Studies on an ionic compound (3-ATz)+ (NTO)–: crystal structure, specific heat capacity, thermal behaviors and thermal safety

A new ionic compound (3-ATz)⁺ (NTO)^?C was synthesized by the reaction of 3-amino-1,2,4-triazole (3-ATz) with 3-nitro-1,2,4-triazol-5-one (NTO) in ethanol. The single crystals suitable for X-ray diffraction measurement were obtained by crystallization at room temperature. The crystal is monoclinic, space group p _2(1)/c with crystal parameters of a?=?0.6519(2)?nm, b?=?1.9075(7)?nm, c?=?0.6766(2)?nm, ???=?94.236(4)°, R ₁?=?0.0305 and wR ₂?=?0.0789. The thermal behaviors were studied, and the apparent activation energy and pre-exponential constant of the exothermic decomposition stage were obtained by Kissinger??s method and Ozawa??s method. The self-accelerating decomposition temperature is 505.40?K, and the critical temperature of the thermal explosion is obtained as 524.90?K. The specific heat capacity was determined with Micro-DSC method and the theoretical calculation method, and the standard molar specific heat capacity is 221.31?J?mol^?1?K^?1 at 298.15?K. The Gibbs free energy of activation, enthalpy of activation, and entropy of activation are 151.55?kJ?mol^?1, 214.52?kJ?mol^?1 and 122.44?J?mol^?1?K^?1. The adiabatic time-to-explosion of the compound was estimated to be a certain value between 5.0 and 5.2?s, and the detonation velocity (D) and pressure (P) were also estimated using the nitrogen equivalent equation according to the experimental density.     

Synthesis,conformational preferences in gas and solution,and molecular gear rotation in 1-(dimethylamino)-1-phenyl-1-silacyclohexane by gas phase electron diffraction (GED), LT NMR and theoretical calculations

1-(Dimethylamino)-1-phenyl-1-silacyclohexane 1, was synthesized, and its molecular structure and conformational properties studied by gas-phase electron diffraction (GED), low temperature ¹³C NMR spectroscopy and quantum-chemical calculations. The predominance of the 1-Ph_ax conformer (1-Ph_eq:1-Ph_ax ratio of 20:80%, ΔG°(317?K)?=??0.87?kcal/mol) in the gas phase is close to the theoretically estimated conformational equilibrium. In solution, low temperature NMR spectroscopy showed analyzable decoalescence of C_ipso and C(1,5) carbon signals in ¹³C NMR spectra at 103?K. Opposite to the gas state in the freon solution employed (CD₂Cl₂/CHFCl₂/CHFCl₂?=?1:1:3), which is still liquid at 100?K, the 1-Ph_eq conformer was found to be the preferred one [(1-Ph_eq: 1-Ph_ax?=?77%: 23%, K?=?77/23?=?2.8; ?ΔG°?=??RT ln K (at 103?K)?=?0.44?±?0.1?kcal/mol]. When comparing 1 with 1-phenyl-1-(X)silacylohexanes (X?=?H, Me, OMe, F, Cl), studied so far, the trend of predominance of the Ph_ax conformer in the gas phase and of the Ph_eq conformer in solution is confirmed.     

Preparation and ionic conductivity of (100−x)(0.8Li2S·0.2P2S5)·xLiI glass–ceramic electrolytes

The glass–ceramic electrolytes of (100?x)(0.8Li₂S·0.2P₂S₅)·xLiI (in mole percent; x?=?0, 2, 5, 10, 15, 20, and 30) were prepared by mechanical milling and subsequent heat treatment. Crystalline phases analogous to the thio-LISICON region II or III in the Li₂S–GeS₂–P₂S₅ system were precipitated. The thio-LISICON III analog phase was mainly precipitated at the composition x?=?0, and the thio-LISICON II analog phase was precipitated in the composition range from x?=?2 to 15. The X-ray diffraction peaks of the thio-LISICON II analog phase shifted to the lower diffraction angle side with increasing the LiI content. High conductivities above 2?×?10^?3?S?cm^?1 at room temperature were observed in the glass–ceramics at the wide composition range from x?=?2 to 15. The glass–ceramic electrolyte at x?=?5 with the highest conductivity of 2.7?×?10^?3?S?cm^?1 showed a wide electrochemical window of about 10 V. The addition of LiI to the 80Li₂S·20P₂S₅ (in mole percent) glass was effective in crystallizing the thio-LISICON II analog phase with high conductivity from the glass.     

Use of Styrene as Sole Carbon Source by the Fungus Exophiala oligosperma: Optimization and Modeling of Biodegradation, Pathway Elucidation, and Cell Membrane Composition

Biodegradation of styrene by Exophiala sp. was tested at different initial concentrations (19.3?C170.6?mg?l^?1), pH (2.8?C8.7), and temperatures (19.8?C45.1?°C), for 120?h according to a 2³ full-factorial central composite design. The specific growth rate (SGR, per hour) and specific styrene utilization rate (SUR, milligrams of styrene per milligram of biomass per hour) values were used as the response variables for optimization purposes. The interactions between concentration and temperature (P?=?0.022), and pH and temperature (P?=?0.010) for SGR, and interactions between concentration and temperature (P?=?0.012) for SUR were found to be statistically significant. The optimal values for achieving high SGR (0.15?h^?1) and SUR (0.3622?mg styrene mg^?1 biomass h^?1) were calculated from the regression model equation. Those values are C _o ?=?89.1?mg?l^?1, pH?=?5.4, and T?=?31.5?°C for SGR and C _o ?=?69.2?mg?l^?1, pH?=?5.5, and T?=?32.4?°C for SUR. It was also observed that the Exophiala strain degrades styrene via phenylacetic acid, involving initial oxidation of the vinyl side chain. Besides, in the presence of styrene, changes in the fatty acids profile were also observed. It is hypothesized that an increasing amount of linoleic acid (18:2) may be involved in the protection of the fungus against toxic substrate.     

Copolymer formation of 9-(2-(benzyloxy)ethyl)-9H-carbazole and 1-tosyl-1H-pyrrole coated on glassy carbon electrode and electrochemical impedance spectroscopy

In this work, 9-(2-(benzyloxy)ethyl)-9H-carbazole (BzOCz) and 1-tosyl-1H-pyrrole (TsP) monomers were chemically synthesized and characterized by Fourier transform infrared reflectance (FTIR) and proton nuclear magnetic resonance (¹H-NMR) spectroscopy. BzOCz and TsP were electrocoated on glassy carbon electrode (GCE) in various molar fractions (X _TsP?=?0.5, 0.83, 0.91, and 0.98) in 0.1?M sodium perchlorate/acetonitrile. The detailed characterization of poly(BzOCz-co-TsP) was studied by cyclic voltammetry, FTIR-attenuated total reflection spectroscopy and electrochemical impedance spectroscopy (EIS). The effects of different molar fractions during the preparation of modified electrodes were studied by EIS technique. The AC impedance technique was used to determine the capacitive behaviors of modified GCE via Nyquist, Bode magnitude, and Bode phase plots. The highest low frequency capacitance value was obtained as C _LF?=?23.94?μF?cm^?2 for X _TsP?=?0.98. Therefore, synthesized copolymer has more capacitive behavior than its homopolymers, such as C _LF?=?7.5?μF?cm^?2 for poly(BzOCz) and C _LF?=?9.44?μF?cm^?2 for poly(TsP). In order to interpret the AC impedance spectra, R(Q(RW)) electrical equivalent circuit was employed with linear Kramers–Kronig test. A mechanism for electropolymerization has been proposed for copolymer formation.     

Partial crystallization in exotic phase stishovite of amorphous silica xerogels induced by incorporation of chlorophyll species

Using the Rietveld refinement, we analyze the structural evolution under thermal treatment of silica xerogel samples with incorporation of extract from frozen spinach leaves, prepared by sol?Cgel method with low molar ratio (R) of water to TEOS of R?=?1, and R?=?5. Partial crystallization of silica xerogel in the form of stishovite has been obtained at atmospheric pressure conditions and temperatures of 200?°C, they both, very lower than those specified by the phase diagram, in samples containing chlorophyll aggregates dispersed in amorphous silica. The results show that the incorporation of spinach extracts leave together with low water contents induce devitrification of the silica matrix in exotic phase stishovite.     

LCST behavior of copolymers of N-isopropylacrylamide and N-isopropylmethacrylamide in water

The lower critical solution temperature (LCST) behavior of copolymers of N-isopropylacrylamide (NiPA) and N-isopropylmethacrylamide (NiPMA) in water was studied as a function of the copolymer composition, using a combination of turbidity measurements and differential scanning calorimetry (DSC). The copolymers were prepared by free radical polymerization using N,N-dimethylformamide as a solvent and α,α′-azobis(isobutyronitrile) as an initiator. The copolymer composition was determined by elemental analysis. It was found that the temperature (T _c) at which the copolymer undergoes a phase transition, i.e., LCST, increases linearly with increasing the mole fraction (f _m) of NiPMA in the copolymer, within the T _c range from 32?°C (at f _m?=?0; NiPA homopolymer) to 42?°C (at f _m?=?1; NiPMA homopolymer). Also found from heating DSC thermograms were the linear dependencies of the enthalpy (ΔH) and entropy (ΔS) changes at T _c upon f _m. However, the ΔH (5.5?kJ/unit-mol) at f _m?=?1 was slightly smaller than that (5.7?kJ/unit-mol) of poly(N-n-propylacrylamide) but considerably smaller than that (7.8?kJ/unit-mol) of poly(N-n-propylmethacrylamide). The same trend was observed in the f _m dependence of ΔS. These results were discussed in terms of the structural effects of the NiPMA monomer unit on the heat-induced phase transition in water of poly(NiPA-co-NiPMA)s. It was suggested that a strong interaction of water with the amide group in the NiPMA would raise the transition temperature, but a local dehydration which occurs around the isopropyl side chain would not lead to large changes in the enthalpy and entropy at T _c.     

Acid–base equilibria of the aqua adducts of Ru(II) arene complexes with functionalised pyridines

Acid?Cbase equilibria of the aqua adducts of Ru(II) arene complexes, general formulae [(??⁶-p-cymene)Ru (L^1?3)Cl₂] where L¹?=?3-acetylpyridine (1), L²?=?4-acetylpyridine (2) and L³?=?2-amino-5-chloropyridine (3), then [(??⁶-p-cymene)Ru(HL⁴)Cl₂] with HL⁴?=?isonicotinic acid (4); [(??⁶-p-cymene)Ru(HL^5?8)Cl] where H₂L⁵?=?2,3-pyridine dicarboxylic acid (5), H₂L⁶?=?2,4-pyridine dicarboxylic acid (6), H₂L⁷?=?2,5-pyridine dicarboxylic acid (7) and H₂L⁸?=?2,6-pyridine dicarboxylic acid (8) have been studied. pK _a values were determined by potentiometry at 25?°C and constant ionic strength of 0.1?M NaNO₃. The assumed equilibria were confirmed by UV and ¹H-NMR spectroscopy.     

Inclusion complexation of naproxen with cyclosophoraoses and succinylated cyclosophoraoses in different pH environments

Cyclosophoraoses [cyclic β-(1,2)-glucan, Cys] isolated from Rhizobium leguminosarum biovar trifolii TA-1 have unique structures and high solubility, which make it a potent solubilizer for host–guest inclusion complexation. Succinylated cyclosophorasoses (S-Cys) were also synthesized by chemically modifying isolated cyclosophoraoses. In ultraviolet-visible studies using naproxen (NAP), Cys was shown to form the most stable complexes with NAP (K _1:1?=?2457.9?M^?1), which was followed by the negatively charged S-Cys (K _1:1?=?357.1?M^?1) at pH 3.4. A further strong reduction in the complex stability constant was observed at pH 7.5. When the reduction in the stability constant was compared with other cyclic oligosaccharides (Cys; 119.2?M^?1, CD; 14.48?M^?1 and HP-CD; 6.75?M^?1), S-Cys (K _1:1?=?5.6?M^?1) was shown to have the highest decrease in stability constant. These results suggest that the S-Cys could regulate the efficiency of inclusion complexation at external pH values. NMR studies of complex formation between NAP and Cys also showed a different correlation pattern at pH 3.4 and 7.5. This difference in correlation demonstrates that the inclusion complexes between Cys and NAP formed as a result of the differential charge distribution of the carboxyl groups of NAP. The pH-dependent inclusion behavior of Cys for NAP was also evaluated using molecular docking simulations.     

Electrochemical Responses and Sensitivities of Films Based on Multi-Walled Carbon Nanotubes in Aqueous Solutions

Novel films consisting of multi-walled carbon nanotubes (MWCNTs) were fabricated by means of chemical vapor deposition with decomposition of either acetonitrile (ACN) or benzene (BZ) using ferrocene as catalyst. The electrochemical responses of MWCNT-based films towards the ferrocyanide/ferricyanide, [Fe(CN)₆]^3?/4? redox couple were probed by means of cyclic voltammetry and electrochemical impedance spectroscopy at 25.0?±?0.5?°C. Both MWCNT-based films exhibit Nernstian response towards [Fe(CN)₆]^3?/4? with some slight kinetic differences. Namely, heterogeneous electron transfer rate constants lying in ranges of 2.69?×?10^?2?C1.7?×?10^?3 and 9.0?×?10^?3?C2.6?×?10^?3?cm·s^?1 were obtained at v?=?0.05?V·s^?1 for MWCNT_ACN and MWCNT_BZ, respectively. The detection limit of MWCNT_ACN, estimated to be about 4.70?×?10^?7?mol·L^?1 at v?=?0.05?V·s^?1, tends to become slightly poorer with the increase of the scan rate, namely at v?=?0.10?V·s^?1 the detection limit of 1.70?×?10^?6?mol·L^?1 was determined. Slightly poorer response ability was exhibited by MWCNT_BZ; specifically the detection limits of 1.57?×?10^?6 and 4.35?×?10^?6?mol·L^?1 were determined at v?=?0.05 and v?=?0.10?V·s^?1, respectively. The sensitivities of MWCNT_ACN and MWCNT_BZ towards [Fe(CN)₆]^3?/4? were determined as 1.60?×?10^?7 and 1.51?×?10^?7?A·L·mol^?1·cm^?2, respectively. The excellent electrochemical performance of MWCNT_ACN is attributed to the presence of incorporated nitrogen in the nanotube??s structure.     

Excess Molar Volumes of Oligo(Oxyethylene Glycol) Monodecyl Ethers in n-Dodecane, and Apparent Dipole Moments of {(Oligo(Oxyethylene Glycol) Monodecyl Ethers?+?n-Heptane, n-Decane or n-Dodecane} at T?=?298.15?K

Excess molar volumes and relative permittivities at a frequency of 30?kHz of oligo(oxyethylene glycol) monodecyl ethers (C₁₀E _m ) for m?=?1?C8 in n-heptane, n-decane or n-dodecane solutions were determined for the mole fraction range 0?<?x?<?0.04 at the temperature of 298.15?K. By using Frohlich??s equation the apparent dipole moments, ??, of C₁₀E _m were calculated, and the limiting values, ?? ₀, were determined by extrapolating to infinite dilution. The values of ?? ₀ increase linearly with increasing number of oxyethylene units (m) of oligo(oxyethylene glycol) monodecyl ethers in the range m?=?2?C8, while ?? ₀ of C₁₀E₁ is less than its extrapolated value. By comparing the present results with our previous ones measured in n-heptane and decane, a solvent effect on ?? ₀ was found. The excess partial molar volumes of oligo(oxyethylene glycol) monodecyl ethers at infinite dilution increase with increasing m. Those results are discussed from the viewpoint of the interactions between oligo(oxyethylene glycol) monodecyl ethers and solvent molecules.     

Thermo-physical properties of the binary mixture of benzaldehyde with bromobenzene at 303.15, 308.15, and 313.15?K

The values of density, viscosity, and ultrasonic velocity for the binary liquid mixture of benzaldehyde with bromobenzene have been measured over the entire range of composition at 303.15, 308.15, and 313.15?K. These values have been used to calculate the excess molar volume (V ^E), deviation in viscosity (????), deviation in velocity (?U), deviation in isentropic compressibility (??? _s), excess internal pressure (???), excess intermolecular free length (?L _f), and excess acoustic impedance (?Z). McAllister??s three-body-interaction model is used for correlating kinematic viscosity of binary mixtures. The excess values were correlated using the Redlich?CKister polynomial equation to obtain their coefficients and standard deviations. The thermo-physical properties (density, viscosity, and ultrasonic velocity) under the study were fitted to the Jouyban?CAcree model.     

Crystal structure and high-temperature electrical conductivity of novel perovskite-related gallium and indium oxides

Novel complex oxides Sr₂Ga_1+x In_1?x O₅, x?=?0.0–0.2 with brownmillerite-type structure were prepared in air at T?=?1,273 K, 24 h. Study of the crystal structure of Sr₂Ga_1.1In_0.9O₅ refined using X-ray powder diffraction data (S.G. Icmm, a?=?5.9694(1) Å, b?=?15.2091(3) Å, c?=?5.7122(1) Å, χ ²?=?2.48, R _F ²? ₌?0.0504, R _p?=?0.0458) revealed ordering of Ga³⁺ and In³⁺ cations over tetrahedral and octahedral positions, respectively. A partial replacement of Sr²⁺ by La³⁺ according to formula Sr_1?y La _y Ga_0.5In_0.5O_2.5+y/2, leads to the formation of a cubic perovskite (a?=?4.0291(5) Å) for y?=?0.3. No ordering of oxygen vacancies or cations was observed in Sr_0.7La_0.3Ga_0.5In_0.5O_2.65 as revealed by electron diffraction study. The trace diffusion coefficient (D _T) of oxygen for cubic perovskite Sr_0.7La_0.3Ga_0.5In_0.5O_2.65 is in the range 2.0?×?10^?9–6.3?×?10^?8 cm²/s with activation energy 1.4(1)?eV as determined by isotopic exchange depth profile technique using secondary ion mass spectrometry at 973–1,223 K. These values are close to those reported for Ca-doped ZrO₂. High-temperature electrical conductivity of Sr_0.7La_0.3Ga_0.5In_0.5O_2.65 studied by AC impedance was found to be nearly independent on oxygen partial pressure. Calculated values of activation energy at T?<?1,073 K for hole and oxide-ion conductivities are 0.96 and 1.10 eV, respectively.     

Supercapacitors based on carbide-derived carbons synthesised using HCl and Cl2 as reactants

Micro- and mesoporous carbide-derived carbons (CDCs) were synthesised from TiC powder via a gas-phase reaction using HCl and Cl₂ within the temperature range of 700–1,100 °C. Analysis of X-ray diffraction results show that TiC-CDCs consist mainly of graphitic crystallites. The first-order Raman spectra showed the graphite-like absorption peaks at ~1,577 cm^?1 and the disorder-induced peaks at ~1,338 cm^?1. The low-temperature N₂ sorption experiments were performed, and specific surface areas up to 1,214 and 1,544 m²?g^?1 were obtained for TiC-CDC (HCl) synthesised at T?=?800 °C and TiC-CDC (Cl₂) synthesised at T?=?900 °C, respectively. For the TiC-CDC powders synthesised, a bimodal pore size distribution has been established with the first maximum in the region up to 1.5 nm and the second maximum from 2 to 4 nm. The energy-related properties of supercapacitors based on 1 M (C₂H₅)₃CH₃NBF₄ in acetonitrile and TiC-CDC (Cl₂) and TiC-CDC (HCl) as electrode materials were also investigated by cyclic voltammetry, impedance spectroscopy, galvanostatic charge/discharge and constant power methods. The specific energy, calculated at U?=?3.0 V, are maximal for TiC-CDC (Cl₂ 800 °C) and TiC-CDC (HCl 900 °C), which are 43.1 and 31.1 W?h?kg^?1, respectively. The specific power, calculated at cell potential U?=?3.0 V, are maximal for TiC-CDC (Cl₂ 1,000 °C) and TiC-CDC (HCl 1,000 °C), which are 805.2 and 847.5 kW?kg^?1, respectively. The Ragone plots for CDCs prepared by using Cl₂ or HCl are quite similar, and at high power loads, the TiC-CDC material synthesised using Cl₂ at 900 °C, i.e. the material with optimal pore structure, delivers the highest power at constant energy.     

Thermodynamic Study on the Protonation and Na<Superscript>+</Superscript>, Ca<Superscript>2+</Superscript>, Mg<Superscript>2+</Superscript>-Complexation of a Biodegradable Chelant (HEIDA) at Different Ionic Strengths and Temperatures

A potentiometric method has been used for the determination of the protonation constants of N-(2-hydroxyethyl)iminodiacetic acid (HEIDA or L) at various temperatures 283.15?≤?T/K?≤?383.15 and different ionic strengths of NaCl_(aq), 0.12?≤?I/mol·kg^?1?≤?4.84. Ionic strength dependence parameters were calculated using a Debye–Hückel type equation, Specific Ion Interaction Theory and Pitzer equations. Protonation constants at infinite dilution calculated by the SIT model are \( \log_{10} \left( {{}^{T}K_{1}^{\text{H}} } \right) = 8.998 \pm 0.008 \) (amino group), \( \log_{10} \left( {{}^{T}K_{2}^{\text{H}} } \right) = 2.515 \pm 0.009 \) and \( \log_{10} \left( {{}^{T}K_{3}^{\text{H}} } \right) = 1.06 \pm 0.002 \) (carboxylic groups). The formation constants of HEIDA complexes with sodium, calcium and magnesium were determined. In the first case, the formation of a weak complex species, NaL, was found and the stability constant value at infinite dilution is log₁₀K_NaL?=?0.78?±?0.23. For Ca²⁺ and Mg²⁺, the CaL, CaHL, CaL₂ and MgL species were found, respectively. The calculated stability constants for the calcium complexes at T?=?298.15 K and I?=?0.150 mol·dm^?3 are: log₁₀β_CaL?=?4.92?±?0.01, log₁₀β_CaHL?=?11.11?±?0.02 and \( \log_{10} \beta_{\text{Ca{L}}_{2}} \)?=?7.84?±?0.03, while for the magnesium complex (at I?=?0.176 mol·dm^?3): log₁₀β_MgL?=?2.928?±?0.006. Protonation thermodynamic functions have also been calculated and interpreted.     

Crystal Structure of a New Ammonium Potassium Selenomolybdate Compound K3.31(NH4)0.69[Se2Mo5O21]·2H2O

An inorganic compound formulated as K_3.31(NH₄)_0.69[Se₂Mo₅O₂₁]·2H₂O has been synthesized by conventional solution method and characterized by scanning electron microscopy, IR, UV-Vis spectroscopies behaviors. The structure of the title compound has been determined from a single-crystal X-ray diffraction. It crystallizes in the monoclinic space group P2₁/n, with a?=?9.9371(2) ?, b?=?23.3545(2) ?, c?=?10.5179(2) ?, β?=?114.12(3)°, V?=?2227.7(5) ?³ and Z?=?4. It was revealed that the Strandberg-type polyoxoselenomolybdate cluster can be considered as a ring formed by five distorted edge- and corner-sharing MoO₆ octahedra, capped on both poles by a selenate pyramids sharing three vertices with the ring molybdenum centers. The Strandberg clusters are connected with ammonium ions and water molecules through hydrogen-bonding interactions which ensure the cohesion of the structure into a three-dimensional network.     

Structural and optical properties of tripod-like ZnO thin film and its application in dye-sensitized solar cell

In this work, we have synthesized Zinc oxide (ZnO) tripods and used its thin film as photoanode in dye-sensitized solar cells. SEM micrographs of the as-prepared sample of ZnO confirmed tripod-like morphology consisting of three cylindrical arms with well-defined ends, joined at a common core. The prepared sample of ZnO tripods was further characterized by EDX, XRD, UV-VIS, and FTIR. The dye N719-sensitized solar cell fabricated with photoanode of ZnO prepared in this work provided the open-circuit photo voltage (V _oc)?=?0.558 V, short-circuit photocurrent (J _sc)?=?6.368 mA?cm^-2, fill factor (FF)?=?0.50, and total conversion efficiency (η)?=?0.88 % under full light illumination (intensity 200 mW?cm^?2). When cell was illuminated by visible light (150 mW/cm²), V _oc?=?0.546 V, J _sc?=?4.437 mA/cm², FF?=?0.54, and η?=?0.88 % were obtained.     

A microcalorimetric titration study on the micelle formation of alkanediyl-α,ω-bis(dimethylalkylammonium bromide) surfactants at a 283.15–343.15?K temperature range

The aim of this study was to investigate the self-assembly process for m-8-m gemini surfactants, for m?=?8 and 12, in water, using the microcalorimetric titration method within the temperature range of 283.15?C343.15?K. The enthalpy of micellization (?H _mic) and critical micelle concentration (c.m.c.) have been calculated by using modified sigmoidal Boltzmann equation. Other thermodynamic parameters ?G _mic, ?S _mic, and ?C _p,mic, associated with micellization process were determined on the basis of the calorimetric results by applying the pseudo-phase separation model. The c.m.c. and ?H _mic values strongly depend on the temperature and the alkyl chain length. The enthalpy of micellization decreases and then changes its sign and becomes negative when temperature increases. The temperature dependence of the c.m.c. for the surfactants investigated exhibits typical U-shape. The results obtained are compared with literature data for other gemini cationic surfactants with a different alkyl chain length. The differences are analyzed in terms of differences in the hydrophobic interactions between the hydrocarbon chains.     

Electrochemical performance of strontium-doped neodymium nickelate mixed ionic–electronic conductor for intermediate temperature solid oxide fuel cells

The Nd_2???x Sr _x NiO_4?+?δ (x?=?0.1–0.5) solid solutions prepared by combustion synthesis are of submicron/superfine crystallite size. The crystal structure estimated by Rietveld analysis reveals increase in space in the rock salt layer on partial replacement of Nd³⁺ by Sr²⁺. The transition from negative temperature coefficient to positive temperature coefficient of conductivity is observed at 913 K. The maximum dc conductivity (σ?=?1.3?±?0.02 S?cm^?1 at 973 K) is obtained for x?=?0.2 in Nd_2???x Sr _x NiO_4?+?δ . The low dc conductivity compared with reported (≈100 S?cm^?1) is due to high porosity (low relative density) resulting from agglomeration of submicron crystallites. The variation in the conductivity with Sr content in Nd_2???x Sr _x NiO_4?+?δ is understood on the basis of defect chemistry. The electrochemical properties of the cathode materials are studied using electrochemical impedance spectroscopy at various temperatures and oxygen partial pressures. Nd_1.8Sr_0.2NiO_4?+?δ cathode exhibits lowest-area-specific resistance?=?0.52?±?0.015 Ohm?cm² at 973 K. At low $ {P_{{{{{\bf O}}_2}}}} $ (<1,000 Pa), oxygen ion transfer from Nd_1.8Sr_0.2NiO_4?+?δ cathode to gadolinium-doped ceria electrolyte is the rate-limiting step, whereas, charge-transfer reaction on the cathode becomes more important at high oxygen partial pressures and temperature (973 K).     

Structural and surface analysis of unsupported and alumina-supported La(Mn,Fe,Mo)O3 perovskite oxides

A series of bulk and Al₂O₃-supported perovskite oxides of the type LaMn_1???x???y Fe _x Mo _y O₃ (x?=?0.00?0.90 and y?=?0.00–0.09) were synthesized by the citric acid complexation–gelation method followed by annealing in air at 800 °C. For all samples, the local environment and the chemical state and concentration of surface species were determined. Mössbauer spectra revealed the only presence of octahedral Fe³⁺ ions dispersed in the perovskite structure, however well-crystallized together with a poorly crystalline LaFeO₃ phases were detected for larger substitutions (x?=?0.90). A similar picture was obtained for Mo-loaded (y?=?0.02 and 0.05) samples but a new phase most likely related to Fe³⁺ ions dispersed aside from the perovskite structure was found for larger substitutions (y?=?0.09). Together with these structures, supported samples showed the presence of LaFeO₃ nanoparticles. Finally, photoelectron spectroscopy indicated that the chemical state and composition of the samples in the surface region (2–3 nm) approaches that of the bulk. For the unsupported substituted samples, iron (and molybdenum) enters into the perovskite structure while manganese tends to be slightly segregated. Moreover, in supported perovskites, a fraction of Mo and La atoms interact with the alumina surface. All these oxides were active in methane combustion and best performance was recorded for the Fe-rich composition (x?=?0.9) in which both Mn³⁺ and Mo³⁺ ions were in the same proportion (y?=?0.05).