Deep Eutectic Solvents Based on N-Methylacetamide and a Lithium Salt as Electrolytes at Elevated Temperature for Activated Carbon-Based Supercapacitors

Kinetics study on thermal dissociation of levoglucosan during cellulose pyrolysis

(Chemical Equation Presented) The mechanisms and kinetics studies of the levoglucosan (LG) primary decomposition during cellulose pyrolysis have been carried out theoretically in this paper. Three decomposition mechanisms (C-O bond scission, C-C bond scission, and LG dehydration) including nine pathways and 16 elementary reactions were studied at the B3LYP/6-31 + G(D,P) level based on quantum mechanics. The variational transi-tion- state rate constants for every elementary reaction and every pathway were calculated within 298-1550 K. The first-order Arrhenius expressions for these 16 elementary reactions and nine pathways were suggested. It was concluded that computational method using transition state theory (TST) without tunneling correction gives good description for LG decomposition by comparing with the experimental result. With the temperature range of 667-1327 K, one dehydration pathway, with one water molecule composed of a hydrogen atom from C3 and a hydroxyl group from C2, is a preferred LG decomposition pathway by fitting well with the experimental results. The calculated Arrhenius plot of C-O bond scission mechanism is better agreed with the experimental Arrhenius plot than that of C-C bond scission. This C-O bond scission mechanism starts with breaking of C1-O5 and C6-O1 bonds with formation of CO molecule (C1-O1) simultaneously. C-C bond scission mechanism is the highest energetic barrier pathway for LG decomposition. © 2013 Elsevier Ltd. All rights reserved.

Thermodynamic Properties of Dichloromethane, Bromochloromethane, and Dibromomethane under Elevated Pressure: Experimental Results and SAFT-VR Mie Predictions

The speeds of sound in dibromomethane, bromochloromethane, and dichloromethane have been measured in the temperature range from 293.15 to 313.15 K and at pressures up to 100 MPa. Densities and isobaric heat capacities at atmospheric pressure have been also determined. Experimental results were used to calculate the densities and isobaric heat capacities as the function of temperature and pressure by means of a numerical integration technique. Moreover, experimental data at atmospheric pressure were then used to determine the SAFT-VR Mie molecular parameters for these liquids. The accuracy of the model has been then evaluated using a comparison of derived experimental high-pressure data with those predicted using SAFT. It was found that the model provide the possibility to predict also the isobaric heat capacity of all selected haloalkanes within an error up to 6%.

On the optical properties of bismuth oxide thin films prepared by pulsed laser deposition

The optical properties of bismuth oxide films prepared by pulsed laser deposition (PLD), absorption in the photon energy range 2.50-4.30 eV and optical functions (n, k, epsilon(1), and epsilon(2)) in the domain 3.20-6.50 eV, have been investigated. As-prepared films (d = 0.05-1.50 mum) are characterized by a mixture of polycrystalline and amorphous phases. The fundamental absorption edge is described by direct optical band-to-band transitions with energies 2.90 and 3.83 eV The dispersion of the optical functions provided values of 4.40-6.25 eV for electron energies of respective direct transitions. In the spectral range 400-1000 nm, bismuth oxide films show a normal dispersion, which can be interpreted in the frame of a single oscillator model. (C) 2004 Elsevier B.V. All rights reserved.

Energy levels, radiative rates and electron impact excitation rates for transitions in He-like Fe XXV, Co XXVI, Ni XXVII, Cu XXVIII and Zn XXIX

We report calculations of energy levels, radiative rates and electron impact excitation cross sections and rates for transitions in He-like Fe XXV, Co XXVI, Ni XXVII, Cu XXVIII and Zn XXIX. The grasp (general-purpose relativistic atomic structure package) is adopted for calculating energy levels and radiative rates. For determining the collision strengths and subsequently the excitation rates, the Dirac atomic R-matrix code (darc) is used. Oscillator strengths, radiative rates and line strengths are reported for all E1, E2, M1 and M2 transitions among the lowest 49 levels of each ion. Additionally, theoretical lifetimes are listed for all 49 levels of the above five ions. Collision strengths are averaged over a Maxwellian velocity distribution and the effective collision strengths obtained listed over a wide temperature range up to 10 ^7.7 K. Comparisons are made with similar data obtained using the flexible atomic code (fac) to highlight the importance of resonances, included in calculations with darc, in the determination of effective collision strengths. Discrepancies between the collision strengths from darc and fac, for some transitions, are also discussed. Finally, discrepancies between the present results of effective collision strengths with the darc code and earlier semi-relativistic R-matrix data are noted over a wide range of electron temperatures for many transitions in all ions. 

Energy levels, radiative rates and electron impact excitation rates for transitions in He-like Ga XXX, Ge XXXI, As XXXII, Se XXXIII and Br XXXIV

We report calculations of energy levels, radiative rates and electron impact excitation cross sections and rates for transitions in He-like Ga XXX, Ge XXXI, As XXXII, Se XXXIII and Br XXXIV. The grasp (general-purpose relativistic atomic structure package) is adopted for calculating energy levels and radiative rates. For determining the collision strengths, and subsequently the excitation rates, the Dirac atomic R-matrix code (darc) is used. Oscillator strengths, radiative rates and line strengths are reported for all E1, E2, M1 and M2 transitions among the lowest 49 levels of each ion. Additionally, theoretical lifetimes are provided for all 49 levels of the above five ions. Collision strengths are averaged over a Maxwellian velocity distribution and the effective collision strengths obtained listed over a wide temperature range up to 10⁸ K. Comparisons are made with similar data obtained using the flexible atomic code (fac) to highlight the importance of resonances, included in calculations with darc, in the determination of effective collision strengths. Discrepancies between the collision strengths from darc and fac, particularly for some forbidden transitions, are also discussed. Finally, discrepancies between the present results for effective collision strengths with the darc code and earlier semi-relativistic R-matrix data are noted over a wide range of electron temperatures for many transitions in all ions. © 2013 The Royal Swedish Academy of Sciences.

Energy levels, radiative rates, and electron impact excitation rates for transitions in Li-like ions with 21≤Z≤28

We report calculations of energy levels, radiative rates, and electron impact excitation rates for transitions in Li-like ions with 21≤Z≤28. The General-Purpose Relativistic Atomic Structure Package is adopted for calculating energy levels and radiative rates, while for determining the collision strengths and subsequently the excitation rates, the Dirac Atomic R-matrix Code is used. Oscillator strengths, radiative rates, and line strengths are listed for all E1, E2, M1, and M2 transitions among the lowest 24 levels of the Li-like ions considered. Collision strengths have been averaged over a Maxwellian velocity distribution, and the effective collision strengths obtained are given over a wide temperature range up to 10^7.8 K. Additionally, lifetimes are listed for all calculated levels of these ions. Finally, extensive comparisons are made with results available in the literature, as well as with our analogous calculations for all parameters with the Flexible Atomic Code, in order to assess the accuracy of the results.

Energy levels, radiative rates and electron impact excitation rates for transitions in Be-like Ti XIX

We report calculations of energy levels, radiative rates and electron impact excitation cross sections and rates for transitions in Be-like Ti XIX. The general-purpose relativistic atomic structure package is adopted for calculating energy levels and radiative rates. For determining the collision strengths and subsequently the excitation rates, the Dirac atomic R-matrix code (darc) is used. Oscillator strengths, radiative rates and line strengths are reported for all E1, E2, M1 and M2 transitions among the lowest 98 levels of the n≤ 4 configurations. Additionally, theoretical lifetimes are listed for all 98 levels. Collision strengths are averaged over a Maxwellian velocity distribution and the effective collision strengths obtained listed over a wide temperature range up to 10 ^7.7K. Comparisons are made with similar data obtained from the flexible atomic code (fac) to highlight the importance of resonances, included in calculations with darc, in the determination of effective collision strengths. Discrepancies between the collision strengths from darc and fac, particularly for forbidden transitions, are also discussed. 

Energy levels, radiative rates and electron impact excitation rates for transitions in He-like Kr XXXV

We report calculations of energy levels, radiative rates and electron impact excitation cross sections and rates for transitions in He-like Kr XXXV. The grasp (general-purpose relativistic atomic structure package) is adopted for calculating energy levels and radiative rates. For determining the collision strengths and subsequently the excitation rates, the Dirac Atomic R-matrix Code (darc) is used. Oscillator strengths, radiative rates and line strengths are reported for all E1, E2, M1 and M2 transitions among the lowest 49 levels. Additionally, theoretical lifetimes are listed for all 49 levels. Collision strengths are averaged over a Maxwellian velocity distribution and the effective collision strengths obtained listed over a wide temperature range up to 10 ^8.1K. Comparisons are made with similar data obtained with the Flexible Atomic Code (fac) to assess the accuracy of the results and to highlight the importance of resonances, included in calculations with darc, in the determination of effective collision strengths. Differences between the collision strengths from darc and fac, particularly for forbidden transitions, are also discussed. Finally, discrepancies between the present results of effective collision strengths from the darc code and earlier semi-relativistic R-matrix data are noted over a wide range of electron temperatures for many transitions of KrXXXV. 

Energy levels, radiative rates and electron impact excitation rates for transitions in He-like Ti XXI, v XXII, Cr XXIII and Mn XXIV

We report calculations of energy levels, radiative rates and electron impact excitation cross sections and rates for transitions in He-like Ti XXI, V XXII, Cr XXIII and Mn XXIV. grasp (general-purpose relativistic atomic structure package) is adopted for calculating energy levels and radiative rates. For determining the collision strengths and subsequently the excitation rates, the Dirac atomic R-matrix code (darc) is used. Oscillator strengths, radiative rates and line strengths are reported for all E1, E2, M1 and M2 transitions among the lowest 49 levels of each ion. Additionally, theoretical lifetimes are listed for all the 49 levels of the above four ions. Collision strengths are averaged over a Maxwellian velocity distribution and the effective collision strengths obtained listed over a wide temperature range up to 10 ^7.5K. Comparisons are made with similar data obtained using the flexible atomic code (fac) to highlight the importance of resonances, included in calculations with darc, in the determination of effective collision strengths. Discrepancies between the collision strengths from darc and fac, in particular for forbidden transitions, are also discussed. Finally, discrepancies between the present results for effective collision strengths with the darc code and earlier semi-relativistic R-matrix data are noted over a wide range of electron temperatures for many transitions in all ions. 

Energy levels, radiative rates, and electron impact excitation rates for transitions in Li-like ions with 12≤Z≤20

We report calculations of energy levels, radiative rates, and electron impact excitation rates for transitions in Li-like ions with 12≤Z≤20. The grasp (general-purpose relativistic atomic structure package) is adopted for calculating energy levels and radiative rates, while for determining the collision strengths and subsequently the excitation rates, the Dirac atomic R-matrix code is used. Oscillator strengths, radiative rates, and line strengths are reported for all E1, E2, M1, and M2 transitions among the lowest 24 levels of the Li-like ions considered. Collision strengths have been averaged over a Maxwellian velocity distribution, and the effective collision strengths obtained are reported over a wide temperature range up to 10^7.4 K. Additionally, lifetimes are also listed for all calculated levels of the ions. Finally, extensive comparisons are made with results available in the literature, as well as with our parallel calculations for all parameters with the Flexible Atomic Code, in order to assess the accuracy of the reported results. 

Energy levels, radiative rates and electron impact excitation rates for transitions in C III

We report energy levels, radiative rates (A-values) and lifetimes for the astrophysically important Be-like ion C III. For the calculations, 166 levels belonging to the n ≤ 5 configurations are considered and the GRASP (General-purpose Relativistic Atomic Structure Package) is adopted. Einstein A-coefficients are provided for all E1, E2, M1 and M2 transitions, while lifetimes are compared with available measurements as well as theoretical results, and no large discrepancies noted. Our energy levels are assessed to be accurate to better than 1 per cent for a majority of levels, and A-values to better than 20 per cent for most transitions. Collision strengths are also calculated, for which the Dirac Atomic R-matrix Code (DARC) is used. A wide energy range, up to 21 Ryd, is considered and resonances resolved in a fine energy mesh in the thresholds region. The collision strengths are subsequently averaged over a Maxwellian velocity distribution to determine effective collision strengths up to a temperature of 8.0 ×10[5]K, sufficient for most astrophysical applications. Our data are compared with the recent R-matrix calculations of Fernández-Menchero et al., and significant differences (up to over an order of magnitude) are noted for several transitions over the complete temperature range of the results.

High-pressure phase equilibrium in the {carbon dioxide (1) + 1-chloropropane (2)} binary system

Abstract The current study reports original vapour-liquid equilibrium (VLE) for the system {CO2 (1) + 1-chloropropane (2)}. The measurements have been performed over the entire pressure-composition range for the (303.15, 313.15 and 328.15) K isotherms. The values obtained have been used for comparison of four predictive approaches, namely the equation of state (EoS) of Peng and Robinson (PR), the Soave modification of Benedict–Webb–Rubin (SBWR) EoS, the Critical Point-based Revised Perturbed-Chain Association Fluid Theory (CP-PC-SAFT) EoS, and the Conductor-like Screening Model for Real Solvents (COSMO-RS). It has been demonstrated that the three EoS under consideration yield similar and qualitatively accurate predictions of VLE, which is not the case for the COSMO-RS model examined. Although CP-PC-SAFT EoS exhibits only minor superiority in comparison with PR and SBWR EoS in predicting VLE in the system under consideration, its relative complexity can be justified when taking into account the entire thermodynamic phase space and, in particular, considering the liquid densities and sound velocities over a wider pressure-volume-temperature range.

Preparation of La2NiO4+δ powders as a cathode material for SOFC via a PVP-assisted hydrothermal route

Uniform submicron La₂NiO_4+δ (sm-LNO) powders have been synthesized by a facile polyvinylpyrrolidone (PVP)-assisted hydrothermal route. In the presence of PVP, sm-LNO of pure phase has been obtained by calcination at the relatively low temperature of 900 °C for 8 h. Compared micron-sized LNO (m-LNO) particles obtained at 1,000 °C by hydrothermal synthesis route without PVP assisted, the sm-LNO-PVP displays regularly shaped and well-distributed particles in the range of 0.3–0.5 μm. The scanning electron microscopy (SEM) results showed that the sm-LNO sample is submicronic and that the m-LNO sample shows agglomerates with a broad size distribution. The electrochemical performance of m-LNO and sm-LNO-PVP has been investigated by electrochemical impedance spectroscopy. The polarization resistance of the sm-LNO-PVP cathode reaches a value of 0.40 Ω cm² at 750 °C, which is lower than that of m-LNO (0.62 Ω cm²). This result indicates that a fine electrode microstructure with submicron particles can help to increase the active sites, accelerate oxygen diffusion, and reduce polarization resistance. An anode-supported single cell with sm-LNO cathode has been fabricated and tested over a temperature range from 650 to 800 °C. The maximum power density of the cell has achieved 834 mW cm⁻² at 750 °C. These results therefore show that this PVP-assisted hydrothermal method is an effective approach to construct submicron-structured cathode and enhance the performance of intermediate temperature solid oxide fuel cell.

Electrochemical promotion of a platinum catalyst supported on the high-temperature proton conductor La0.99Sr0.01NbO4-δ

The recently discovered, high-temperature proton conductor, La_0.99Sr_0.01NbO_4-δ, was used as a support for the electrochemical promotion of a platinum catalyst. Ethylene oxidation was used as a probe reaction in the temperature range 350-450 °C. Moderate non-Faradaic rate modification, attributable to a protonic promoting species, occurred under negative polarisation; some permanent promotion was also observed. In oxidative atmospheres, both the p_O2 of the reaction mixture and the temperature influenced the type and magnitude of the observed rate modification. Rate-enhancement values of up to ρ = 1.4 and Faradaic-efficiency values approaching Λ = -100 were obtained. Promotion was observed under positive polarisation and relatively dry, oxygen-rich atmospheres suggesting that some oxygen ion conductivity may occur under these conditions. Impedance spectroscopy performed in atmospheres of 4 kPa O₂/N₂ and of 5 kPa H₂/N₂ under dry and slightly humidified (0.3 kPa H₂O) conditions indicated that the electrical resistivity is heavily dominated by the grain-boundary response in the temperature range of the EPOC studies; much lower grain-boundary impedances in the wetter conditions are likely to be attributable to proton transport. © 2009 Elsevier B.V. All rights reserved.