced with LiAlH₄ (298 K) and H₂ (673–873 K) reveals two types of metal ion species: species I^′ located inside the pore walls and species I^′′ located at the pore surface. The reduced species I^′′ are highly reactive towards oxygen and form M(O₂^−·) radicals. The M(O₂^−·) radicals were also observed when the samples were reacted with aqueous H₂O₂ or tert-butylhydroperoxide (TBHP). ESR studies reveal that Ti-MCM-41 is easier to reduce and reoxidize than Zr-MCM-41. The DRUV–Vis spectra are consistent with a monoatomic dispersion of the metal ions. In the samples with high metal loading the presence of a nanocrystalline metal oxide phase cannot be ruled out. Both Ti-MCM-41 and Zr-MCM-41 catalyze the hydroxylation of 1-naphthol with aqueous H₂O₂ and the epoxidation of norbornylene with TBHP.     

Further aspects of the differential capacitance of iron

The differential capacitance of high purity zone-refined iron was measured using a single pulse technique. Capacitance behaviour in dilute solutions of sodium perchlorate showed that an unambiguous assignment of a value to the pzc is not possible from the capacitance minima. Measurements in sodium halides showed a different behaviour with I⁻ than with F⁻, Cl⁻ and Br⁻. Electrode capacitance in an aqueous solution of furoic-acid-sodium-furoate buffer was determined over 300 mV on either side of the open-circuit potential. The effect of specifically adsorbed furoate ions on the morphology of the capacitance curves is very striking.     

Untersuchung über die anionenadsorption mit hilfe markierter ionen

From previous work, the adsorption of anions is regarded as an essential factor for the different corrosion behaviour of metals in solutions containing different anions. Adsorption is measured by means of ³⁶Cl⁻, ⁸²Br⁻, ¹⁸ F⁻, ³⁶ClO₄⁻, ³⁵O₄²⁻, H³⁵S⁻ and ¹⁴CN⁻ on Pt, Ni and Fe in the form of sheets and evaporated films. Besides the determination of the adsorption after dipping into the solution, a method has been developed for the measurement of adsorption in contact with the solution and for the determination of its kinetics. The method can also be applied to O₂-free metal surfaces produced under vacuum. In this case, however, very rapid adsorption is observed, whereas normally saturation is reached only after many hours. It is concluded that, in general, exchange between oxygen on the metal and the anion takes place rather than simple adsorption.

The distribution of the anions adsorbed on the metal surface has been studied by autoradiography; adsorption takes place preferentially at the grain boundaries and increases when the crystal size decreases.

These results confirm the interpretation of passivation as a competition between various processes: metal dissolution, coverage by a passivating oxide film, and displacement of oxygen by anions.     

Adsorption of methane/ethane mixtures on dry coal at elevated pressure

The binary adsorption characteristics of methane and ethane on dry coal to 40 atm pressure have been calculated from pure-component isotherms. In some coal seams, pressures exceeding 40 atm have been recorded and the methane sampled from the virgin coal often shows a few percent of ethane. The binary adsorption characteristics were calculated by employing the ideal adsorbed solution theory of Myers and Prausnitz, and experimentally-determined (Type I) pure gas isotherms at 0, 30 and 50 °C. The coal used in this investigation was high-volatile ‘A’ bituminous (hvab) from the Pennsylvania Pittsburgh seam. Gas nonideality was accounted for by replacing pressure with fugacity. Adsorption of methane on dry coal is purely physical; the isosteric heat of adsorption does not exceed 2.4 kcal/mol^* at 30 °C on the above coal. Isobars on the resulting binary equilibrium diagram exhibited an unexpected phenomenon of intersecting each other which might be attributable to the above nonideality considerations. The region of a few percent of ethane, which is of practical importance from the viewpoint of coal seams, was expanded and reduced to an equation: V(CH₄) = −21.52 + 7.18(VF) + 16.88(VF)² −0.395(P) − 0.00661(P)² + 0.824(T) − 0.00030(T)² + 0.928(VF)(P) − 0.858(VF)(T). V(Total) = 25.9 − 23.6(VF) + 0.655(P) − 0.00875(P)² − 0.795(T) + 0.743(VF)(T) where V(CH₄) and V(Total) = cm³(STP)CH₄ and total gas respectively adsorbed per g dry coal; VF = vol. fraction of methane as analysed at 1 atm (0.94 VF 1.0); P = seam pressure, atm (0 P 40); T=seam temperature, °C(−10 T 50).     

A kinetic interpretation of the photocurrents obtained with [Fe(CN)6], Fe(II), and I at n-type MoSe2- and WSe2-electrodes

Hole-photocurrents have been measured at MoSe₂- and WSe₂-crystals with high sensitivity in an electrochemical cell. The different magnitude of the photocurrents obtained with [Fe(CN)₆]⁴⁻ and Fe(II) can be explained with the known difference in the respective rate constants of electron transfer without having to postulate adsorption. The model yields an estimate of the hole concentration at the crystal surface and suggests an effective blockade of recombination centers at the surface as cause for the high photocurrent obtained with I⁻.     

The influence of halide ions at submonolayer levels on the formation of oxide layer and electrodissolution of copper in neutral solutions

The formation of submonolayers of copper (I) halide preceding anodic oxide layer growth and copper electrodissolution has a remarkable influence on these two processes. Chloride electroadsorption on copper at the submonolayer level takes place as two successive stages at potentials 0.7 V lower than the reversible potential of the Cu/CuCl redox couple. Similar results are obtained for iodide, bromide and fluoride ions although the driving force for electroadsorption decreases in the order I⁻ > Br⁻ > Cl⁻ > F⁻. The relative contributions of OH⁻ and halide ion electroadsorption can be modified through the solution composition, applied potential and electroadsorption time. The increase surface coverage by the electroadsorbate diminishes the amount of the passive oxide layer and strongly increases the metal electrodissolution rate, particularly when the amount of passive oxide layer becomes smaller than that required to form a compact monolayer.     

Etude electrochimique de l''iode et de ses derives en solution dans la pyridine variation des proprietes d''oxydo-reduction en fonction du pH

The electrochemical behaviour of iodine and redox derivatives in solution in pyridine was studied by the use of voltammetric method. By controlling the pH value, it is possible to establish the normal apparent thermodynamic diagram of stability of iodine in this solvent. In acid media, the four chemical species I⁻, I⁻₃, I₂ and I⁺ are stable; their respective stability constants are evaluated. In basic media, one observes the disproportionation reaction of iodine, at first into triodide and into a base complexing with iodine in (I⁺), then into iodide and iodate. A salt of positive univalent iodine was isolated by neutralizing I⁺ with an excess of tetraethylammonium hydroxide.     

XPS studies on the oxygen species of LaMn1−xCuxO3+λ

The electronic states of LaMn_1−xCu_xO_3+λ (x=0–0.4) have been studied with X-ray photoelectron spectroscopy (XPS). The valence states of substituted copper ions were Cu²⁺ and the manganese ions were a highly mixed state of Mn³⁺ and Mn⁴⁺. The nonstoichiometry and electronic state of lattice oxygen have been studied. The samples at x=0 and 0.1 had an excess of lattice oxygen but those at x=0.2–0.4 had lattice oxygen deficiency. A modified Auger parameter (Δ′) was used to evaluate the electronic states of oxygen ions. The Δ′ of lattice oxygen increased with increasing substitute quantity. This increase of Δ′ reflected the decrease of ionic bond character of lattice oxygen. The adsorbed oxygen species on LaMn_1−xCu_xO_3+λ was assigned mainly as O⁻ from the peak positions of spectra for the O 1s and O KLL levels, and the Δ′ of this O⁻ decreased with x. This decrease, i.e., the increase of ionic bond character of adsorbed oxygen was correlated well with the value of nonstoichiometry of lattice oxygen.

The rate of CO oxidation at 448 K was increased by the substitution till x=0.4. We consider that this enhancement of reactivity comes from the change of electronic state of adsorbed oxygen, O⁻ itself, i.e., a weak interaction between O⁻ and low coordinated metal site brings about a high reactivity.     

Electrocatalysis of the charge-transfer process for the Sb(III)/Sb(V) couple at a platinum electrode in concentrated HCl

Electrocatalysis of the electrochemical oxidation and reduction of Sb(V) and Sb(III) by adsorbed I⁻ and I₂ at a rotating Pt disc electrode was investigated in 12 M HCl. The heterogeneous rate constant in the absence of adsorbed halogen was increased by 200x for a maximum surface coverage by halogen. This large rate increase cannot be predicted on the basis of an electrostatic argument and a mechanism based on electron-transfer bridging is proposed.     

Transfer of iodine through graphite in aqueous iodide solutions

A polycrystalline graphite diaphragm separating two aqueous KI solutions containing different amounts of I₂ is a bipolar electrode and the whole system behaves like a short-circuited concentration cell in which the graphite diaphragm is the bipolar electrode and its acts in the meantime also as the separatory diaphragm. Transfer of iodine from the more concentrated to the more diluted side of the diaphragm is accomplished by electrochemical reduction of I⁻₃ to I⁻ on the side facing the concentrated solution and simultaneous oxidation of I⁻ to I⁻₃ on the other side. The overall transfer process results to be much faster than a simply diffusive phenomenon, because it is driven by electrical potentials and it is not simply related to the concentration gradient. The transfer rate seems to be mainly dependent from the electrical mobility of the positive ions in the solution contained in the graphite pores.     

The interaction of NO with Co/Co redox centres in CoAPOs catalysts: FTIR and UV–VIS investigations

The interaction of NO with Co²⁺/Co³⁺ redox sites in CoAPO-18 and CoAPO-5 catalysts was studied by means of FTIR and diffuse reflectance UV–Vis spectroscopy both at 298 and 85 K. Two families of Co²⁺ sites were found in the CoAPO-18 structure. (A) Ions in framework [Co²⁺(OH)P], associated with Brønsted acid sites which adsorb NO to produce dinitrosyls absorbing at 1903 and 1834 cm⁻¹; these dinitrosyl complexes are reactive, in that Co²⁺ is oxidized to Co³⁺ and N₂O is formed. (B) Structural defects Co²⁺ (Lewis acid sites) which stabilize dinitrosyls absorbing at 1900 and 1813 cm⁻¹. The NO adsorption both on reduced and, more significantly, on oxidised CoAPO-18 also leads to the formation of NO₂^δ+ adsorbed species. It was found that the two kinds of dinitrosyl complexes have different reactivity in presence of oxygen. Both families of sites are also present in CoAPO-5 catalysts on which, however, the redox reaction upon NO adsorption does not occur significantly.     

Photocatalytic degradation kinetics of di- and tri-substituted phenolic compounds in aqueous solution by TiO2/UV

In this study, photocatalytic degradation of 2,4,6-trimethylphenol (TMP), 2,4,6-trichlorophenol (TCP), 2,4,6-tribromophenol (TBP), 2,4-dimethylphenol (DMP), 2,4-dichlorophenol (DCP) and 2,4-dibromophenol (DBP) has been studied by TiO₂/UV. Although degraded phenolic compound concentration increased by increasing initial concentration photocatalytic decomposition rates of di- and tri-substituted phenols at 0.1–0.5 mM initial concentrations decreased when the initial concentration increased. The fastest degradation observed for TCP and the slowest for TMP. Photodegradation kinetics of the compounds has been explained in terms of Langmuir–Hinshelwood kinetics model. Degradation rate constants have been observed to be extremely depended on electronegativity of the substituents on phenolic ring. Degradation rate constant and adsorption equilibrium constant of TCP were calculated as k 0.0083 mM min⁻¹ and K 9.03 mM⁻¹. For TBP and TMP the values of k and K were obtained as 0.0040 mM min⁻¹, 19.20 mM⁻¹, and 0.0017 mM min⁻¹, 51.68 mM⁻¹, respectively. Degradation rate constant of DBP was similar as DCP (0.0029 mM min⁻¹ for DBP and 0.0031 mM min⁻¹ for DCP) whereas adsorption equilibrium constants differed (48.40 mM⁻¹ for DBP and 30.52 mM⁻¹ for DCP). K and k of DMP found as 83.68 mM⁻¹ and 0.0019 mM min⁻¹, respectively. The adsorption equilibrium constants in the dark were ranged between 1.11 and 3.28 mM⁻¹ which are lower than those obtained in kinetics. Adsorption constants have inversely proportion with degradation rate constants for all phenolic compounds studied.     

Effect of anions and cations on the aqueous phase catalytic hydrogenation of C=C bonds

The influence of solution composition (nature of anions and cations, pH) in the aqueous phase catalytic hydrogenation of C=C bonds (maleic acid) has been investigated.

In weakly acidic solutions (of pH 3 and 6) the influence of the commonly used anions (ClO₄⁻, HSO₄⁻/SO₄²⁻, Cl⁻) is less important than that obtained in solutions of pH 0.3, found in previous works [Electrochim. Acta 45 (2000) 4299]. This difference can be ascribed to a weaker adsorption of the anion on platinum, as well as, to the different nature of the competitively adsorbed maleic acid species (molecular form or anionic adsorption) depending on the solution pH. In the presence of (hydrogeno)phosphates the lowest activities are obtained implying that these anions are the most strongly adsorbed on platinum.

An important promotion of platinum activity in the presence of cations has also been found. This effect depends on the size of the cation and can be attributed to the modification of the work function and, consequently, of the adsorption properties of platinum.     

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.     

Differential capacitance of the platinum/aqueous-solution interphase

The differential capacitance of polycrystalline platinum in aqueous H₂SO₄ and NaOH solutions has been investigated as a function of bias potential. A capacitance minimum is observed at 0·56 V in H₂SO₄ and − 0·34 V in NaOH solution. There is strong evidence for the irreversible adsorption of oxygen/OH⁻ ions and oxide-film formation. Addition of n-butylamine hinders the adsorption of oxygen/OH⁻ ions and it is itself strongly adsorbed.     

Catalytic performance of quaternary ammonium salts in the reaction of butyl glycidyl ether and carbon dioxide

The synthesis of cyclic carbonate from butyl glycidyl ether (BGE) and carbon dioxide was performed in the presence of quaternary ammonium salt catalysts. Quaternary ammonium salts of different alkyl group (C₃, C₄, C₆ and C₈) and anions (Cl⁻, Br⁻ and I⁻) were used for this reaction carried out in a batch autoclave reactor at 60–120 °C. The catalytic activity increased with increasing alkyl chain length in the order of C₃ < C₄ < C₆. But, the quaternary ammonium salt with longer alkyl chain length (C₈) decreased the conversion of BGE because it is too bulky to form an intermediate with BGE. For the counter anion of the tetrabutyl ammonium salt catalysts, the BGE conversion decreased in the order Cl⁻ > Br⁻ > I⁻. The effects of carbon dioxide pressure and reaction temperature on this reaction were also studied to better understand the reaction mechanism.     

Phase transition phenomena of the adsorbed 1-dodecanol monolayer at the air–water interface

Phase transition phenomenon of the 1-dodecanol monolayer at the air/water interface was studied by the dynamic γ(t) curves and the adsorption isotherm obtained by ellipsometry at 20 °C. The surface-concentration adsorption isotherm clearly showed three abrupt increases at bulk concentration C of 1.3 × 10⁻⁹, 2 × 10⁻⁹ and 3.7 × 10⁻⁹ mol/mL, respectively. The 1st and the 3rd transitions observed herein, that were typical 2D first-order transitions, were consistent with the gas to liquid expanded (G–LE) and the liquid expanded to liquid condensed (LE–LC) phase transitions observed in a previous tensiometry study. The 2nd transition that occurred at C = 2 × 10⁻⁹ mol/mL was not identified from any previous dynamic surface-tension profiles. Judging from the substantial increase in the film thickness of the transition, it was believed that the orientation change of the adsorbed molecule was involved in the LE phase. A LE_h and a LE_v phase, that denoted the “lie-down” and “stand-up” types of adsorption, respectively, was used to describe this transition and a cusp, instead of a constant surface-tension region, was observed in the dynamic γ(t) curves for this transition. This suggested that, since the surface tension varied during the transition process, the newly identified LE_h and LE_v transition might not be the typical first-order type of phase transition.     

NO–NH3 coadsorption on vanadia/titania catalysts: determination of the reduction degree of vanadium

Diffuse reflectance infrared fourier transform spectroscopy (DRIFTS) has been used to study NH₃ and NO adsorption over a 15% w/w vanadia/titania catalyst. NH₃ is adsorbed as coordinate NH₃ and NH₄⁺ species over the oxidised catalyst, leading to the reduction of the vanadia surface. At 300°C, adsorbed nitrosyls species are detected, suggesting that the oxidation of gaseous or adsorbed ammonia species takes place over the V=O sites. Coadsorption experiments show that NO is able to reoxidise about the 57% of the reduced V=O groups, resulting in N₂, according to a NO+V_□→1/2N₂+V=O reaction. On the other hand, NO is only adsorbed over vanadia reduced surfaces. The measure of the area of the 2ν(V=O) bands results in an estimate of the oxidation state of vanadium. From this estimate it can be concluded that nitrosyls species are adsorbed on the catalyst surface for vanadium atoms having an oxidation state ranging from +4 to +3.1.