Volumetric properties and viscosities of the 2-pyrrolidone + 1,2-propanediol + water ternary system and its binary constituents at T = 313.15 K

Densities and viscosities of ternary mixtures of 2-pyrrolidone + 1,2-propanediol + water and corresponding binary mixtures of 1,2-propanediol + water, 2-pyrrolidone + water and 2-pyrrolidone + 1,2-propanediol have been measured over the whole composition range at 313.15 K. From the obtained data, the excess molar volumes (V^E), the deviations in viscosity (Δη) and the excess Gibbs free energy of activation (ΔG^?E) have been calculated. The V^E, Δη and ΔG^?E results were correlated and fitted by the Redlich–Kister equation for binary mixtures and by the Cibulka equation for ternary mixtures, as a function of mole fraction. Several predictive empirical relations were applied to predict the excess molar volumes of ternary mixtures from the binary mixing data.     

Excess molar volumes,viscosity deviations,excess isentropic compressibilities and deviations in relative permittivities of (alkyl acetates (methyl,ethyl, butyl and isoamyl) + n-hexane, + benzene, + toluene, + (o-, m-, p-) xylenes, + (chloro-, bromo-, nitro-) benzene at temperatures from 298.15 to 313.15 K

The experimental densities (ρ), dynamic viscosities (η), speeds of sound (υ) and relative permittivities (ε_r) of thirty six binary mixtures of esters (methyl acetate, ethyl acetate, butyl acetate and isoamyl acetate) + organic solvents (n-hexane, benzene, toluene, o-, m-, p- xylenes), + halogenated benzene (chloro-, bromobenzene), + nitrobenzene have been measured over the complete composition range at atmospheric pressure and temperatures (298.15 to 313.15 K). The excess molar volumes, V_m^E, excess isentropic compressibilities, κ_s^E, deviations in relative permittivities, δε_r have been calculated and fitted to Redlisch–Kister type equation. The dynamic and kinematic viscosities have been correlated through Grunberg–Nissan and MacAllister equations. The qualitative analysis of various functions revealed that i.) esters lose their dipolar association in presence of inert and unlike n-hexane, ii.) specific but weaker n…π type interactions predominate in binary mixtures of esters + aromatic organic solvents and iii.) weak electron donor–acceptor complexes predominate in the mixtures of esters with halogenated and nitrated benzene.     

(p, ρ, T) and (ps, ρs,Ts) properties,and apparent molar volumes Vϕ of LiI (aq) at T = 298.15 to 398.15 K and at pressures up to p = 60 MPa

(p, ρ, T) and (p_s, ρ_s, T_s) properties, and apparent molar volumes V_ϕ of LiI (aq) at T = 298.15 to 398.15 K, at pressures up to p = 60 MPa were reported, and apparent molar volumes at infinite dilution V_ϕ⁰ have been evaluated. An empirical correlation for density of lithium iodide (aq) with pressure, temperature and molality was derived. The experiments were carried out at molalities m = 0.11053, 0.32532, 0.70013, 1.40459, 2.95059, and 4.88147 mol kg^− 1 of lithium iodide.     

Ion conduction in proton- and related defect (super) ionic conductors: Mechanical,electronic and structure parameters

We find the relationships among optical dielectric constant ε_∞, activation energy E_ac, averaged atomic mass per a formula unit, ∑_jm_j / N, volume V and transition temperature T_c for various type ion conductors with forms of E_ac = α / (ε_∞ ? β), E_ac = A₀ + δ / [(∑_jm_j / N) ? d], E_ac = A_v / V^2/3, and ln(T_c) = g ? hln(∑_jm_j), where α, β, δ, A₀, d, A_v, g and h are constants depending on the kinds of conduction elements. We derive those proportional forms from a simple equation of motion under the assumption of ion hopping assisted by enhanced vibration displacement of host lattice. The enhancement is induced from the large fourth-order term of the host lattice potential originating from the electronic shielding effect of Coulomb force, heavy atomic mass of constituent ion, and volume expansion under the long-range periodicity of crystal structure. This mechanism is ascertained from characteristic phenomena of various kinds of conduction elements. For impurity-type H⁺-ion or defect conductor, the proportional form is shifted from that of superionic conductor because of weakened effect of host lattice vibration mode on H⁺-ion or O-ion defect. Photo-induced spectra of mobile ion in AgCl are understood, and a small quantum effect of H⁺ -ion is suggested.     

Densities, excess molar volumes, and viscosities of the binary and ternary mixtures of {diethylcarbonate (1) + p-chloroacetophenone (2) + 1-hexanol (3)} at 303.15 K for the liquid region and at ambient pressure

Densities ρ, dynamic viscosities η, of the ternary mixture (diethylcarbonate + p-chloroacetophenone + 1-hexanol) and the involved binary mixtures (diethylcarbonate + p-chloroacetophenone), (diethylcarbonate + 1-hexanol), and (p-chloroacetophenone + 1-hexanol) have been measured over the whole composition range at 303.15 K for the liquid region and at ambient pressure. The data obtained are used to calculate excess molar volumes V_m^E, excess partial molar volumes V¯_m,i^E, limiting excess partial molar volumes V¯_m,i^E,∞, and viscosity deviations Δη, of the binary and ternary mixtures. The data of excess molar volumes of the binary systems were fitted to the Redlich–Kister equation while for the ternary system the Cibulka equation was used. The McAllister's four body, and Kalidas and Laddha interaction models are used to correlate the kinematic viscosities of binary and ternary mixtures, respectively, to determine the fitting parameters and the standard deviations. The experimental data of the constitute binaries and ternary are analyzed to discuss the nature and strength of intermolecular interactions in these mixtures.     

Antiferromagnetic phase transition in garnet-type AgCa2Mn2V3O12 and NaPb2Mn2V3O12

Ferrimagnetism has been extensively studied in garnets, whereas it is rare to find the antiferromagnet. Present work will demonstrate antiferromagnetism in the two Mn–V-garnets. Antiferromagnetic phase transition in AgCa₂Mn₂V₃O₁₂ and NaPb₂Mn₂V₃O₁₂ has been found, where the magnetic Mn²⁺ ions locate only on octahedral A site. The heat capacity shows sharp peak due to antiferromagnetic order with the Néel temperature T_N=23.8 K for AgCa₂Mn₂V₃O₁₂ and T_N=14.2 K for NaPb₂Mn₂V₃O₁₂. The magnetic entropy change over a temperature range 0–50 K is 13.9 J K^?1 mol-Mn²⁺-ions^?1 for AgCa₂Mn₂V₃O₁₂ and 13.6 J K^?1 mol-Mn²⁺-ions^?1 for NaPb₂Mn₂V₃O₁₂, which are in good agreement with calculated value of Mn²⁺ ion with spin S=5/2. The magnetic susceptibility shows the Curie–Weiss behavior over the range 29–350 K. The effective magnetic moment μ_eff and the Weiss constant θ are μ_eff=6.20 μ_B Mn²⁺-ion^?1 and θ=?34.1 K (antiferromagnetic sign) for AgCa₂Mn₂V₃O₁₂ and μ_eff=6.02 μ_B Mn²⁺-ion^?1 and θ=?20.8 K for NaPb₂Mn₂V₃O₁₂.     

Synthesis,characterization and photovoltaic properties of novel molecules based on triarylamine dyes

We report the synthesis, electrochemical and photovoltaic properties of triphenylamine based novel organic sensitizer, comprising donor, electron-conducting and anchoring group. Different triphenylamines were synthesized as donor unit and connected to cyano-acidic acid acceptor over vinyl group. In this work, we studied on two novel dyes (TPA2, TPA3) by attaching methyl to m-position and diphenylamine to p-position of the basic triphenylamine structure, respectively. All derivatives absorb at visible region of solar spectrum in the range of 350–632 nm. By introducing strong electron injection groups to triphenylamine ring, band gap becomes narrower while E_HOMO–E_LUMO levels are tuned. All current voltage (I–V) measurements were done under 100 mW/cm² light intensity and AM 1.5 conditions. TPA3 chromophore with the lowest band gap shows the best cell performance with an efficiency (η) of 4.12%, a short-circuit photocurrent density (I_sc) of 8.07 mA/cm², an open-circuit voltage (V_oc) of 714 mV and a fill factor (FF) of 0.72.     

Influence of MgO on structure and optical properties of alumino-lithium-phosphate glasses

MgO doped lithium alumino phosphate glasses (PLA: P₂O₅+Li₂O+Al₂O₃+MgO) were prepared by melt quenching technique. Raman spectra display three significant peaks at 698, 1164 and 1383 cm⁻¹ attributed to: symmetric stretching vibrations of the bridging oxygen (BO) in the P–O–P chains, symmetric stretching vibrations of the PO₂ groups, and the asymmetric vibrations vas(PO₂) of the non-bridging oxygen (NBO) atoms, respectively. Also, the density, molar volumes and ion concentration have been discussed and correlated with the structural changes within the glassy matrix. Some optical constants such as refractive index and dispersion parameters (E_o: single-oscillator energy and E_d: dispersive energy) of the glasses were determined. Finally, the values of the optical band gap for direct and indirect allowed transitions have been determined from the absorption edge studies. It is deduced that the values of E_opt increase with increasing MgO content. It was assigned to structural changes induced from the formation of non-bridging oxygen. The Urbach energy (ΔE) was found to decrease from 0.578 to 0.339 eV with increasing MgO content from 0.5 to 2 mol.     

Kinetic studies of the electrochemical nitrogen reduction and incorporation into yttria stabilized zirconia

The kinetics of the electrochemical reduction of molecular nitrogen at gold micro electrodes on yttria stabilized zirconia (YSZ) solid oxide electrolyte is studied by steady state polarization measurements. From the η / lg i plot for both cathodic and anodic polarization the apparent transfer coefficients α_a and α_c are evaluated. The sum of α_a + α_c exceeds unity and thus a multistep electron transfer process is suggested. The concept of the stoichiometric number is applied to the electrode reaction N₂ + 6e⁻ = 2N³⁻ supposing that the overall process involves at least two intermediate species. On the basis of the evaluation of the experimental results the reaction N₂⁻ + e⁻ ⇌ N₂²⁻ is suggested as the rate determining reaction step for the cathodic nitrogen reduction and nitride formation.     

Effect of series resistance on the performance of silicon Schottky diode in the presence of tin oxide layer

The current–voltage (I–V) characteristics of Al/SnO₂/p-Si (MIS) Schottky diodes prepared by means of spray deposition method have been measured at 80, 295 and 350 K. In order to interpret the experimentally observed non-ideal Al/SnO₂/p-Si Schottky diode parameters such as, the series resistance R_s, barrier height Φ_B and ideality factor n, a novel calculation method has been reported by taking into account the applied voltage drop across interfacial oxide layer V_i and ideality factor n in the current transport mechanism. The values obtained for V_i were subtracted from the applied voltage values V and then the values of R_s were recalculated. The parameters obtained by accounting for the voltage drop V_i have been compared with those obtained without considering the above voltage drop. It is shown that the values of R_s estimated from Cheung’s method were strongly temperature-dependent and decreased with increasing temperature. It is shown that the voltage drop across the interfacial layer will increase the ideality factor and the voltage dependence of the I–V characteristics. The interface state density N_ss of the diodes has an exponential growth with bias towards the top of the valance band for each temperature; for example, from 2.37 × 10¹³ eV⁻¹ cm⁻² in 0.70−E_v eV to 7.47 × 10¹³ eV⁻¹ cm⁻² in 0.62−E_v eV for 295 K. The mean N_ss estimated from the I–V measurements decreased with increasing the temperature from 8.29 × 10¹³ to 2.20 × 10¹³ eV⁻¹ cm⁻².     

Excess molar volumes of ternary mixtures {n-butylacetae + 1-butanol + 1, 2-butanediol} and {n-butylacetate + 1-butanol + 1, 3-butanediol} at T = 303.15 K

Excess molar volumes of the ternary systems formed by {n-butylacetate + 1-butanol + 1,2-butanediol } and {n-butylacetate + 1-butanol + 1,3-butanediol} were measured at 303.15 K for the whole composition range. The excess molar volumes, V_m^E, for binary mixtures of {n-butylacetate + 1-butanol, + 1,2-butanediol and + 1,3-butanediol} are positive and for the binary mixtures of {1-butanol + 1,2-butanediol and + 1,3-butanediol} are negative. Several empirical expressions are used to predict and correlate the ternary excess molar volumes from experimental results on the constituted binaries and analyzed to gain insight about liquid mixture interactions.     

Oxygen nonstoichiometry and defect equilibrium in La2 − xSrxNiO4 + δ

Nonstoichiometric variation of oxygen content in La_2 ? xSr_xNiO_4 + δ (x = 0, 0.1, 0.2, 0.3, 0.4) and decomposition P(O₂) were determined by means of high temperature gravimetry and coulometric titration. The measurements were carried out in the temperature range between 873 and 1173 K and the P(O₂) range between 10^? 20 and 1 bar. La_2 ? xSr_xNiO_4 + δ showed the oxygen excess and the oxygen deficient compositions depending on P(O₂), temperature, and the Sr content. The value of partial molar enthalpy of oxygen approaches zero as δ increases in the oxygen excess region, which indicate that the interstitial oxygen formation reaction is suppressed as δ increase. The relationship between δ and logP(O₂) were analyzed by two types of defect equilibrium models. One is a localized electron model, and the other is a delocalized electron model. Both models can well explain the oxygen nonstoichiometry of La_2 ? xSr_xNiO_4 + δ with a regular solution approximation.     

Recombination luminescence of CsI(Tl) under electron pulse irradiation

The luminescence kinetics of CsI(Tl) exposed to an electron pulse irradiation (E_e = 250 keV, t_1/2 = 10 ns, j = 2 ÷ 160 mJ/cm²) has been studied. It has been discovered that the slow emission rise is due to hole V_k–Tl⁰ recombination luminescence at temperature from 100 to 160 K and electron–V_kA recombination, where electrons released from single Tl⁰ at temperature from 180 to 300 K. The effect of Tl concentration on both processes has been investigated.     

Effects of Ga contents on properties of CIGS thin films and solar cells fabricated by co-evaporation technique

This study examined the effects of Ga content in the CIGS absorber layer on the properties of the corresponding thin films and solar cells fabricated using a co-evaporation technique. The grain size of CIGS films decreased with increasing Ga content presumably because Ga diffusion during the 2nd stage of the co-evaporation process is more difficult than In diffusion. The main XRD peaks showed a noticeable shift to higher diffraction angles with increasing Ga content, which was attributed to Ga atoms substituting for In atoms in the chalcopyrite structure. Band gap energy and the net carrier concentration of CIGS films increased with Ga/(In + Ga) ratios. Regarding the solar cell parameters, the short circuit current density (J_SC) decreased linearly with Ga/(In + Ga) ratios due to the lack of absorption in the long-wavelength portion of the spectrum, while the open circuit voltage (V_OC) increase with those. However, V_OC values at high Ga/(In + Ga) regions (>0.35) was far below than those extrapolated from the low Ga contents regions, finally resulting in an optimum Ga/(In + Ga) ratio of 0.28 where the solar cell showed the highest efficiency of 15.56% with V_OC, J_SC and FF of 0.625 V, 35.03 mA cm⁻² and 0.71, respectively.     

Near limit behavior of the detonation velocity

The behavior of the detonation velocity near the limits is investigated. Circular tubes of diameters 65, 44 and 13 mm are used. To simulate a quasi two-dimensional rectangular geometry thin annular channels are also used. The annular channels are formed by a 1.5 m long insert of a smaller diameter tube into the larger outer diameter detonation tube. Premixed mixtures of C₂H₂ + 2.5O₂ + 70%Ar, CH₄ + 2O₂ and C₂H₂ + 5N₂O + 50%Ar are used in the present study. The high argon dilution stoichiometric C₂H₂ + 2.5O₂ mixture has a regular cell size and piecewise laminar reaction zone and thus referred to as “stable”. The other two mixtures give highly irregular cell pattern and a turbulent reaction zone and are hence, referred to as “unstable” mixtures. Pressure transducers and optical fibers spaced 10 cm apart along the tube are used for pressure and velocity measurements. Cell size of the three mixtures studied is also determined using smoked foils in both the circular tubes and annular channels. The ratio d/λ (representing the number of cells across the tube diameter) is found to be an appropriate sensitivity parameter to characterize the mixture. The present results indicate that well within the limit, the detonation velocity is generally a few percent below the theoretical Chapman–Jouguet (CJ) value. As the limit is approached, the velocity decreases rapidly to a minimum value before the detonation fails. The narrow range of values of d/λ of the mixture where the velocity drops rapidly is found to correspond to the range of values for the onset of single headed spinning detonations. Thus we may conclude that the onset of single headed spin can be used as a criterion for defining the limits. Spinning detonations are also observed near the limits in annular channels.     

1H NMR study of proton dynamics in (NH4)3H(SO4)2

Proton dynamics in (NH₄)₃H(SO₄)₂ has been studied by means of ¹H solid-state NMR. The ¹H magic-angle-spinning (MAS) NMR spectra were traced at room temperature (RT) and at Larmor frequency of 400.13 MHz. ¹H static NMR spectra were measured at 200.13 MHz in the range of 135–490 K. ¹H spin-lattice relaxation times, T₁, were measured at 200.13 and 19.65 MHz in the ranges of 135–490 and 153–456 K, respectively. The ¹H chemical shift for the acidic proton (14.7 ppm) indicates strong hydrogen bonds. In phase III, NH₄⁺ reorientation takes place; one type of NH₄⁺ ions reorients with an activation energy (E_a) of 14 kJ mol^− 1 and the inverse of a frequency factor (τ₀) of 0.85 × 10^− 14 s. In phase II, a very fast local and anisotropic motion of the acidic protons takes place. NH₄⁺ ions start to diffuse translationally, and no proton exchange is observed between NH₄⁺ ions and the acidic protons. In phase I, both NH₄⁺ ions and the acidic protons diffuse translationally. The acidic protons diffuse with parameters of E_a = 27 kJ mol^− 1 and τ₀ = 4.2 × 10^− 13 s. The translational diffusion of the acidic protons is responsible for the macroscopic proton conductivity, as the NH₄⁺ translational diffusion is slow and proton exchange between NH₄⁺ ions and the acidic protons is negligible.     

7Li and 51V NMR study on Li+ ionic diffusion in lithium intercalated LixV2O5

Li_xV₂O₅ (0.4 < x < 1.4) prepared by solid-state reaction were studied by ⁷Li and ⁵¹V NMR spectroscopy. ⁷Li NMR spectra showed a narrowing of the line width in relation to Li⁺ionic diffusion. Analysis of Li_xV₂O₅ using a Debye-type relaxation model showed a low activation energy ∼0.07 eV in the sample of x = 0.4 below room temperature, and revealed a Li⁺ionic diffusion with larger activation energy ∼0.5 eV above 450 K in lithium-rich samples. The latter is ascribed to the existence of a multi-phase system comprising stable ɛ- and γ-phases, resulting from complicated phase transitions at high temperature. These shapes and shifts enable the classification of the β-, ɛ-, δ-, and γ-phases. The ionic diffusion of Li⁺ ions is discussed in relation to the complicated phase transitions.     

High resolution emission spectroscopy of the E2Π–X2Σ+ transition of SrH and SrD

Emission spectra of SrH and SrD have been studied at high resolution using a Fourier transform spectrometer. The molecules have been produced in a high temperature furnace from the reaction of strontium metal vapor with H₂/D₂ in the presence of a slow flow of Ar gas. The spectra observed in the 18 000–19 500 cm^?1 region consist of the 0–0 and 1–1 bands of the E²Π–X²Σ⁺ transition of the two isotopologues. A rotational analysis of these bands has been obtained by combining the present measurements with previously available pure rotation and vibration–rotation measurements for the ground state, and improved spectroscopic constants have been obtained for the E²Π state. The present analysis provides spectroscopic constants for the E²Π state as ΔG(½) = 1166.1011(15) cm^?1, B_e = 3.805503(32) cm^?1, α_e = 0.098880(47) cm^?1, r_e = 2.1083727(89) Å for SrH, and ΔG(½) = 839.1283(23) cm^?1, B_e = 1.918564(15) cm^?1, α_e = 0.034719(23) cm^?1, r_e = 2.1121943(83) Å for SrD.     

Comprehensive visualization of detonation-diffraction structures and sizes in unstable and stable mixtures

The geometry and characteristic length of diffraction and re-initiation during a two-dimensional detonation propagation were revealed by visualization. C₂H₄ + 3O₂ (unstable), 2C₂H₂ + 5O₂ + 7Ar (stable) and 2C₂H₂ + 5O₂ + 21Ar (stable) were used as the test mixtures. Experiments were performed over the deviation angle range from 30° to 150° and the initial pressure range from 15.8 to 102.3 kPa. By self-emitting photography, we confirmed that the geometry and the characteristic length of diffraction are not different among test gases, with the exception of the fan-like structure of re-initiation that occurred regardless of whether the mixture was unstable or stable. We conducted a compensative experiment by changing the deviation angle and initial pressure, and summarized the detonation diffraction by shadowgraph. At deviation angles larger than 60°, we measured the distances from the vertex of the channel corner to the point where the transverse detonation wave reflected on the under wall (= wall reflection distance) and confirmed that wall reflection distances are approximately in the range of 10–15 times the cell width, whether the mixture is unstable or stable.     

On the rate constants of OH + HO2 and HO2 + HO2: A comprehensive study of H2O2 thermal decomposition using multi-species laser absorption

Hydrogen peroxide (H₂O₂) and hydroperoxy (HO₂) reactions present in the H₂O₂ thermal decomposition system are important in combustion kinetics. H₂O₂ thermal decomposition has been studied behind reflected shock waves using H₂O and OH diagnostics in previous studies (Hong et al. (2009) [9] and Hong et al. (2010) [6,8]) to determine the rate constants of two major reactions: H₂O₂ + M → 2OH + M (k₁) and OH + H₂O₂ → H₂O + HO₂ (k₂). With the addition of a third diagnostic for HO₂ at 227 nm, the H₂O₂ thermal decomposition system can be comprehensively characterized for the first time. Specifically, the rate constants of two remaining major reactions in the system, OH + HO₂ → H₂O + O₂ (k₃) and HO₂ + HO₂ → H₂O₂ + O₂ (k₄) can be determined with high-fidelity.No strong temperature dependency was found between 1072 and 1283 K for the rate constant of OH + HO₂ → H₂O + O₂, which can be expressed by the combination of two Arrhenius forms: k₃ = 7.0 × 10¹² exp(550/T) + 4.5 × 10¹⁴ exp(?5500/T) [cm³ mol^?1 s^?1]. The rate constants of reaction HO₂ + HO₂ → H₂O₂ + O₂ determined agree very well with those reported by Kappel et al. (2002) [5]; the recommendation therefore remains unchanged: k₄ = 1.0 × 10¹⁴ exp(?5556/T) + 1.9 × 10¹¹⁺exp(709/T) [cm³ mol^?1 s^?1]. All the tests were performed near 1.7 atm.