Interaction of Cl<Subscript>2</Subscript> and SO<Subscript>2</Subscript> with Finely Divided In<Subscript>2</Subscript>O<Subscript>3</Subscript>

The effect of O₂, Cl₂, and SO₂ on electrophysical and sorption properties of powdered In₂O₃ with a large specific area is studied at 23–200°C. The specimen is most sensitive to Cl₂ and SO₂ at near-room temperatures.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 529–536.Original Russian Text Copyright © 2005 by Vinokurova, Derlyukova.     

Mechanism of the Formation of O2? Radical Anions on CeO2 and (0.5–10)%CeO2/ZrO2 during the Adsorption of an NO-O2 Mixture

It is established by ESR that the adsorption of an NO + O₂ mixture at 20°C on oxidized CeO₂ (O₂, T = 400–700°C) produces radical anions O ₂ ⁻ located both on isolated Ce⁴⁺ cations (O ₂ ⁻ (1)) and in associated anionic vacancies (O ₂ ⁻ (2)). These species differ in thermal stability. For example, O ₂ ⁻ (2) decomposes at 20°C, while O ₂ ⁻ (1) decomposes at 50°C. Only O ₂ ⁻ (1) species are observed at −196°C in ZrO₂-supported CeO₂. In the case of NO + O₂ adsorption at 20°C, O ₂ ⁻ is stabilized on Zr⁴⁺ cations and decomposes at 270°C. Increasing the cerium oxide content of the ZrO₂ surface from 0.5 to 10% only partially inhibits the formation of O ₂ ⁻ -Zr⁴⁺. The Zr⁴⁺ cation is shown to possess a higher Lewis acidity than the Ce⁴⁺ cation, and the ionic bond in O ₂ ⁻ -Zr⁴⁺ complexes is stronger than that in O ₂ ⁻ -Ce⁴⁺ complexes. ESR, temperature-programmed desorption, and IR spectroscopic data for various adsorption complexes of NO on CeO₂ suggest that, in the key step of O ₂ ⁻ formation, free electrons appear on the surface owing to the conversion of adsorbed NO molecules into nitrito chelates on coordinately unsaturated ion pairs Ce⁴⁺-O ₂ ⁻ .__________Translated from Kinetika i Kataliz, Vol. 46, No. 3, 2005, pp. 414–422.Original Russian Text Copyright © 2005 by Il’ichev, Shibanova, Ukharskii, Kuli-zade, Korchak.     

Heterogeneous Equilibria in the System M<Superscript>m</Superscript>(BUO<Subscript>5</Subscript>)<Emphasis Type="Italic">m</Emphasis>·<Emphasis Type="Italic">n</Emphasis>H<Subscript>2</Subscript>O-Aqueous HCl

A quantitative model of the system crystalline uranoborate-aqueous solution was proposed on the basis of the experimental solubilities of Mm(BUO₅)m⋅nH₂O (M^m are alkaline and alkaline-earth metals) in aqueous HCl at 25°C. The model was used to predict the state of the heterogeneous systems under study under various conditions and to calculate the standard thermodynamic functions of the uranoborates.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 1, 2005, pp. 46–52.Original Russian Text Copyright © 2005 by Chernorukov, Nipruk, Knyazev, Khomyakova.     

Studies on synthesis, characterization and thermochemistry of Mg2[B2O4(OH)2]·H2O

A new magnesium borate Mg₂[B₂O₄(OH)₂]·H₂O has been synthesized by the method of phase transformation of double salt at hydrothermal condition and characterized by XRD, IR, TG and DSC. The enthalpy of solution of Mg₂[B₂O₄(OH)₂]·H₂O in 0.9764 mol L^–1 HCl was determined. With the incorporation of the enthalpies of solution of H₃BO₃ in HCl (aq), of MgO in (HCl+H₃BO₃) (aq), and the standard molar enthalpies of formation of MgO(s), H₃BO₃(s), and H₂O(l), the standard molar enthalpy of formation of –(3185.78±1.91) kJ mol^–1 of Mg₂[B₂O₄(OH)₂]·H₂O was obtained.This revised version was published online in November 2005 with corrections to the Cover Date.     

Synthesis and characterization of a novel crystalline AlPO4 molecular sieve,CFAP-7

The novel crystalline aluminophosphate CFAP-7, having a characteristic X-ray powder diffraction pattern, has been synthesized hydrothermally in a system consisting of di-n-butylamine-(NH₄)₂O–P₂O₅–Al₂O₃–H₂O at 120 to 140°C, the P₂O₅ and Al₂O₃ sources of which were provided by (NH₄)₃PO₄·3H₂O and Al₂(SO₄)₃ in aqueous solution, respectively. Investigations by DTA, TG, DTG, XRD, and IR indicate transformation of the original product (form A) into more stable crystal forms B and C on heating at about 180°C and 240°C, respectively, while liberating water and amine. Isotherms for the adsorption of water and methanol at 23°C show that both form B and form C are molecular sieves with a window dimension of 4.3–4.9 Å, and a methanol volume adsorbtion greater than that of water.     

The effect of pressure and temperature of self-diffusion coefficients in several concentrated deuterium oxide diamagnetic electrolyte solutions

The pressure dependences of the self-diffusion coefficients of deuterium oxide in 4.5m solutions of LiCl–D₂O and CsCl–D₂O (also 7m) and 3.06m CaCl₂–D₂O have been measured by the NMR spin-echo method at 30°C, 60°C, and 90°C. Shear viscosities and densities of these solutions have also been determined over the same range of experimental conditions. The experimental data show that the diffusion constantD decreases with the increasing structure-making ability of the electrolyte cation Ca⁺²>Li⁺. In contrast, the diffusion coefficient for D₂O in the 4.5 and 7m CsCl solutions is equal to that for pure D₂O at 30°C but lower at 60°C and 90°C. It has been found that the Stokes-Einstein equation relates well the diffusion coefficients to shear viscosity in these concentrated electrolyte solutions.     

Water-vapor pressure and thermodynamics of the dehydration of manganese,nickel, cadmium,and lead perchlorate hydrates

The water-vapor pressure has been measured by a static method, the temperature limits for existence have been determined, and the parameters of the equation lgp [Torr]=b —a/T have been calculated for the following crystal hydrates: Mn(ClO₄)₂ · 2H₂O (90–130°C, a=3527.0,b=8.487), Ni(ClO₄)₂ · 4H₂O (60–100°C,a=3606.7,b=9.704), Ni(C1O₄)₂ · 2H₂O (110–160°C,a = 4261.7,b = 10.103), Cd(ClO₄)₂ · 6H₂O (25–58.2°C,a = 3143.7,b = 9.356), Cd(ClO₄)₂ · 2H₂O (90–144.8°C,a=3823.3,b = 9.472), Pb(ClO₄)₂ · 3H₂O (10–47°C,a = 2932.9,b = 9.391 and 47–81.5°C,a = 2448.1,b=7.877), Pb(ClO₄)₂ · H₂O (60–102.4°C,a=3610.2,b = 9.857). A hitherto unknown metastable hydrate Cd(ClO₄)₂ · 4H₂O with a phase transition at 30.9°C (20–30.9°C,a = 3669.5,b = 11.343 and 30.9–63.7°C,a=3058.6,b = 9.339) has been detected.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 466–470, March, 1993.     

Formation of α-Alumina Around 500°C in Alkoxy-Derived Alumina Gels Under Ambient Pressure—Effects of Starting Solution Composition and Seeding

The hydrolysis of aluminum-sec-butoxide (ASB) in the ASB-H₂O-C₂H₅OH-HCl solutions at 0°C for 18 h and subsequent aging of the sol for 30 days at 5°C provided an alumina gel which was partially (20–30 wt%) transformed to -Al₂O₃ when heat-treated at 500°–600°C under ambient pressure. In addition to the hydrolysis and aging conditions, the amounts of water and HCl in the starting solution were found to be very important factors for the low temperature formation of -Al₂O₃ in the resultant gel. Some difference in the chemical environment of involved OH groups was found between the alumina gel forming -Al₂O₃ at 500°–600°C and the conventional gel. Corundum seeding was found to be effective; thus, 1 wt% seeding brought about an increase in the fraction of -Al₂O₃ formed at 600°C to 40–50 wt%.     

Zur Kenntnis der Reaktionsfähigkeit alkylsubstituierter Thiomorpholine, 2. Mitt.

Zusammenfassung Die Oxydation des 2-Methyl-3-äthylthiomorpholins (1) bzw. seines Hydrochlorids (1·HCl) mit 30proz. H₂O₂ liefert bei 0°C 87 bzw. 84% 2-Methyl-3-äthylthiomorpholin-1-oxid (4), bei 50°C 41 bzw. 46% 2-Methyl-3-äthylthiomorpholin-1,1-dioxid (7). Aus 2-Methyl-3-äthyl-4-formylthiomorpholin (2) bzw. 2-Methyl-3-äthyl-4-acetylthiomorpholin (3) erhält man die entspr. Sulfoxide (5 83%] bzw.6 [80%]), wenn man mit 30proz. H₂O₂ bei 0°C in Wasser bzw. Eisessig oxydiert, dagegen die entspr. Sulfone (8 [93%] bzw.9 [73%]), wenn in Ameisensäure bzw. Eisessig mit überschüss. 85proz. H₂O₂ bei 100°C oxydiert wird.8 und9 lassen sich mit verd. HCl glatt (ca. 90%) zu7 verseifen.Auf Basis von4 und7 werden zahlreiche s-Triazin-Derivate (10–26) und durch Addition von4 und7 an Isocyanate und Senföle einige Harnstoff- (27–31, 35–38) und Thioharnstoff-Derivate (32–34) dargestellt.

---

On the reactivity of alkyl substituted thiomorpholines, II¹ (Joint action of elemental sulfur and gaseous ammonia upon ketones, LXXXI²)

Oxidation of 2-methyl-3-ethyl-thiomorpholine (1) and the corresponding hydrochloride (1·HCl) with 30% H₂O₂ leads to the 2-methyl-3-ethyl-thiomorpholine-1-oxide (4) at 0°C in a yield of 87 and 84%, resp.; at 50°C 2-methyl-3-ethyl-thiomorpholine-1.1-dioxide (7) is formed in a yield of 41 and 46%, resp. By oxidation of 2-methyl-3-ethyl-4-formyl-thiomorpholine (2) and 2-methyl-3-ethyl-4-acetyl-thiomorpholine (3) with a 30% solution of H₂O₂ at 0°C in water or acetic acid, resp., the corresponding sulfoxides (5 [83%] and6 [80%]) are obtained; with an excess of 85% H₂O₂ in formic or acetic acid at 100°C the respective sulfones (8 [93%] and9 [73%]) are formed.8 and9 are easily saponified with dilute HCl to7 in a yield of about 90%.A large number of s-triazine derivatives (10–26) are prepared from4 and7; by addition of isocyanates and thio isocyanates to4 and7 urea- (27–31, 35–38) and thiourea derivatives (32–34) are obtained.

---

---

1. Mitt.:F. Asinger, H. Offermanns, A. Saus, C. Dudeck, D. Neuray undE. Wilms, Mh. Chem.104, 118 (1973).

---

80. Mitt.:F. Asinger, A. Saus undD. Neuray, Ann. Chem. (im Druck).

---

Teil der DiplomarbeitE. Wilms, Techn. Hochschule Aachen, 1969; Teil der DissertationE. Wilms, Techn. Hochschule Aachen 1971.     

Preparation and characterization of silicate gel glasses containing Cr2O3

The effect of thermal treatment on the structural incorporation of Cr₂O₃ in xCr₂O₃·(100 – x)SiO₂ and 5R _n O·xCr₂O₃·(95 – x)SiO₂ (where x=0.01–1 mol.% and R=Li, Na and Ca) gel glasses was studied by optical absorption spectrophotometry, DTA-TG, XRD and electron microscopy.Samples heat treated at 60°C have green color due to the presence of Cr³⁺ in octahedral coordination. The optical transmission, and color (yellow, orange or ambar), of the samples heat treated between 200 and 700°C prove that Cr³⁺ (octahedrally coordinated) and Cr⁶⁺ (tetrahedrally coordinated) are both present. Segregation of Cr₂O₃ take place at temperatures above 800°C.In reducing conditions the gel glasses were green due to the presence of a high content of Cr³⁺ ions. Samples containing Li or Na show crystalline phases at temperatures below 850°C.     

Redox Equilibria in the System Fe(OH)3(H2SO4)-Na2SO3-H2O Involving Precipitation of Iron(II) Sulfite as a Fe2O3 Precursor

Experimental data on the equilibria Fe²⁺/Fe³⁺ and SO₃ ²⁻/SO₄ ²⁻ in the system Fe(OH)₃(H₂SO₄)-Na₂SO₃-H₂O are presented. The quantitative relations between the reduction of Fe(III) and the precipitation of FeSO₃·2.5H₂O as a Fe₂O₃ precursor have considered graphically.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 1, 2005, pp. 41–44.Original Russian Text Copyright © 2005 by Vasekha, Motov.     

Effects of SO 4 2− , S2O 3 2− and HSO 4 − ion additives on the pitting corrosion of pure aluminium in 1 M NaCl solution at 40–70 °C

Effects of sulphate (SO₄^2–), thiosulphate (S₂O₃^2–) and hydrogensulphate (HSO₄^–) ion additives on the pitting corrosion of pure aluminium in 1 M NaCl solution have been investigated at various solution temperatures T_s, 40–70 °C using potentiodynamic polarisation experiment, double current step experiment and scanning electron microscopy (SEM). From the analysis of the galvanostatic potential transients obtained from the double current step experiment, it was suggested that both SO₄^2– and S₂O₃^2– ions retard the initiation of the etch pits, and that they also inhibit the passivation of the etch pits during the current interruption to promote the subsequent re-activation of the etch pits over the whole range of T_s. In contrast, it was found that HSO₄^– ions promote the initiation of the etch pits and at the same time, they enhance the passivation of the etch pits during the current interruption with rising T_s. From the SEM micrographs, it was revealed that as T_s increased the pit morphology changed from circular shape to irregular shape with rough surface in the presence of SO₄^2– or S₂O₃^2– ions, but it changed to strip-like shape in the presence of HSO₄^– ions. The beneficial effects of anion additives on the increase in surface area were discussed on the basis of the morphological change of the etch pits in the presence of anion additives.     

Ionic conduction of a high-temperature modification of Lu<Subscript>2</Subscript>Ti<Subscript>2</Subscript>O<Subscript>7</Subscript>

A nanoceramic product of the composition Lu₂Ti₂O₇ is synthesized by a coprecipitation method with a subsequent sublimation drying and an annealing at 650–1650°C. The conduction of Lu₂Ti₂O₇ synthesized at 1650°C is ionic (10^–3 S cm^–1 at 800°C). Thus, a new material with a high ionic conduction has been discovered. The ordering in Lu₂Ti₂O₇ is studied by methods of RFA, RSA, IK spectroscopy, electron microscopy, and impedance spectroscopy. The existence of a low-temperature phase transition fluorite-pyrochlore at 800°C and a high-temperature conversion order-disorder at 1650°C are established.Translated from Elektrokhimiya, Vol. 41, No. 3, 2005, pp. 298–303.Original Russian Text Copyright © 2005 by Shlyakhtina, Ukshe, Shcherbakova.     

Kinetics of diamminesilver(I)-catalysed oxidation of sulphur(IV) by dioxygen in ammonia buffers

The kinetics of the silver(I)-catalysed autoxidation of SO₃ ^2– into SO₄ ^2– in ammonia–ammonium nitrate buffer obeyed the rate law:R _obs=k₁ k₂ K[Ag^I]_T[SO₃ ^2-}][O₂] / ([NH₃]+K[SO₃ ^2-])(k₁+k₂[O₂])The values of k ₁, k ₂/k _–1 and K were found to be 1.2l mol^–1 s^–1, 5.3 × 10² l mol^–1 and 0.6 respectively at 30 °C. Two alternative free radical mechanisms have been proposed.     

The acidity functionsH 0 s of HCl solutions in EtOH with low water content

The acidity functionsH ₀ ^s of HCl solutions in EtOH-H₂O solvents containing 1.09, 3.0, and 5.0% water have been measured at 25 and 40 °C by the indicator method. The concentration of HCl changes from 10^–2 to 36m. Nitroanilines, for which a protonation mechanism is realized in the studied systems, were used as indicators.For each solvent,H ₀ ^s is temperature independent atm _HCl < 4, and acidity atm _HCl > 4 mol L^–1 increases more rapidly at 25 °C than at 40 °C. The acidity functions of aqueous and water-ethanol solutions of HCl were compared, and the concentrations of proton solvates of different compositions and their relative protonating ability were evaluated.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1722–1725, October, 1994.This work was financially supported by the Russian Foundation for Basic Research (Project No. 93-03-18356).     

The Solubility of Sodium Sulfate and the Reduction of Aqueous Sulfate by Magnetite under Near-Critical Conditions

The solubility of Na₂SO₄ (s) (thenardite) and the interactions between magnetiteand aqueous Na₂SO₄ near the critical point of water have been determined in azirconium-alloy flow reactor at temperatures 350°C t 375°C and isobaricpressures 190 p 305 bar. The experimental solubility data are describedwell as a function of temperature and solvent density ₁ byln x(Na₂SO₄, aq.) = –10.47 – 27550/T +(4805/T) ln ₁.The interaction between magnetite and Na₂SO₄ (aq.) was examined from 250 to370°C at molalities near the saturation composition of Na₂SO₄ (s). While no solidreaction products were observed, HS^– (aq.) was observed to form above 350°Cby sulfate reduction, as a product of the reaction8 Fe₃O₄(s) + Na₂SO₄ (aq.) + H₂O(l)= 12 Fe₂O₃ (s) + NaHS (aq.) + NaOH (aq.).The reduction reaction appears to be controlled by surface reaction kinetics, ata level well below the equilibrium molality of HS^– (aq.). Metallic iron reactedwith Na₂SO₄ (aq.) in a similar fashion at temperatures above 350°C, to yieldhigher molalities of HS^– (aq.).     

Conduction and Ion Transport in LaYO<Subscript>3</Subscript> Doped with CaO

Values of partial conductions (ionic: protonic, oxygen, hole) and their activation energies in LaYO₃ are determined at 700–1050°C, pO₂ ranging from air to 10⁻¹⁵ Pa, and pH₂O = 0.04–13.5 kPa for different versions of doping with calcium (when introduced into the lanthanum or yttrium sublattices, or into both sublattices simultaneously). The conductivity increases in the series La_0.97Ca_0.03YO_{3 − α} < LaY_0.97Ca_0.03O_{3 − α} < La_0.985Y_0.985Ca_0.03O_{3 − α}, which means that the stoichiometric composition with a 1 : 1 ratio between Y and La has the highest conductivity.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 610–615.Original Russian Text Copyright © 2005 by Balakireva, Stroeva, Gorelov.     

Solid state thermal isomerisation of diethylenetriamine complexes of NiX2 (X=NO3, ClO4, BF4 and CF3SO3)

Summary [Ni(dien)₂]X₂·nH₂O (dien=diethylenetriamine; n=0, X=NO₃ or CF₃SO₃; n=0.5, X=ClO₄ or BF₄ and n=2, X=CF₃SO₃) complexes have been prepared and investigated thermally in the solid state. [Ni(dien)₂](NO₃)₂ (1) and [Ni(dien)₂](CF₃SO₃)₂ (2) undergo endothermic irreversible phase transitions (209–247°C and 184–205°C; H=5.6 kJ mol^–1 and 7.7 kJ mol^–1 for (1) and (2), respectively). [Ni(dien)₂](ClO₄)₂·0.5H₂O (3) shows an endothermic irreversible phase transition after deaquation (201–216°C; H=7.7 kJ mol^–1). [Ni(dien)₂](BF₄)₂·0.5H₂O also shows an endothermic irreversible phase transition after deaquation, accompanied by partial decomposition. All the complexes possess octahedral geometry with the ligands arranged meridionally. The phase transitions are explained in terms of conformational changes of the triamine chelate rings.Author to whom all correspondence should be directed. Supplementary data available: i.r. spectra (Table 4) and x-ray diffraction patterns (Table 5).     

Effect of Copper on Solid Electrolytes (Ce0.8Sm0.2)1 ? xCuxO2 ? δ and Composite Cathodes Based on La0.8Sr0.2MnO3

The phase composition and electroconduction in air of solid electrolytes (Ce_0.8Sm_0.2)_{1 − x} Cu_xO_{2 − δ} (CSCu), where x = 0, 2, 5, 10, and 20 mol % and which are synthesized using the ceramic technology, are studied. Adding an additive of CuO lowers the CSCu sintering temperature by 100– 200°C and leads to the formation of single-phase solid solutions of a fluorite type up to x = 10 mol %. The electroconductivity of the CSCu electrolytes remains practically invariant upon adding up to 5 mol % Cu and equals 0.089–0.095 and 0.017–0.021 S cm⁻¹ at 800 and 600°C. The sintering, adhesion, and electroconductance of composite cathodes based on La_0.8Sr_0.2MnO₃ with 40% CSCu and their electrochemical behavior in air in the temperature interval 900–1000°C on carrying electrolyte Zr^0.9Y_0.1O_1.95 with a CSCu sublayer containing 2 mol % Cu are studied.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 656–661.Original Russian Text Copyright © 2005 by Bogdanovich, Gorelov, Balakireva, Dem’yanenko.     

Insect pheromones and their analogues. XVI. Practical synthesis of hexadec-9Z-enal — A component of the sex pheromone of the cotton bollwormHeliothis armigera

A synthesis of hexadec-9Z-enal — a component of the sex pheromone of the cotton boll-wormHeliothis armigera (Hübner) — based on cyclooctene (I) is proposed. Through a solution of 22 g of (I), 250 ml of cyclohexane, and 40 ml of MeOH is passed (at 5°C) 0.2 M O₃/O₂, the solution is decanted off, and the precipitated ozonide is dissolved in 200 ml of MeOH and is reduced with 19 g of NaBH₄ (40°C) with the isolation, after the usual working up, of 23.4 g of octane-1,8-diol (II). From 0.5 mole of (II) and 0.6 mole of 45% HBr 8-bromooctan-1-ol (III) is obtained and this is converted into 1-(2-THPL)oxy)-8-bromooctane (IV). The condensation of (IV) with oct-1-yne (Ar, LiNH₂, HMPTA, 10°C, 1 h, and then 55°C, 10 h) leads to 1-(2-THPL-oxy)hexadec-9-yne (V) the hydrolysis of which (MeOH, H₂O, p-TsOH, 20°C for 20 h) yields hexadec-9-yn-ol (VI). The reduction of (VI) (Et₂O, iso-BuMgBr, Cp₂TiCl₂, 0°C, 15 min, then 20°C, 1 h) yieldshexadec-9Z-en-l-ol (VII). The oxidation of (VII) (PyHCrO ₃ ⁺ Cl^–, CH₂Cl₂, 20°C, 2 h) gives hexadex-9Z-enal (VIII). Characteristics of the compounds (yield (%), n _D ^{20 (25)}: (II) – 80, mp 61–62°C; (III) – 75, 1.4807; (IV) – 99, —; (V) – 52, 1,4650; (VI) – 85, 1.4657; (VII) – 99, 1.4650; (VIII) – 98, 1.4600. Characteristics of the IR and PMR spectra of compounds (V–VII) are given.Institute of Chemistry, Bashkir Branch, Academy of Sciences of the USSR, Ufa. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 286–289, March–April, 1987.