Electrophilic chlorination of methane over superacidic sulfated zirconia

Catalytic chlorination of methane was studied over SO ₄ ^2– /ZrO₂, Pt/SO ₄ ^2– /ZrO₂, and Fe/Mn/SO ₄ ^2– /ZrO₂ solid superacid catalysts. The reactions were carried out in a continuous flow reactor under atmospheric pressure, at temperatures below 240°C, with a gaseous hourly space velocity of 1000 ml/g h and a methane to chlorine ratio of 4 to 1. At 200°C with 30% chlorine converted the selectivity in methyl chloride exceeds 90%. At more elevated temperatures, the selectivity decreases but stays above 80% in methyl chloride at 225°C using the sulfated zirconia catalysts. The selectivity can be enhanced by adding platinum to sulfated zirconia catalysts. An iron and manganese-doped catalyst exhibited excellent selectivities at somewhat lower conversions. Methyl chloride is obtained at 235°C in selectivities greater than 85%. No chloroform or carbon tetrachloride is formed. The electrophilic insertion involves electron-deficient metal-coordinated chlorine into the methane C-H bond.Catalysis by solid superacids, 29. For part 28 see ref. [14].     

The Effect of Aluminum Ions on the DC Etching of Aluminum Foil

A study has been made of the electrochemical etching of 99.99% aluminum foils at a current density of 50 mA cm^–2in AlCl₃–HCl solutions (1 m Cl^–) at 80 °C. The solutions were made by dissolving metallic aluminum into 1m HCl solution, to give a Cl^– concentration of 1 m. The number density of etch tunnels and the homogeneity of tunnel length decreased, and the mean pit size and its standard deviation increased with increasing Al³⁺ concentration. The results were discussed based on potential transients at a current density of 50 mA cm^–2, current–potential curves at a scan rate of 10 m Vs^–1 and electrochemical impedance spectra.     

Raman spectroscopy studies of concentrated vanadium redox battery positive electrolytes

Spectroscopic changes in highly concentrated vanadium(V)-sulfate solutions to be used in the vanadium redox battery are consistent with the presence of more than one V(V)-sulfate species. The results of Raman spectroscopy indicate that the major species in highly acidic conditions are VO₂SO₄ ^–, VO₂(SO₄)₂ ^3–, VO₂(HSO₄)₂ ^–, VO₃ ^–, V(V) dimers with V₂O₃ ⁴⁺ and V₂O₄ ²⁺ central units. The nature and amount of these species depends upon the V(V) and total sulfate concentrations as well as on S to V and H⁺ to V ratios in the positive half-cell electrolyte. V(V) forms V₂O₃ ⁴⁺, VO₂(SO₄)₂ ^3– and their copolymer species at higher total sulfate concentrations, which tends to stabilize the vanadium (V) positive electrolyte in the vanadium redox battery. The V(V) and V(IV) species show the least interaction with each other. Ageing of concentrated V(V) solutions at elevated temperature (50 °C) produces decomposition of species causing formation of V₂O₅ precipitates with a decrease in the amount of vanadium polymer.     

Low-Temperature SCR of NO with NH3 over USY-Supported Manganese Oxide-Based Catalysts

A series of catalysts of manganese oxide, manganese–cerium and iron–manganese oxide supported on USY (ultra-stable Y zeolite) were studied for the low-temperature selective catalytic reduction (SCR) of NO with ammonia in the presence of excess oxygen. It was found that MnO_x/USY have high activity and high selectivity to N₂ in the temperature range 80-180 °C. The addition of iron and cerium oxide increased NO conversion significantly although the single-component Fe/USY and Ce/USY catalysts had low activities. Among the catalysts studied in this work, the 14% Ce-6% Mn/USY showed the highest activity. The results showed that this catalyst yielded nearly 100% NO conversion at 180 °C at a space velocity of 30 000 cm³ g^-1 h^-1. The only product is N₂ (with no N₂O) below 150 °C. The effects of the concentration of oxygen, NO and NH₃ were studied and the steady-state kinetics were also investigated. The reaction order is 1 with respect to NO and zero with respect to NH₃ on the 14% Ce-6% Mn/USY catalyst at 150 °C.     

Osmium ligand deficient clusters as catalysts for liquid phase hydrocarbon transformations

Reduction of OsO₄ by molecular hydrogen in alkane (cycloalkane) or benzene media at 20–150 °C yields small osmium clusters of the Os₁C_0.34-0.48H_0-0.6 composition with a specific surface area of 34–46 m²/g. The systems obtained are shown to be ligand deficient osmium clusters (LDC) of 7–16 Å in diameter, stabilized by a small amount of carbonaceous ligands with Os-Os = 2.68-1.70 Å and Os-C = 2.11-2.19 Å. The characteristics of these chemically prepared Os-LDC are similar to those of Ni- and Co-LDC, prepared by a vapour phase synthesis. The novel Os-LDC effectively catalyze hydrogenolysis of alkanes and cycloalkanes at 100–150 ° C and initial H₂ pressure of 5 MPa, hydrogenation of cyclopentadiene and arenes at 20 ° C, multiple H/D exchange between CH₄ and D₂ at 100–120 ° C and methanation of CO₂ at 150–180 ° C.     

Low-temperature SCR of NO with NH3 over noble metal promoted Fe-ZSM-5 catalysts

We have reported previously the excellent performance of Fe-exchanged ZSM-5 for selective catalytic reduction (SCR) of NO with ammonia at high temperatures (300–400 °C). In this work, we found that the reaction temperature could be decreased to 200–300 °C when a small amount of noble metal (Pt, Rh, or Pd) was added to the Fe-ZSM-5. The SCR activity follows the order Pt/Fe-ZSM-5 > Rh/Fe-ZSM-5 > Pd/Fe-ZSM-5 at 250 °C. On the Pt promoted Fe-ZSM-5, 90% NO conversion was obtained at 250 °C at GHSV = 1.1 × 10⁵ h^–1. Moreover, the noble metal improved the resistance to H₂O and SO₂. The presence of H₂O and SO₂ decreased the SCR performance only very slightly.     

First In Situ Raman Study of Vanadium Oxide Based SO2 Oxidation Supported Molten Salt Catalysts

In situ Raman spectroscopy at temperatures up to 500°C is used for the first time to identify vanadium species on the surface of a vanadium oxide based supported molten salt catalyst during SO₂ oxidation. Vanadia/silica catalysts impregnated with Cs₂SO₄ were exposed to various SO₂/O₂/SO₃ atmospheres and in situ Raman spectra were obtained and compared to Raman spectra of unsupported model V₂O₅–Cs₂SO₄ and V₂O₅–Cs₂S₂O₇ molten salts. The data indicate that (1) the V^V complex V^VO₂(SO₄)₂ ^3– (with characteristic bands at 1034 cm^–1 due to (V=O) and 940 cm^–1 due to sulfate) and Cs₂SO₄ dominate the catalyst surface after calcination; (2) upon admission of SO₃/O₂ the excess sulfate is converted to pyrosulfate and the V^V dimer (V^VO)₂O(SO₄)₄ ^4– (with characteristic bands at 1046 cm^–1 due to (V=O), 830 cm^–1 due to bridging S–O along S–O–V and 770 cm^–1 due to V–O–V) is formed and (3) admission of SO₂ causes reduction of V^V to V^IV (with the (V=O) shifting to 1024 cm^–1) and to V^IV precipitation below 420°C.     

Electrical conductivity and oxygen semipermeability of terbia and yttria stabilized zirconia

This paper reports an electrochemical study on terbia and yttria stabilized zirconia. (Tb, Y)-ZrO₂ solid solutions with a fluorite type structure were prepared by using citrate synthesis and sintered at 1500°C. They are mixed electronic and oxygen ionic conductive, as well as oxygen semipermeable materials at elevated temperatures. The total electrical conductivity reaches 3.8 S m^–1 at 900°C and the oxygen permeation is about 6.5 × 10^–6 mol m^–2 s^–1 at 1100°C. The electrical conductivity of zirconia doped with a total of 30 mol % of terbia and yttria increases with oxygen partial pressure when P _{O 2} is below 10^–2 atm, and decreases as the oxygen partial pressure rises above 10^–2 atm. This is ascribed to the defect association and the predomination of oxygen ionic conductivity. The oxygen semipermeation is proportional to the square root of the oxygen partial pressure, and is not influenced by the variation of oxygen ionic or electronic conduction. The results indicate that the surface exchange reaction is most probably the rate limiting step for the oxygen semipermeation.     

Anionic Clays as Potential Slow-Release Fertilizers: Nitrate Ion Exchange

Several nitrate containing anionic clays were synthesized at different temperatures and the kinetics of NO₃ ^– release were determined to test their suitability as slow-release N fertilizers. A sample (Mg:Al = 2:1) synthesized at 60°C with smaller particle size released 75, 86 and 100% of its NO₃ ^– in 1, 3 and 7 days, respectively when equilibrated with a simulated soil solution. On the other hand, the 175°C/2 hrs sample with larger particle size released 65, 77 and 84% of its nitrate in 1, 3 and 7 days, respectively. Another anionic clay (synthesized at 175°C/24 hrs) of higher charge density (Mg:Al = 2:1) containing NO₃ ^– was equilibrated with a 0.012 N NaCl or Na₂CO₃ to test the role of different anions in releasing the NO₃ ^– anion from the interlayers. The results showed that Cl^– released more NO₃ ^– than did CO₃ ^2– from this anionic clay after all the treatment times probably as a result of the CO₃ ^2– anion blocking the release of NO₃ ^– from the interior of the crystals. When a lower charge density (Mg:Al = 3:1) sample (synthesized at 175°C/48 hrs) was equilibrated with 0.02N solution of anions the release of nitrate was as follows: Cl^– < F^– < SO₄ ⁼ CO₃ ^2–. These results suggest that the divalent SO₄ ⁼ and CO₃ ^2– anions are more effective in the release of NO₃ ^– from this lower charge density anionic clay. Time-resolved structural analysis of NO₃ ^– exchange with CO₃ ^2– in the above anionic clay using synchrotron x-ray diffraction showed that ion exchange is rapid because of small crystal size and lower charge density. Thus the release of NO₃ ^– from anionic clays is an interplay among the type of anions present in soil solution, their concentration, pH of soil solution, the charge density and crystal size of anionic clay etc.     

Measurements on the temperature dependence of the cationic polymerization of styrene in CH2Cl2 with CF3SO3H as catalyst

Summary The cationic polymerization of styrene in CH₂Cl₂ with CF₃SO₃H as catalyst and at low monomer concentrations shows, at –15°C, –45°C and –60°C, the same formal dependence on monomer concentration. The dependence on the catalyst concentration is approximately but not exactly of a third order.The unimodal molecular weight distributions at [M]_o<0.2 mol·1^–1 become broader with decreasing polymerization temperature and increasing monomer concentration and change to bimodal or trimodal distributions at [m]_o>0.2 mol·1^–1. The addition of (Bu)₄N⁺CF₃SO₃ ^– to the polymerization system shows that the two higher molecular peaks are produced by free ions. The activation energy of the total reaction is found to be 3.5 kcal·mol^–1.I thank Prof. G. V. Schulz for interesting discussions and the possibility to work in his group, G. Greschner for a computer program and the Alexander von Humboldt Stiftung for their financial help.     

Decomposition voltage for the electrolysis of alumina at low temperatures

The apparent decomposition voltage for the electrolysis of alumina in an equimolar Na₃AlF₆-Li₃AlF₆ electrolyte was measured over a temperature range of 800 to 1000° C by the extrapolation of voltagecurrent plots to zero current. Temperature coefficients of –1.9 and –2.4 mV° C^–1 were determined for conditions of variable alumina activity (constant concentration) and unit activity (saturated), respectively. The overvoltage contribution to the temperature dependency was estimated to be about –1.6mV° C^–1 (versus a –0.6 mV° C^–1 dependency for the reversible decomposition voltage). Reduced alumina solubility at low temperatures also appeared to increase the overvoltage, but was of secondary importance.Based on work partially supported by the US Department of Energy (Contract DE-AC03-76CS40215: Energy Savings Through the Use of an Improved Reduction Cell Cathode).     

Thermal battery cells utilizing molten nitrates as the electrolyte and oxidizer

The Ca/LiNO₃-LiCl-KCl (50-25-25 mol%) thermal battery cell can be activated at 160° C and operated over a temperature range of 250–450° C to produce 2.5–2.8 V at open-circuit and initial operating voltages above 2 V at 10 mA cm^–2. At operating temperatures between 250 and 350° C, this system shows promise for applications requiring a sixty-minute thermal battery. Cell lifetimes decrease at higher temperatures due to the accelerating reaction of calcium with the molten nitrate salt to form gaseous products. An experimental energy density value of 142 Whkg^–1 was obtained at 300° C during constant current discharge at 10 mAcm^–2. Effects of applied face pressure on cell discharge characteristics were small. At current densities above 20–30 mA cm^–2, the cell performance deteriorates due to polarization at the anode. This is probably caused by the precipitation of CaO which blocks the active sites at the anode.     

Effect of coating thickness and surface treatment of titanium on the properties of IrO2-Ta2O5 anodes

The effect of coating thickness and the effect of surface treatment of the titanium base metal on the surface morphology and electrochemical properties of IrO₂-Ta₂O₅ anodes were investigated. It was observed that for an iridium content of 0.45–1.2 mg cm^–2 the service life is proportional to the iridium content in the coating. During etching of titanium in 5% HF at 25 °C a surface with macroroughness is formed, while during etching in HCl at 30, 50 and 80°C a microrough surface with visible pitting is formed. The morphology of the IrO₂-Ta₂O₅ active layer (0.32–0.39 mg Ir cm^–2) depends strongly on the pretreatment of the titanium base metal. After etching of titanium in HF, the resulting IrO₂-Ta₂O₅ layer is adherent to the macrorough surface of the titanium base metal. After etching of titanium in HCl the resulting surface of the IrO₂-Ta₂O₅ layer is microrough with partly filled pitting holes. The service life of IrO₂-Ta₂O₅ coating with different roughness does not differ and has a value of 1500 ± 400 h (0.5 M H₂SO₄, 25 °C and j = 2 A cm^–2).     

Mechanical properties and recrystallization of alumina ceramics reinforced by silicon carbide whisker

The mechanical properties and recrystallization of a material consisting of Al₂O₃ and SiC whisker are considered for different hot pressing regimes. The best properties are obtained at an SiC whisker content of 20% in hot pressing in an argon medium at 1600°C (the ultimate bending strength is 600 MPa, the critical coefficient of stress intensityK _Ic=5.5 MPa · m^1/2). The bending strength measured at 1000°C is at least 400 MPa for the material pressed at 1700°C in air. It is established that the presence of SiC whisker on grain boundaries of Al₂O₃ noticeably impedes the growth of alumina grains in recrystallization for all chosen regimes of hot pressing (1650 – 1900°C, 15 – 45 min). The dominant grain size is 1 –5 µm. A mathematical model is suggested for evaluating the maximum grain size in uniform grain growth, which isD*=0.571 [1++(1+16.151/f)^1/2]d, whered, f are the diameter and the volume fraction of SiC whisker. The material can be recommended for use under conditions of thermomechanical stress and abrasive wear.Translated from Ogneupory, No. 5, pp. 8 – 12, May, 1995.     

A rechargeable battery of the type polyaniline/propylene carbonate-LiClO4/Li-Al

A secondary battery of the type polyaniline/propylene carbonate-LiClO₄/Li–Al is described. The polymer is made by aniline oxidation with ammonium persulphate in NH₄F, 2.3 HF as solvent. The discharge capacity of the polymer is 100 Ah kg^–1 at 25°C and 140 Ah kg^–1 at 40°C for current densities of 0.5 mA cm^–2 and for an amount of material giving a capacity of 10 mAh. The voltage in open circuit for the fully charged battery is 3.6 V. The average usable potential is 2.8–3 V. The energy density for the polymer lies between 280 and 420 Wh kg^–1. The ratio of the amounts of electricity in discharge and charge is one for several hundred deep cycles. The behaviour with regard to self discharge and to constant applied voltage (floating life) is excellent.     

Determination of the diffusion coefficient of yttrium in the Ni2Y phase

A uniform Ni₂Y layer was formed on a nickel substrate by electrolysis of yttrium ions in molten LiC-KCl-NaCl at 500°C, and the diffusion coefficient of yttrium in Ni₂Y was found to be (2.84 ± 0.40) × 10^–8 cm²s^–1 using an electrochemical transient technique.     

Effects of calcining conditions of kaolinite on pore structures of mesoporous materials prepared by the selective leaching of calcined kaolinite

This paper describes the effects of calcining conditions of kaolinite on pore structures of the porous materials obtained from the selective leaching of calcined kaolinite using KOH solution. Mesoporous -Al₂O₃ was the predominant crystalline phase in the samples calcined in the temperature range between 950°C and 1050°C for 24 h. The mean specific surface area of these samples was approximately 250 m² · g^–1 and the mean total pore volume was approximately 0.8 ml · g^–1. The pore size distribution curves of these samples showed a sharp peak at around 2–3 nm pore radius. This peak was sharper for the sample calcined at 1000°C for 24 h. On the other hand, the pore sizes of the sample calcined at 1100°C for 24 h increased abruptly to 10–20 nm and this change corresponded to the formation of mullite in the sample. The pore sizes of the samples calcined at 1100°C varied with calcining time. The specific surface area and total pore volume decreased, the longer the calcining time of the samples, and this was correlated with an increase in the amount of mullite in the samples.     

Studies on the redox behaviour of La1.867Th0.100CuO4 and its catalytic performance for NO decomposition

La_1.867Th_0.100CuO₄ was prepared by means of the citric acid complexing method. The reduction–oxidation (redox) properties of this composite oxide have been investigated by using the XRD, TGA, EPR, TPD, and SEM methods. The fresh (non-reduced) La_1.867Th_0.100CuO₄ catalyst is single phase with tetragonal K₂NiF₄-type structure. There were three reduction steps observed over La_1.867Th_0.100CuO₄ in the temperature ranges of 25–100, 100–300, and 300–500 °C, respectively. After reduction at 300 °C, the material still retained its original single phase but there were oxygen vacancies generated in the lattice. After reduction at 500 °C, it decomposed to a mixture of oxides. In the course of reduction, trapped electrons were generated. During the oxidation of the reduced sample, O ₂ ^– was detected. Apparently, oxygen vacancies are able to stabilise O ₂ ^– on the surface of the -1ptcatalyst. NO adsorption on both the fresh and reduced La_1.867Th_0.100CuO₄ samples generated NO radicals and O ₂ ^– species. On a La_1.867Th_0.100CuO₄ sample reduced at 300 °C, [O₂NO₂]^2– was generated in NO adsorption and decomposed to N₂ and O^2– at ca. 730 °C. After reduction, the O ₂ ^– inside the La_1.867Th_0.100CuO₄ lattice became more mobile and participated in the decomposition of [O₂NO₂]^2–. The fresh (non-reduced) La_1.867Th_0.100CuO₄ sample with cation defects in its lattice shows higher NO decomposition activity than the fresh La₂CuO₄ sample in which there are no cation defects. The 300 °C-reduced La_1.867Th_0.100CuO₄ with cation defects and oxygen vacancies is more active than the fresh one for NO decomposition. The redox action between Cu⁺ and Cu²⁺ is an essential process for NO decomposition.     

Properties of RO-Y2O3-Al2O3-SiO2 glasses

The coefficient of linear expansion, glass-transition temperature, temperature at the orset of deformation (strain point), density. Young modulus, microhardness, crystallizability, and contact angle are studied as a function of the composition in RO–Y₂O₃–Al₂O₃–SiO₂ (R=Ca and/or Mg) glass systems. The composition ranges for glasses (with strain point >900°C and coefficient of linear expansion of (32–45)×10^–7°C^–1) that can be used for soldering silicon-nitride ceramics were established.Translated from Steklo i Keramika, No. 12, pp. 5–7, December, 1996     

Preparation of Li–Mn–O thin films by r.f.-sputtering method and its application to rechargeable batteries

Spinel-LiMn₂O₄ thin films were fabricated on stainless steel substrate by the r.f.-sputtering method. They were annealed within the range 400–700 °C for 1 h in O₂ and their electrochemical performance was compared to that of as-deposited film. The thin films were characterized by X-ray diffractometry and electron spectroscopy for chemical analysis (ESCA). Charge–discharge tests were carried out in an LiClO₄/propylene carbonate solution. The films heat-treated at 400–700 °C exhibited excellent cyclability over a wide potential region from 2.0 to 4.3 V vs Li/Li⁺.