Dissociation et hydratation de nitrates alcalins dans le carbonate de propylene aqueux

Dissociation of lithium, sodium, potassium and tetraethylammonium nitrates and perchlorates in propylene carbonate has been studied by conductometry. Dissociation constants of alkali nitrates are 3·14 × 10^?3 (LiNO₃), 8·35 × 10^?3 (NaNO₃ and 1·92 × 10^?2 (KNO₃) at 25°C. The perchlorates and tetraethylammonium nitrate are strong electrolytes. The solubility products are 4·1 × 10^?4 (LiNO₃), 1·2 × 10^?5 (NaNO₃ and 2·5 × 10^?5 (KNO₃). The conductivity of saturated solutions of nitrates in the aqueous solvent has been determined up to 0·6 M water. Results are used to calculate the equilibrium constants for the reaction I^± + H₂O = I^± H₂O; Li⁺ 6·5, Na⁺ 2·5, K⁺ 0·5 and NO^?₃ 2·4. Dissociation constants, solubility products and hydration constants are compared with values reported for other solvents.     

Kinetics of leaching of tunisian phosphate ore particles in dilute phosphoric acid solutions

Van der Sluis et al.'s model was used to determine the rate of the partial dissolution of a Tunisian phosphate rock with dilute phosphoric acid (1.5 mass% P₂O₅). When the temperature rises from 25 to 90°C, for a given particle size, the mass-transfer coefficients, k_L°, vary from 3 × 10^?3 to 8 × 10^?3 m ·s^?1. The corresponding diffusion coefficients, D, lies between 6 × 10^?7 and 27 × 10^?7 m²·s^?1. Activation energy is equal to 14 kJ·mol^?1 and values of k_L°, at 25°C, are in the range of 0.28 × 10^?3 and 4 × 10^?3 m·s^?1 when the agitation speed goes from 220 to 1030 rpm, showing that the leaching process is controlled by diffusion rather than by chemical reaction.     

Photoelectrocatalytic humic acid degradation kinetics and effect of pH,applied potential and inorganic ions

This study addresses the removal of humic acid (HA) dissolved in an aqueous medium by a photoelectrocatalytic process. UV₂₅₄ removal and the degradation of color (Vis₄₀₀) followed pseudo‐first order kinetics. Rate constants were 1.1 × 10^?1 min^?1, 8.3 × 10^?2 min^?1 and 2.49 × 10^?2 min^?1 (R² > 0.97) for UV₂₅₄ degradation and 1.7 × 10^?1 min^?1, 6.5 × 10^?2 min^?1 and 2.0 × 10^?2 min^?1 for color removal from 5 mg dm^?3, 10 mg dm^?3 and 25 mg dm^?3 HA respectively. Following a 2 h irradiation time, 96% of the color, 98% of the humic acid and 85% of the total organic carbon (TOC) was removed from an initial 25 mg dm^?3 HA solution in the photoanode cell. Photocatalytic removal on the same photoanode was also studied in order to compare the two methods of degradation. Results showed that the photoelectrocatalytic method was much more effective than the photocatalytic method especially at high pH values and with respect to UV₂₅₄ removal. The effect of other important reaction variables, eg pH, external potential and electrolyte concentration, on the photoelectrocatalytic HA degradation was also studied. Copyright © 2003 Society of Chemical Industry     

Ionization equilibria in solutions of nickel(II) chloride in dimethyl-sulphoxide

Visible absorption spectra and the molar conductance curve of NiCl₂ dissolved in dimethyl-sulphoxide (DMSO) have been determined at 25°C. The results indicate the formation of the [NiCl(DMSO)₅]⁺ inner-sphere complex followed by the formation of the {NiCl(DMSO)₅]⁺Cl^?} outersphere ion-pair as the concentration of NiCl₂ increases. The [NiCl₂(DMSO)₄] inner-sphere complex in pure dimethyl sulphoxide at 25°C is formed to but a small extent, but its relative content increases upon addition of the non-coordinating diluent, chlorobenzene. Dilutions with chlorobenzene also enhance coordination disproportionation producing the [NiCl₃ DMSO]^? tetrahedral complex. The stability constant of the monochloro complex derived from the conductometric data has the value of 297 (^±10)M^?2 at 25°C, and the estimated value of the association constant of the [NiCl (DMSO)₅]⁺Cl^? complex electrolyte, dominating in moderately concentrated solutions at room temperature, is 7(±3)M^?1.     

Adsorption of chlorophyll-a from acetone solution on natural and activated bentonite

The adsorption of chlorophyll-a on bentonite desiccated at 110°C, untreated and acid-treated with H₂SO₄ solutions over a concentration range between 0·25 and 2·50 mol dm^?3, from acetone solution at 25°C has been studied. The adsorption isotherms may be classified as using Giles' classification, as type S (untreated sample and 0·25 mol dm^?3 H₂SO₄-treated sample), type H (0·50 mol dm^?3 H₂SO₄-treated sample) and type L (1·00 and 2·50 mol dm^?3 H₂SO₄-treated samples). This fact suggests that the bentonite surfaces (low, high and medium affinity, respectively) behave in differently relation to the adsorption of the chlorophyll-a molecules. The experimental data points have been fitted to the Freundlich equation in order to calculate the adsorption capacities (K_f) of the samples; K_f values range from 0·43 mg kg^?1 for the untreated bentonite up to 108·89 mg kg^?1 for the 0·50 M H₂SO₄-treated bentonite. The removal efficiencies (R) have also been calculated and range from 5·71% for the untreated bentonite up to 85·18% for the 0·50 M H₂SO₄-treated bentonite.     

Rare-earth-tantalate high-entropy ceramics with sluggish grain growth and low thermal conductivity

A series of rare-earth-tantalate high-entropy ceramics ((5RE_0.2)Ta₃O₉, where RE = five elements chosen from La, Ce, Nd, Sm, Eu and Gd) were prepared by conventional sintering in air at 1500 ^°C for 10 h. The (5RE_0.2)Ta₃O₉ high-entropy ceramics exhibit an orthogonal structure and sluggish grain growth. No phase transition occurs in the test temperature of 25–1200 ^°C. The thermal conductivities of all (5RE_0.2)Ta₃O₉ ceramics are in the range of 1.14–1.98 W m^?1 K^?1 at a test temperature of 25–500 ^°C, approximately half of that of YSZ. The sample of (Gd_0.2Ce_0.2Nd_0.2Sm_0.2Eu_0.2)Ta₃O₉ exhibits a low glass-like thermal conductivity with a value of 1.14 W m^?1 K^?1 at 25 ^°C. The thermal expansion coefficient of (5RE_0.2)Ta₃O₉ ceramics ranges from 5.6 × 10^?6 to 7.8 × 10^?6 K^?1 at 25–800 ^°C, and their fracture toughness is high (3.09–6.78 MPa·m^1/2). The results above show that (5RE_0.2)Ta₃O₉ ceramics could be a promising candidate for thermal barrier coatings.     

Conductance and spectroscopy of protonic beta and beta″-aluminas

Five protonic beta and beta″-aluminas; viz hydrated sodium beta-alumina (1,24Na₂O·11Al₂O₃), hydronium beta-alumina (1.24H₂O·11Al₂O₃·2.6H₂O), partially dehydrated hydronium beta-alumina (1.24H₂O·11Al₂O₃·1.3H₂O), hydrogen beta-alumina (1.24H₂O·11Al₂O₃) and hydronium beta″-alumina (0.84H₂O·0.8MgO·5Al₂O₃·2.8H₂O) were examined by broad band nuclear magnetic resonance from ?196°C to 200°C. The spectra of hydronium beta-alumina and hydronium beta″-alumina are consistent with a mixed composition of H₂O, H₃O⁺ and H⁺ species in the conducting plane. Hydrogen beta-alumina and partially dehydrated hydronium beta-alumina appear to contain only relatively isolated (2.6–2.7Å) protons; no evidence of molecular water or hydronium ions is found. Water molecules intercalated into the conduction plane of sodium beta-alumina do not appear to be in rapid motion, even at 167°C, but are relatively stationary. The onset of motional narrowing in hydronium beta″-alumina occurs at ?40°C but not until +30°C in hydronium beta-alumina. This is consistent with the higher conductivity reported for hydronium beta″-alumina, 10^?3–10^?5 (ohm-cm)^?1 at 25°C, in comparison to 10^?10–10^?11 (ohm-cm)^?1 for hydronium beta-alumina at 25°C.     

Kinetics of Estrone Ozone/Hydrogen Peroxide Advanced Oxidation Treatment

Ozone/hydrogen peroxide batch treatment was utilized to study the degradation of the steroidal hormone estrone (E1). The competition kinetics method was used to determine the rate constants of reaction for direct ozone and E1, and for hydroxyl radicals and E1 at three pH levels (4, 7, and 8.5), three different molar O₃/H₂O₂ ratios (1:2, 2:1, and 4:1) and a temperature about 20°C. The average second-order rate constants for direct ozone-E1 reaction were determined as 6.2?×?10³?±?3.2?×?10³ M^?1s^?1, 9.4?×?10⁵?±?2.7?×?10⁵ M^?1s^?1, and 2.1?×?10⁷?±?3.1?×?10⁶ M^?1s^?1 at pH 4, 7, and 8.5, respectively. It was found that pH had the greatest influence on the reaction rate, whereas O₃/H₂O₂ ratio was found to be slightly statistically significant. For the hydroxyl radical-E1 reaction, apparent rate constants ranged from 1.1?×?10¹⁰ M^?1s^?1 to 7.0?×?10¹⁰ M^?1s^?1 with an average value of 2.6?×?10¹⁰ M^?1s^?1. Overall, O₃/H₂O₂ is shown to be an effective treatment for E1.     

High oxide ion conduction in sintered oxides of the system Bi2O3-Y2O3

The ionic conduction in sintered Bi₂O₂-Y₂O₃ was investigated by measuring the conductivity and the emf of an oxygen concentration cell using the specimen tablet as electrolyte. The face centred cubic phase in this system was found to show high oxide ion conduction accompanied by a little electronic conduction when exposed to air. This phase was stable with a composition of 25 ～ 43 mol % Y₂O₃ over a wide range of temperatures, and the oxide ion conductivity increased with decrease in Y₂O₃. The conductivities of (Bi₂O₃)_0.75 (Y₂O₃)_0.25 were 1.6×10^?1 Ω^?1 cm^?1 at 700°C and 1.2×10^?2 Ω^?1 cm^?1 at 500°C values which are many times higher than those of stabilized zirconia (ZrO₂)_0.90(Y₂O₃)_0.10 at corresponding temperatures. Specimens containing less than 25 mol % Y₂O₃ showed a phase transition at 700 ～ 580°C and the conductivities decreased remarkably below these temperatures. High oxide ion conduction in the fcc phase is attributed to the migration of oxide ion vacancies which were present in an appreciable amount.     

Kinetics of aluminium deposition from aluminium chloride—alkali chloride melts

The kinetics of aluminium deposition from NaClAlCl₃ and NaClKClAlCl₃ melts (c_AlCl3 < 0.4 mol%) was studied by linear sweep voltammetry and potential step amperometry. The reduction of AlCl₃ on tungsten and aluminium electrodes was found to be diffusion controlled. The diffusion coefficients of AlCl₃ were: 3.5 × 10^?5 cm² s^?1 at 820°C in NaClAlCl₃, 2.7 × 10^?5cm²s^?1 at 825°C, and 2.1 × 10^?5cm²s^?1 at 705°C in KClNaClAlCl₃. The rate constant for AlCl₃ reduction at these conditions was found to be in the order of 0.2 cm s^?1, in good agreement with extrapolated literature data.     

Acidogenic fermentation of blended food‐waste in combination with primary sludge for the production of volatile fatty acids

The performance of a laboratory‐scale anaerobic acidogenic fermenter fed with a mixture of blended kitchen food‐waste and primary sludge from a sewage treatment plant was investigated for the production of volatile fatty acids (VFA). The operating variables for acidogenic fermentation were kitchen food‐waste content (10 and 25 wt %), hydraulic retention time (HRT: 1, 3 and 5 days), temperature (ambient: 18 ± 2 °C, and mesophilic: 35 ± 2 °C) and pH (varied from 5.2 to 6.7). The experimental results indicated that effluent VFA concentrations and VFA production rates were higher at ambient temperature than at mesophilic conditions. The net amount of VFA with 10 wt % food‐waste increased up to 920 mg dm^?3 with an increase of HRT, but contrasting results (a decrease of 2610 mg dm^?3) were found due to the conversion of VFA into biogas in the case of 25 wt % food‐waste, which increased significantly at HRT of 3–5 days. In terms of biogas composition (CO₂ and CH₄), the organic matter was converted into CO₂ through the oxidative pathway by facultative species at low temperature while mesophilic temperature and optimum pH (6.3–7.8) played a pivotal role in increasing rate of conversion of VFA into biogas by methanogenesis. Rates of VFA production and their conversion are dependent on the food‐waste content in the mixture. Yet, the higher concentration of food‐waste (25% compared with 10%) did not produce VFA proportionally due to the increased rate of conversion of VFA into gaseous products. The maximum VFA production rate (0.318 g VFA_produced g^?1 VS_fed day^?1) was achieved in the 10 wt % food‐waste at ambient temperature and at a 5‐day HRT. Copyright © 2005 Society of Chemical Industry     

A novel multienzyme electrode for the determination of citrate

A novel amperometric biosensor for the determination of citric acid in food samples and fermentation broths has been developed. The sensor is composed of citrate lyase (CL, EC 4.1.3.6), oxaloacetate decarboxylase (OAC, EC 4.1.1.3) and pyruvate oxidase (POP, EC 1.2.3.3), co-immobilized in gelatin, and an amperometric transducer. A Clark-type O₂-electrode and a modified Clark-type H₂O₂-electrode were alternatively used as a transducer. The biosensor covers a linear detection range from 1 μmol dm^?3 to 1 mmol dm^?3 citrate, with a response time of 2·5 min for the steady state response. The lower detection limit for citrate is 0·5 μmol dm^?3. The response of the sensor remained constant for 8 days and decreased to 25% after 18 days at 20–23°C. The results obtained from citrate determinations in food samples and fermentation broths agree well with those determined by enzymatic sample anlaysis. The relative standard deviation for citrate determinations with the new biosensor was 2·2% (n = 7).     

Preparation of a polymer containing indole groups by RAFT polymerization and one‐phase synthesis of AuNPs‐polymer nanocomposites

A one‐phase synthesis of AuNPs‐polymer nanocomposites using HAuCl₄ as the precursor is reported in this article. A flexible polymer, poly(2‐(4‐(di(1H‐indol‐3‐yl)methyl)phenoxy) ethyl methacrylate) (PMPEM), containing indole groups on the side chain was utilized as both a reducing reagent and soft template in the system. The PMPEM‐Au nanocomposites with three different sizes of AuNPs (25–50, 2, and 5 nm) were obtained just through choosing different solvents such as toluene, tetrahydrofuran (THF), and N,N‐dimethylformamide, respectively. Nanocomposites including the size of 25–50 and 2 nm AuNPs showed strong NLO absorption and refraction behaviors. The nonlinear refractive index n₂ of PMPEM‐Au nanocomposites prepared in toluene and THF were 9.35 × 10^?11 and 1.85 × 10^?10 m²/W, third‐order susceptibility χ⁽³⁾ were 2.55 × 10^?11 and 4.26 × 10^?11 esu, respectively. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Anionic polymerization of styrene in triglyme-benzene mixtures

Living anionic polymerization of styrene was kinetically investigated in triglyme-benzene mixtures. At low concentrations of triglyme the overall propagation rate constant, k_p, was much larger than at the same concentration of monoglyme (DME) in DME-benzene mixtures. The Szwarc-Schulz plot did not have negative slopes for lithium and sodium salts at triglyme contents of 5～20vol%, and no contribution of free anions to the propagation was observed for the sodium salt. The sodium ion pair was more highly reactive than the lithium ion pair; thus at 25°C, the ion pair rate constant, k′_p, for the lithium salt was 43, 102, 135 and 165 M^?1sec^?1 at triglyme concentrations of 5, 10, 15, and 20%, respectively, while that for the sodium salt was 410, 920, and 1460 M^?1sec^?1 in 5, 10, and 15% triglyme, respectively. The dissociation constant, K, for the lithium salt was 2·4×10^?11, 1·9×10^?10 and 1·3×10^?9 M in 10, 15, and 20% triglyme, respectively and the free ion rate constant, k″_p, was 2～2·5×10⁴ M^?1sec^?1 for the lithium salt.     

Acidic Characterization of Copper Oxide and Niobium Pentoxide Supported on Silica–Alumina

Copper oxide and niobium pentoxide were supported on silica–alumina with 2, 5, 10, 15 and 25 mass% loadings and 1:1 mass ratio of CuO:Nb₂O₅. XRD and BET measurements confirmed that monolayer coverage is reached with loadings between 5–10 mass% (～308 m² g^?1). The DRIFTS spectra of pyridine adsorbed catalysts showed bands associated with Brönsted, Lewis and a combination of both acidic sites. Thermal analysis and liquid phase microcalorimetry provided the parameters for the best catalyst (10 mass%), which has the highest number of acidic sites (0.38 mmol g^?1) and enthalpies of interaction with pyridine for Brönsted and Lewis sites (ΔH₁ = ?107.5 and ΔH₂ = ?64.4 kJ mol^?1, respectively).     

Crosslinked hydroxyl‐conductive copolymer/silica composite membranes based on addition‐type polynorbornene for alkaline anion exchange membrane fuel cell applications

Crosslinked hydroxyl‐conductive copolymer/silica composite membranes based on addition‐type polynorbornene, poly(dodoxymethylene norbornene‐co‐norbornene‐3‐(trimethylpropyl ammonium)‐functionalized silica (QP(DNB/NB‐SiO₂), were prepared by a sol–gel method. Copolymer composite membranes with different degree of quaternary ammonium functional silica, designated as QP(DNB/NB‐SiO₂‐X) (X = 5, 10, 15 and 25 wt%, respectively), displayed good dimensional stabilities with low in‐plane swelling rate of 1.32–3.7%, good mechanical properties with high elastic modulus of 605.4–756.8 MPa and high tensile strength of 13.2–20 Mpa. The achieved copolymer composite membranes could self‐assemble into a microphase‐separated morphology with randomly oriented long‐range aliphatic chain/cylinder ionic channels that were imbedded in the hydrophobic PNB matrix. Among these membranes, the QP(DNB/NB‐SiO₂‐25) showed the parameter with ionic conductivity of 9.33 × 10^?3S cm^?1, methanol permeability of 2.89 × 10^?7cm² s^?1, and ion‐exchange capacity(IEC) of 1.19 × 10^?3 mol g^?1. A current density of 82.3mA cm^?2, the open circuit voltage of 0.65 V and a peek power density of 32 mW cm^?2 were obtained. POLYM. ENG. SCI., 58:13–21, 2018. © 2017 Society of Plastics Engineers     

Proton Transfer in Liquid Ammonia Solutions Containing Water and Hydroxide Ion

The rate of proton transfer in ammonia solutions containing water and hydroxide ion was determined as a function of temperature and concentration by means of PMR spectroscopy. A first order dependence on hydroxide ion and second order dependence on water concentration was found with a rate constant of k₃ = 6.1 ± 1.2 × 10³ M^?2 sec^?1 at 25°C and ΔE^? = 4.5 ± 0.5 kcal/mole. The value of k₃ is in good agreement with that reported by other workers.     

Potential study of biopolymer-based carboxymethylcellulose electrolytes system for solid-state battery application

This paper focused on study of potential biopolymer carboxymethylcellulose (CMC) as electrolyte system for application in solid-state battery, which was prepared via solution casting technique. The highest conducting CMC biopolymer electrolytes (BE) was achieved at 1.12 × 10^?4 Scm^?1 with addition of 25 wt% NH₄Br and was improved to 3.31 × 10^?3 Scm^?1 when plasticized with 8 wt% EC. The solid-state battery was assembled using both systems with the configuration Zn +ZnSO₄.7H₂O // highest conducting BE // MnO₂ and showed promising performance at room temperature. This work implies that the possible practical application of the present biopolymer CMC as a new invention of electrolytes system in the fabrication of electrochemical devices.     

Preparation of pyridinemonocarboxylic acids by catalytic vapour phase oxidation of alkylpyridines. I. Oxidation of 2- and 3-picoline and decarboxylation of 2- and 3-pyridinecarboxylic acid in the vapour phase

The vapour phase oxidation of 2-picoline with air using a singly promoted vanadium catalyst (V₂O₅/SnO₂, mole ratio 1/1.5), at a temperature of 375°C and a space velocity of 6130 h^?1, gave a 69% conversion with a selectivity of 64% for 2-pyridinealdehyde. No pyridoin formation was detected. In the vapour phase oxidation of 3-picoline using a doubly promoted vanadium catalyst (V₂O₅-TiO₂-Na₂O with V/Ti/Na=100/20/1.15) at a temperature of 400°C and a space velocity of 1450 h^?1, a 94% conversion of 3-picoline was obtained with a selectivity of 51% for niacin (3-pyridinecarboxylic acid) and 1% for 3-pyridinealdehyde. By varying the atom ratio V/Ti, the catalyst V/Ti = 100/25 was found to be the most active one. The decarboxylation of 2- and 3-pyridinecarboxylic acid in the vapour phase was also investigated under the conditions used in the oxidation of the picolines to the acids. At 350°C about 90% decarboxylation of picolinic acid occurs under these conditions, while only a few per cent of the niacin decarboxylated to pyridine between 300 and 500°C.     

Adsorption of cadmium and zinc from aqueous solution on natural and activated bentonite

The adsorption of cadmium and zinc ions on natural bentonite heat-treated at 110°C or at 200°C and on bentonite acid-treated with H₂SO₄ (concentrations: 0·5 mol dm^?3 and 2·5 mol dm^?3), from aqueous solution at 30°C has been studied. The adsorption isotherms corresponding to cadmium and zinc may be classified respectively as H and L types of the Giles classification which suggests the samples have respectively a high and a medium affinity for cadmium and zinc ions. The experimental data points have been fitted to the Langmuir equation in order to calcualte the adsorption capacities (X_m) and the apparent equilibrium constants (K_a) of the samples; X_m and K_a values range respectively for 4·11 mg g^?1 and 1·90 dm³ g^?1 for the sample acid-treated with 2·5 mol dm^?3 H₂SO₄ [(B)-A(2·5)] up to 16·50 mg g^?1 and 30·67 dm³ g^?1 for the natural sample heat-treated at 200°C [B-N-200], for the adsorption process of cadmium, and from 2·39 mg g^?1 and 0·07 dm³ g^?1, also for B-A(2·5), up to 4·54 mg g^?1 and 0·45 dm³ g^?1 [B-N-200], for the adsorption process of zinc. X_m and K_a values for the heat-treated natural samples were higher than those corresponding to the acid-treated ones. The removal efficiency (R) has also been calculated for every sample; R values ranging respectively from 65·9% and 8·2% [B-A(2·5)] up to 100% and 19·9% [B-N-200], for adsorption of cadmium and zinc.