A faradaic impedance study of the reduction of oxygen from aqueous alkaline solution at the dropping mercury electrode

The reduction of oxygen to hydrogen peroxide at a dropping mercury electrode in an aqueous solution of 1 M KNO₃+0.04 M KOH (pH=12.35) has been studied by means of impedance measurements as a function of frequency and d.c. potential. The reaction appears to be nearly reversible in the dc sense, but quasi-reversible in the ac sense. The impedance data obey the Randles' equivalent circuit with the following apparent values for the kinetic parameters: standard heterogeneous rate constant k_sh^a=0.035 cm s^?1 and cathodic transfer coefficient α^a_c=0.22. The results are interpreted in terms of a two-step charge transfer mechanism with the step O₂+eO₂^? being rate-determining.     

The photolysis of water vapor at 1470 Å. H2 production in the primary process

The primary processes in the photolysis of water vapor at 1470 Å are due to H₂O + hν(λ = 1470 Å) → H₂ + O(¹D), H₂O + hν(λ = 1470 Å) → H + OH with the H₂ yield of the first process accounting for 23% of the overall H₂ production. The quantum yield of this process is estimated to be 0.08 by using O₂ as a scavenger for H-atoms. Secondary reactions involving the photolytic products and added O₂ are discussed.     

A study of the cathodic reduction of ozone at the rotating disc electrode in acid electrolyte

The cathodic reduction of ozone according to O₃+2H⁺+2e^?→H₂O+O₂ was studied at a rotating disc electrode consisting of bright platinum in 1 M HClO₄ at 20°C. The current-potential curves obtained potentiostatically are determined by slow charge transfer in the range of low polarization (Tafel region) and diffusion as rate controlling step at high overvoltage. From the exchange current densities (i₀), obtained by extrapolation of Tafel lines to the reversible potentials, the heterogeneous rate constant k was evaluated giving an average value of 2.5×10^?7 cm s^?1. Likewise the diffusion coefficient (D_O3=1.7×10^?5 cm² s^?1) was calculated from the limiting currents measured at various partial pressures of ozone and different values of rotation rate. An equation for the total current-polarization curve was developed. The computed curves are in good agreement with the data which were obtained experimentally.     

Phase formation in the system Zn(VO<Subscript>3</Subscript>)<Subscript>2</Subscript>–HCl–VOCl<Subscript>2</Subscript>–H<Subscript>2</Subscript>O

The phase and chemical compositions of precipitates formed in the system Zn(VO₃)₂–HCl–VOCl₂–H₂O at pH 1?3, molar ratio V⁴⁺: V⁵⁺ = 0.1?9, and 80°C were studied. It was shown that, within the range 0.4 ≤ V⁴⁺: V⁵⁺ ≤ 9, zinc vanadate with vanadium in a mixed oxidation state forms with the general formula Zn_xV⁴⁺ _yV⁵⁺ _2-yO₅ ? nH₂O (0.005 ≤ x ≤ 0.1, 0.05 ≤ y ≤ 0.3, n = 0.5?1.2). Vanadate Zn_xV₂O₅ ? nH₂O with the maximum tetravalent vanadium content (y = 0.30) was produced within the ratio range V⁴⁺: V⁵⁺ = 1.5?9.0. Investigation of the kinetics of the formation of Zn_xV₂O₅ ? nH₂O at pH 3 determined that tetravalent vanadium ions VO2+ activate the formation of zinc vanadate, and its precipitation is described by a second-order reaction. It was demonstrated that, under hydrothermal conditions at pH 3 and 180°C, zinc decavanadate in the presence of VOCl₂ can be used as a precursor for producing V₃O₇ ? H₂O nanorods 50–100 nm in diameter.     

Fast-neutron radiolysis of acid water at elevated temperatures

Determination of G-values of water decomposition products in acid formed by irradiation of fast neutrons from a reactor YAYOI at elevated temperatures up to 275°C was carried out with a combination of an aerated and a deaerated Fricke dosimeters and a cerium dosimeter. As a first step, the dosimetry of the radiation field revealed that the average energy of the fast neutrons is 0.8 MeV, and over 90% of the total dose absorbed by the aqueous solutions comes from fast neutrons. At room temperature, G-values evaluated for water decomposition products, G_H + Ge^-_aq = 1.25, G_OH = 0.68, G_H2 = 0.99, G_H2O2 = 1.27 and G_-H2O = 3.21, coincide with those at initial LET of about 4 eV/Å. With increasing temperature, radical products increase and molecular products decrease, and above 150°C, relative G-values of the products seem to be similar to those obtained in γ-radiolysis at room temperature; however, G_-H2O decreases slightly. On the basis of the above results, the temperature effect of water decomposition with fast neutron at elevated temperatures is concluded to be very different from that by γ-rays, where no drastic change in the decomposition pattern with temperature was found.     

Mediated bioelectrocatalytic O2 reduction to water at highly positive electrode potentials near neutral pH

Combinations of bilirubin oxidase and metal complexes: [W(CN)₈]^3−/4−, [Os(CN)₆]^3−/4− and [Mo(CN)₈]^3−/4− (the formal potentials, E^0′(M), being 0.320, 0.448, and 0.584 V vs. Ag|AgCl, respectively, at pH 7.0), allowed bioelectrocatalytic reduction of O₂ to water at their formal potentials near neutral pH. The O₂ reduction current appeared even at the standard potential of the O₂/H₂O redox couple, E^0′(O₂/H₂O), when [Mo(CN)₈]^3−/4− was used at pH 7.4, though the magnitude was small. The magnitude of the bioelectrocatalytic current systematically decreased with the decrease in the potential difference between E^0′(O₂/H₂O) and E^0′(M). A limiting current as large as 17 mA/cm² of a projected electrode surface area was obtained at 0.25 V (−0.37 V vs. E^0′(O₂/H₂O)) for the O₂ reduction at pH 7.0 with a carbon felt electrode modified with electrostatically entrapped bilirubin oxidase and [W(CN)₈]^3−/4− at the electrode rotation rate of 4000 rpm.     

Promotional effect of nitrogen-doped and pore structure for the direct synthesis of hydrogen peroxide from hydrogen and oxygen by Pd/C catalyst at ambient pressure

Nitrogen-doped porous carbon is potential support for directly synthesizing H₂O₂ from H₂ and O₂. Here, density functional theory (DFT) was used to study the effect of N-doped porous carbon on H₂O₂ directly synthesized. The theoretical calculation results showed that N-doped improved H₂O₂ productivity and H₂ conversion by increasing the dispersion of Pd nanoparticles and the Pd⁰/Pd²⁺ ratio. However, N-doped decreased H₂O₂ selectivity by reducing oxygen's dissociation energies. The experimental results showed that adjusting the pore structure of N-doped porous carbon could improve the adverse effects of N-doping for H₂O₂ selectivity. The H₂O₂ productivity and selectivity of Pd/C catalyst with a macropore-mesoporous-microporous hierarchical porous structure were up to 328.4 mol_H2O2·kg_cat^-1·h^?1 and 71.9 %, respectively, at ambient pressure. The macropore structure enhances the transfer and diffusion performance of the catalyst and effectively inhibits the effect of N-doping on OO bond dissociation, which improves H₂O₂ productivity and selectivity. This research provides a possible solution for designing a high-performance Pd/C catalyst to directly synthesize H₂O₂ from H₂ and O₂ at ambient pressure.     

Rate coefficients at 297 K for proton transfer reactions with H2O. Comparisons with classical theories and exothermicity

Rate coefficients for proton transfer reactions of the type XH⁺ + H₂O → H₃O⁺ + X where X = H₂, CH₄, CO, N₂, CO₂ and N₂O and the type H₂O + X^? → XH + OH^? where X = H, NH₂ and C₂H₅NH have been measured at 297 K using the flowing afterglow technique. The results compare favourably with the predictions of the average-dipole-orientation theory. A trend is observed with exothermicity on a plot of (k_exp/k_ADO)_{298 K} versus ?ΔH_{298 K}⁰. The question is raised whether the relatively low probability observed for slightly exothermic proton transfer reactions is a consequence of reaction mechanism or results from the presence of a small activation energy barrier.     

On Reactions of Oxygenated Cobalt(II) Complexes. XI. Note on the Mechanism of O2 Uptake by Cobalt(II) Chelates with Tetra- and Pentadentate Amines

The synthesis of two new polyamines containing 2-pyridyl and 6-methyl-(2-pyridyl) groups is described. The equilibria between H⁺ and Co²⁺ and the new ligand 1,9-di(2-pyridyl)-2,5,8-triazanonane (dptn) as well as the protonation of the hydroxo complexes of 1,6-di(2-pyridyl)-2,5-diazahexane-Co(II) (Co(dpdh) and 1-(6-methyl-2-pyridyl-6-(2-pyridyl)-2,5-diazahexane-Co(II) (Co(mdpdh)) have been studied in aqueous solution using the pH method. The coordination ability of the pyridine containing ligand dptn is compared with the chelating tendency of the analogous aliphatic amine (tetren). In spite of the lower basicity of the pyridine derivative the stability constants of its Co(II) complex is higher by a factor of thirty. The absorption spectra give evidence for a pseudooctahedral geometry of Co(dpdh) (H²O) and Co(dpdh)(H₂O)(OH)⁺. Oxygen-uptake measurements indicate the formation of binuclear peroxo species. The potentiometric equilibrium data indicate the presence of dibridged species (dpdh)Co(O₂, OH)Co(dpdh)³⁺ and (mdpdh)Co(O₂, OH)Co-(mdpdh)³⁺. The kinetics of the rapid O₂-uptake was measured over a wide pH range on a stopped-flow apparatus. For Co(dpdh)²⁺ and Co(mdpdh)²⁺ we found a second order rate constant independent of pH up to pH 9, but in more alkaline solutions it increases and reaches an upper limit around pH 12.3. The data could be fitted by a rate law of the form k₁ = (k′₁[H⁺] + k″₁ K_H) ([H⁺] + K_H)^?1. This variation with pH was explained by a rapid equilibrium Co(dpdh) (H₂O) ? Co(dpdh)(H₂O)(OH)⁺ + H⁺(K_H). The enhanced rate constants of the hydroxo species must arise from a rate determining H₂O replacement by O₂, dominated by Co-OH₂ bond breaking and the expected ability of an OH^? group to labilize neighboring H₂O molecules. The protonation constant of the hydroxo complex obtained by equilibrium measurements (pK_H = 11.19 ± 0.03) was in good agreement with that derived from kinetic data (11.12 ± 0.04). The hydrolysis of Co(dptn)(H₂O)²⁺ influences the rate of O₂-incorporation in a different way. In this system retardation occurs as a result of hydrolysis ascribed to the slower leaving of OH^? compared to H₂O. This was expected if a mechanism with rate determining H₂O replacements by O₂ holds.     

Oxygenation of Co(II) Complexes with Tripodal Ligands

The kinetics of O₂-uptake of five-coordinated Co²⁺/tren complexes (tren = 2,2′, 2″-tris(2-aminoethyl)amine) have been studied extensively. The kinetics of formation of (tren)Co(O₂, OH)Co(tren)³⁺ exhibits two steps. The rate law of O₂-addition, the first step, was of the form: rate = (k[H⁺] + kK_a)/([H⁺] + K_a) [Co(tren)²⁺][O₂]. Second-order rate constants k = 220 ± 19 M ^?1s^?1 and k = 1.8 ± .035 · 10³M ^?1s^?1 agreed well from O₂-uptake and (stopped-flow) spectrophotometric measurements. The protonation constant of the hydroxo complex obtained by equlibrium measurements (spectrophotometric and by pH-titration) in anaerobic conditions (pK_a = 10.03) agreed well with that derived from kinetic data (p K_a = 9.93); k and k are about a factor 100 smaller than those for the pseudooctahedral Co(trien) (H₂O). This and the fact that several other Co(II) complexes with five-coordinated geometry do not exhibit oxygen affinity led to the proposal that the oxygenation mechanism for Co²⁺/tren complexes involves fast preequilibria between Co(tren) (H₂O)²⁺ and Co(tren) (H₂O) and only the latter is assumed to be reactive. The enhanced rate at high pH is explained by rate determining H₂O-exchange in the O₂-addition step and the ability of coordinated OH^? to labilize the neighbouring H₂O. This mechanism is furthermore supported by the formation of one kinetically preferred isomer of the peroxo-bridged dicobalt(III) complex (O₂ cis to the tertiary N-atom) and the large negative activation entropy (?30 eu). The second step is the intramolecular bridging reaction: is independent of [Co(tren)²⁺] and [O₂] but exhibits a pH-dependence of the form k₃ = k′₃[H + ]/(K_a + [H⁺]); k_?3 ( = 5 · 10^?5 s^?1) was determined independently and from the two rate constants the equilibrium constant was calculated as ≈ 10⁵. The ligand combination as in Co(tren)²⁺ was shown to provide an excellent balance to form a reversible oxygen carrier; possible reasons for this are discussed.     

UV light-assisted mineralisation and biodetoxification of Ponceau S with hydroxyl and sulfate radicals

The present study reports simultaneous mineralisation and biodetoxification of Ponceau S (3-hydroxy-4-(2-sulfo-4-[4-sulfophenylazo]phenylazo)-2,7-naphthalenedisulfonic acid sodium salt), an azo dye, by UV light assisted oxidation with hydroxyl and sulfate radicals. Metal ion catalysts used in the work were: Fe²⁺ and Ag⁺, and the oxidants used were: hydrogen peroxide and S₂O₈^2?. Strategies adopted to make the processes environmentally benign and economically viable by achieving maximum mineralisation in the shortest possible time are described. Mineralisation efficiency (Em) of various systems was found to follow the order: E_m(Fe²⁺/H₂O₂/UV) > E_m(Fe²⁺/S₂O₈^2?/UV) > E_m(Ag⁺/H₂O₂/UV) ≈ E_m(Ag⁺/S₂O₈^2?/UV). Thus, Fe²⁺ and HP are the most suitable metal ion catalyst and oxidant respectively, showing higher efficiency at pH 3 followed by that at pH 6.6. It is possible to enhance the Fe²⁺/H₂O₂/UV process electrical energy efficiency by maintaining the concentration of Fe at either 0.05 mM or 0.03 mM and that of the oxidant at 2.5 mM. The bioassay study revealed that the Fe²⁺/S₂O₈^2?/UV process biodetoxification efficiency is higher at pH 3 (93.7 %) followed by that at pH 6.6 (80.1 %) at the concentration of Fe ²⁺ and S₂O₈^2? of 0.03 mM and 2.5 mM, respectively. Thus, not only the concentration of Fe²⁺, but also the nature of the oxidant and pH play an important role in the biodetoxification process and S₂O₈^2? possesses higher biodetoxification efficiency than H₂O₂.     

Synergistic cocatalytic effect of MoO3 and creatinine on Cu–Fenton reactions for efficient decomposition of H2O2

The key scientific problems with conventional Fenton reactions are the acidic pH dependence and low ROS production due to inefficient decomposition of H₂O₂. Although Cu–Fenton reactions can break the pH limitation, there is still an urgent need to improve the overall reaction efficiency, and thus broaden its applicability. Herein, we describe a synergistic strategy by introducing MoO₃ cocatalyst and creatinine (Cr) assistant to enhance the efficiency of Cu–Fenton reactions at near-neutral pH. In this strategy, Cu²⁺ interacts with Cr to form a complex (CuCr₂), which is then mainly linked to MoO₃ via the Cu²⁺ binding site (CuCr₂/MoO₃). Experimental and theoretical calculation results manifest that the CuCr₂/MoO₃ exhibits an excellent cocatalytic activity, which significantly facilitates the rate-limiting step of Cu–Fenton reactions, and enables the efficient decomposition of H₂O₂ for the generation of three reactive oxygen species (ROS, ?OH, ¹O₂, ?O₂^?). More significantly, this cocatalytic system with high oxidation activity can be applied for the detection of Cu²⁺ and ROS-based chemodynamic therapy (CDT), as well as sterilization of Escherichia coli. This study represents a new breakthrough in improving the efficiency of Fenton-based reactions with a facile and promising strategy, and drives great progress in practicality.     

Complexation of the [Rh(H2O)6]3+ ion with phosphoric acid as probed by 31P NMR

The kinetics of the reaction [Rh(H₂O)₆]³⁺ + H₃PO₄ ? [Rh(H₂O)₅H₂PO₄]²⁺ + H₃O⁺ has been studied by ³¹P NMR; E _a = 142 ± 12 kJ/mol, logA = 17 ± 2. An empirical dependence of the ³¹P NMR chemical shift on the equilibrium pH value has been found. The acid dissociation constant of the coordinated ion has been evaluated: pK = 1.5. The ³¹P NMR chemical shifts of individual [Rh(H₂O)₅H₂PO₄]²⁺ and [Rh(H₂O)₅HPO₄]⁺ complex ions are, respectively, 14.5 and 15.8 ppm at 323 K.     

Synthesis, crystal structure and characterization of a 2-D network organic-inorganic hybrid polymer with [α-BW12O40]5− as building blocks

A two-dimensional network compound [Ce(DMF)₄(H₂O)][α-BW₁₂O₄₀]·H₂O·(HDMA)₂ (HDMA = protoned dimethylamine, DMF = N,N-dimethylformamide) was synthesized from α-H₅BW₁₂O₄₀·nH₂O, Ce(NO₃)₃·6H₂O and DMF and characterized by IR, UV spectra and TG-DTA. The result of the X-ray single crystal diffraction indicates that the crystal is monoclinic, space group P2₁/n, with unit cell dimensional: a = 1.1983(3), b = 2.4216(5), c = 1.9517(4) nm, β = 92.91(3)°, Z = 4, R ₁ = 0.07710, wR ₂ = 0.1416. Structural analysis indicates that every [Ce(DMF)₄(H₂O)]³⁺ building block is surrounded by three adjacent [α-BW₁₂O₄₀]^5? polyanions, meanwhile, every [α-BW₁₂O₄₀]^5? polyanion interconnects with three neighboring [Ce(DMF)₄(H₂O)]³⁺ subunits, by making use of which two-dimensional network structure can be constructed. The result of thermogravimetric analysis manifests that the title compound has two-stage weight loss and the decomposition temperature of the title polyanionic framework is 560°C. The electrochemical analysis shows the title polyanion has three-step redox processes in the pH = 4–7 media.     

Elucidation of methyl tert-butyl ether degradation with Fe/H2O2 by purge-and-trap gas chromatography-mass spectrometry

Degradation of methyl tert-butyl ether (MTBE) with Fe²⁺/H₂O₂ was studied by purge-and-trap gas chromatography-mass spectrometry. MTBE was degraded 99% within 120 min under optimum conditions. MTBE was firstly degraded rapidly based on a Fe²⁺/H₂O₂ reaction and then relatively slower based on a Fe³⁺/H₂O₂ reaction. The dissolved oxygen decreased rapidly in the Fe²⁺/H₂O₂ reaction stage, but showed a slow increase in the Fe³⁺/H₂O₂ reaction stage. tert-Butyl formate, tert-butyl alcohol, methyl acetate and acetone were identified as primary degradation products by mass spectrometry. A preliminary reaction mechanism involving two different pathways for the degradation of MTBE with Fe²⁺/H₂O₂ was proposed. This study suggests that degradation of MTBE can be achieved using the Fe²⁺/H₂O₂ process.     

Acid–base chemistry at the single ion limit

We present the results of acid–base experiments performed at the single ion (H⁺ or OH⁻) limit in ∼6 aL volume nanopores incorporating electrochemical zero-mode waveguides (E-ZMWs). At pH 3 each E-ZMW nanopore contains ca. 3600H⁺ ions, and application of a negative electrochemical potential to the gold working electrode/optical cladding layer reduces H⁺ to H₂, thereby depleting H⁺ and increasing the local pH within the nanopore. The change in pH was quantified by tracking the intensity of fluorescein, a pH-responsive fluorophore whose intensity increases with pH. This behavior was translated to the single ion limit by changing the initial pH of the electrolyte solution to pH 6, at which the average pore occupancy 〈n〉_pore ∼3.6H⁺/nanopore. Application of an electrochemical potential sufficiently negative to change the local pH to pH 7 reduces the proton nanopore occupancy to 〈n〉_pore ∼0.36H⁺/nanopore, demonstrating that the approach is sensitive to single H⁺ manipulations, as evidenced by clear potential-dependent changes in fluorescein emission intensity. In addition, at high overpotential, the observed fluorescence intensity exceeded the value predicted from the fluorescence intensity-pH calibration, an observation attributed to the nucleation of H₂ nanobubbles as confirmed both by calculations and the behavior of non-pH responsive Alexa 488 fluorophore. Apart from enhancing fundamental understanding, the approach described here opens the door to applications requiring ultrasensitive ion sensing, based on the optical detection of H⁺ population at the single ion limit.

Visualizing dynamic change in the number of protons during electroreduction of protons in attoliter volume zero-mode waveguides.     

Tandem mass spectrometry studies of acetone and acetone/water cluster ions

Ion clusters were formed in a temperature-variable high-pressure ion source from neat acetone and acetone/water mixtures and subjected to tandem mass spectrometry studies-unimolecular and collisionally activated mass-analyzed ion kinetic energy spectroscopy. The predominance of water loss from H⁺(H₂0)(A) _l=3, where A = acetone, suggests that the solvation sphere around H₃O⁺ does not close at l = 3, contrary to the case of acetonitrile or dimethyl ether. The results may be interpreted in terms of suggested ion structures which involve isomerization enroute to dissociation. The virtual absence of H/D scrambling in the collisionally activated dissociation of H₃O⁺(DA)₃, DA =acetone-d ₆, and of D₃O⁺(A)₃ means that if enolization takes place, it is a rate-determining step in an irreversible isomerization. The stability of H⁺(H₂O)(A)₃ is a dominant factor in the observation of acetone loss from H⁺(H₂0)(A)₄.     

Macrocycle complexation chemistry. 37. The isolation and crystallographic characterization of the U4+ and UO2+ extraction complexes [(H5O2)(dicyclohexano-24-crown-8)]2[U02Cl4]⁗MeOH and [(H5O2) (dicyclohexano-24-crown-8)]2[UCl6]⁗MeOH

The reaction of dicyclohexano-24-crown-8 with UCl₄ in 3/1 THF:MeOH under anhydrous conditions and with exposure to air, resulted in the isolation of the hydronium ion complexes, [(H₅O₂)(dicyclohexano-24-crown-8)]₂[UO₂Cl₄]-MeOH and [(H₅O₂)(dicyclohexano-24-crown-8)]₂[UCI₆]-MeOH. The [UO₂Cl₄]^2? complex crystallizes in the monoclinic space group,P2₁/n, witha = 15.200(8),b = 26.565(9),c = 16.977(8)Å, β = 95.89(6)° andD _calc = 1.40 g cm^?3 forZ = 4 formula units. A finalR value of 0.051 was obtained utilizing 5913 independent observed [F _o ≥ 5σ(F _o)] reflections. One ether is complexed by an ordered H₅O _inf2 ^sup+ ion, while the second crown ether is hydrogen bonded to a disordered H₅O _inf2 ^sup+ ion. The [UCl₆]^2? complex is tetragonal,P4/n, with (at ?150°C)a = 16.320(4),c = 12.542(2)Å andD _calc = 1.47 g cm^?1 forZ = 2. A finalR value of 0.038 was obtained utilizing 2466 observed reflections. The anion resides on a four-fold axis and the crown ether cation around a crystallographic two-fold axis. The H₅O _inf2 ^sup+ ion is disordered into two orientations within the macrocycle cavity. All three crystallographically independent crown ether environments in these two structures have essentially identical conformations.     

Standard pH values for potassium hydrogenphthalate reference buffer solutions in 10, 30 and 50% (w/w) 1,4-dioxane/water mixed solvents at temperatures from 288.15 to 318.15 K

Standard pH(S) values for 0.05 mol kg^?1 potassium hydrogenphthalate (KHpH) reference buffer solutions in 10, 30 and 50% (w/w) 1,4-dioxane/water solvent mixtures within the temperature range 288.15–318.15 K are determined from e.m.f. measurements of the cell without transference Pt|H₂|KHPh + KCl|AgCl|Ag|Pt. The consistency of the results is analysed by a recently described method of multilinear regression of the quantity p(a_Hγ_Cl) as a function of both solution composition and temperature. The standard pH(S) determined can be reproduced to within ±0.01 by the equation pH(S) - 4.004 + 3.309w + 0.408z + 1.037w³ - 14.95zw² + 27.1zw³, where w is the weight fraction of dioxane in the solvent mixture,z = (T –θ)/θ, and θ - 298.15 K. Values of the first ionization constant of phthalic acid (H₂Ph; benzene-1,2-dicarboxylic acid) in the above solvent mixtures are also determined from e.m.f. measurements of the cell without transference Pt|H₂|H₂Ph + KHPh + KCl|AgCl|Ag|Pt.     

Hydrolytic precipitation of calcium polyvanadates from vanadium(IV) and vanadium(V) solutions

The effect of VO²⁺ ions on the composition and kinetics of calcium polyvanadate precipitation from solutions with 1.5 ≤ pH ≤ 9 at 80–90°C has been studied. For 1,5 ≤ pH < 3 and V⁴⁺/V⁵⁺ = 0.11–9, the precipitated compounds have the general formula Ca _x V _y ⁴⁺ V _12?y ⁵⁺ O_31?δ · nH₂O (0.8 ≤ x ≤ 1.06, 2 ≤ y ≤ 3, 0.94 ≤ δ ≤ 1.5). The maximum vanadium(IV) proportion (y = 3) in the precipitates is achieved when V⁴⁺/V⁵⁺ = 0.5?1.0 in the solution and pH is 3. Polyvanadate precipitation at pH 1.7 has a long induction period (up to 30 min), which is not observed for V⁴⁺/V⁵⁺ > 0.1. Precipitation in solutions with pH 3 occurs only when VO²⁺ ions are added, with a maximum rate near V⁴⁺/V⁵⁺ = 0.2 and in presence of chloride ions. The processes are controlled by a secondorder reaction on the polyvanadate surface.