Thermochemical Properties of Dissolution of Nicotinic Acid C<Subscript>6</Subscript>H<Subscript>5</Subscript>NO<Subscript>2</Subscript>(s) in Aqueous Solution

Nicotinic acid (also known as niacin) was recrystallized from anhydrous ethanol. X-ray crystallography was applied to characterize its crystal structure. The crystal belongs to the monoclinic system, space group P2₍₁₎/c. The crystal cell parameters are a = 0.71401(4) nm, b = 1.16195(7) nm, c = 0.71974(6) nm, α = 90°, β = 113.514(3)°, γ = 90° and Z = 4. Molar enthalpies of dissolution of the compound, at different molalities m/(mol·kg^?1) were measured with an isoperibol solution–reaction calorimeter at T = 298.15 K. The molar enthalpy of solution at infinite dilution was calculated, according to Pitzer’s electrolyte solution model and found to be \( \Delta_{\text{sol}} H_{m}^{\infty } = ( 2 7. 3 \pm 0. 2) \) kJ·mol^?1 and Pitzer’s parameters (\( \beta_{{\text{MX}}}^{{\text{(0)}L}} \), \( \beta_{{\text{MX}}}^{{\text{(1)}L}} \) and \( C_{{\text{MX}}}^{\phi L} \)) were obtained. The values of apparent relative molar enthalpies (\( {}^{\phi }L \)) and relative partial molar enthalpies (\( \overline{{L_{2} }} \) and \( \overline{{L_{1} }} \)) of the solute and the solvent at different molalities were derived from the experimental enthalpy of dissolution values of the compound. Also, the standard molar enthalpy of formation of the anion \( {\text{C}}_{ 6} {\text{H}}_{ 4} \text{NO}_{2}^{-} \) in aqueous solution was calculated to be \( {\Delta_{\text{f}}^{} H}_{\text{m}}^{\text{o}} ({\text{C}}_{ 6} {\text{H}}_{ 4} {\text{NO}}_{2}^{-} \text{,aq}) = - \left( {603.2 \pm 1.2} \right)\;{\text{kJ}}{\cdot}{\text{mol}}^{-1} \).     

Conductivity and thermal expansion of the Ce<Subscript>0.8</Subscript>Gd<Subscript>0.2</Subscript>O<Subscript>1.9</Subscript> solid electrolyte in the oxidizing and reducing atmospheres

Highly compact (99%) solid electrolyte Ce_0.8Gd_0.2O_1.9 with submicron (0.3 μm) grains is synthesized. The dilatometric (20–850°C) and conductivity (180–350°C) measurements are performed on the electrolyte in air and as a function of the partial oxygen pressure \(p_{O_2 } \) (0.21?1×10^?25 atm) at 600, 700, and 800°C. An inflection is found in the temperature dependences of the thermal coefficient of linear expansion and conductivity (impedance measurements) at ～230°C, which is the evidence for a phase transition. The activation energies for conduction in the grain bulk and boundaries differ only slightly, indicating that the grain boundaries’ resistance is caused not by the precipitation of the second phase at the boundaries, but most probably by the presence of intergranular nanopores. The dilatometric measurements confirm a significant increase in the linear dimensions of Ce_0.8Gd_0.2O_1.9 in the reducing atmospheres with a parallel increase in its electron conductivity. The electron conductivity and specific elongation increase proportionally to \(p_{O_2 }^{ - 1/4} \) at all temperatures. The \(p_{O_2 } \) values, at which the transport numbers of ions t _i = 0.5, are determined. They are 10^?22.5, 10^?20, and 10^?18 atm at 600, 700, and 800°C, respectively.     

Thermodynamic Properties of Ternary Ionic Liquid Mixture Containing a Common Ion: Excess Molar Volumes,Excess Isentropic Compressibilities,Excess Molar Enthalpies and Excess Heat Capacities

In the present investigations, the excess molar volumes, \( V_{ijk}^{\text{E}} \), excess isentropic compressibilities, \( \left( {\kappa_{S}^{\text{E}} } \right)_{ijk} \), and excess heat capacities, \( \left( {C_{p}^{\text{E}} } \right)_{ijk} \), for ternary 1-butyl-2,3-dimethylimidazolium tetrafluoroborate (i) + 1-butyl-3-methylimidazolium tetrafluoroborate (j) + 1-ethyl-3-methylimidazolium tetrafluoroborate (k) mixture at (293.15, 298.15, 303.15 and 308.15) K and excess molar enthalpies, \( \left( {H^{\text{E}} } \right)_{ijk} \), of the same mixture at 298.15 K have been determined over entire composition range of x _i and x _j . Satisfactorily corrections for the excess properties \( V_{ijk}^{\text{E}} \), \( \left( {\kappa_{S}^{\text{E}} } \right)_{ijk} \), \( \left( {H^{\text{E}} } \right)_{ijk} \) and \( \left( {C_{p}^{\text{E}} } \right)_{ijk} \) have been obtained by fitting with the Redlich–Kister equation, and ternary adjustable parameters along with standard errors have also been estimated. The \( V_{ijk}^{\text{E}} \), \( \left( {\kappa_{S}^{\text{E}} } \right)_{ijk} \), \( \left( {H^{\text{E}} } \right)_{ijk} \) and \( \left( {C_{p}^{\text{E}} } \right)_{ijk} \) data have been further analyzed in terms of Graph Theory that deals with the topology of the molecules. It has also been observed that Graph Theory describes well \( V_{ijk}^{\text{E}} \), \( \left( {\kappa_{S}^{\text{E}} } \right)_{ijk} \), \( \left( {H^{\text{E}} } \right)_{ijk} \) and \( \left( {C_{p}^{\text{E}} } \right)_{ijk} \) values of the ternary mixture comprised of ionic liquids.     

Solvent extraction of calcium and strontium into nitrobenzene by using synergistic mixture of hydrogen dicarbollylcobaltate and diphenyl-<Emphasis Type="Italic">N</Emphasis>-butylcarbamoylmethyl phosphine oxide

Extraction of microamounts of calcium and strontium by a nitrobenzene solution of hydrogen dicarbollylcobaltate (H⁺B^?) in the presence of diphenyl-N-butylcarbamoylmethyl phosphine oxide (DPBCMPO, L) has been investigated. The equilibrium data have been explained assuming that the species HL⁺, \( {\text{HL}}_{2}^{ + } \), \( {\text{ML}}_{2}^{2 + } \), \( {\text{ML}}_{3}^{2 + } \) and \( {\text{ML}}_{4}^{2 + } \) (M²⁺ = Ca²⁺, Sr²⁺) are extracted into the organic phase. The values of extraction and stability constants of the cationic complexes in nitrobenzene saturated with water have been determined. In the considered nitrobenzene medium, it was found that the stability of the \( {\text{SrL}}_{2,{\text{org}}}^{2 + } \) complex is somewhat higher than that of species \( {\text{CaL}}_{2,{\text{org}}}^{2 + } \), while the stability constants of the remaining strontium complexes \( {\text{SrL}}_{3,{\text{org}}}^{2 + } \) and \( {\text{SrL}}_{4,{\text{org}}}^{2 + } \) are smaller than those of the corresponding complex species \( {\text{CaL}}_{n}^{2 + } \) (n = 3, 4).     

The diffusion of oxygen and ion transport in lanthanum cobaltite LaCoO<Subscript>3-δ</Subscript>

The chemical diffusion coefficient of oxygen vacancies and oxygen ion conductivity in lanthanum cobaltite LaCoO₃ were determined by the polarization method as functions of oxygen partial pressure \(p_{O_2 } \) (atm) and temperature T(K) over the ranges ?4 ≤ log \(p_{O_2 } \) ≤ 0 and 1173 K ≤ T ≤ 1323 K. The mobilities (cm²/(V s)) of oxygen vacancies calculated over the temperature range studied satisfy the inequalities 1.8 × 10^?5 ≤ \(v_{v_0 } \) ≤ 3.4 × 10^?5. The transfer numbers of oxygen vacancies were calculated. These numbers change depending on oxygen partial pressure over the range 5 × 10^?7 ≤ t ₀ ≤ 1 × 10^?5. The activation energy of self-diffusion of oxygen vacancies was found to be E _a= 104 ± 10 kJ/mol (1.1 ± 0.1 eV).     

Structure of the Cu(Salen) molecule Cuo<Subscript>2</Subscript>N<Subscript>2</Subscript>C<Subscript>16</Subscript>H<Subscript>14</Subscript> according to gas-phase electron diffraction data and quantum chemical calculations

In the framework of synchronous gas-phase electron diffraction and mass spectrometry experiment, the saturated vapor of N,N′-ethylenebis(salicylaldiminate) copper(II) CuO₂N₂C₁₆H₁₄ is studied at a temperature T 574(5) K. It is found that evaporation is congruent and the saturated vapor consists of monomeric molecules. Electron diffraction data are proved to correspond to the geometric model for the CuO₂N₂C₁₆H₁₄ molecule of C ₂ symmetry with an almost planar structure of the CuN₂O₂ coordination fragment and internuclear distances \(r_{h_1 } \)(Cu-O) = 1.917(13) Å and \(r_{h_1 } \)(Cu-N) = 1.931(15) Å. The stuctural parameters obtained are compared to those quantum chemically calculated and molecular parameters in crystals.     

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.     

Thermo Physical and Spectroscopic Properties of Binary Liquid Systems: Ethanoic Acid/Propanoic Acid/Butanoic Acid with 2-Methylaniline

Densities (ρ), speeds of sound (u), and viscosities (η) are reported for binary mixtures of 2-methylaniline with carboxylic acids (ethanoic acid, propanoic acid and butanoic acid) over the entire composition range of mole fraction at T?=?(303.15–318.15) K and at atmospheric pressure (0.1 MPa). The excess properties such as excess molar volume (V _m ^E ), excess isentropic compressibility (κ _S ^E ) and excess Gibbs energy of activation of viscous flow (G^*E) are calculated from the experimental densities, speeds of sound and viscosities. Excess properties are correlated using the Redlich–Kister polynomial equation. The partial molar volumes, \( \bar{V}_{\text{m,1}} \) and \( \bar{V}_{\text{m,2}} \), partial molar isentropic compressibilities, \( \bar{K}_{\text{s,m,1}} \) and \( \bar{K}_{\text{s,m,2}} \), excess partial molar volumes, \( \bar{V}_{\text{m,1}}^{\text{E}} \) and \( \bar{V}_{\text{m,2}}^{\text{E}} \), and excess partial molar isentropic compressibilities, \( \bar{K}_{\text{s,m,1}}^{\text{E}} \) and \( \bar{K}_{\text{s,m,2}}^{\text{E}} \), over whole composition range, partial molar volumes, \( \bar{V}_{\text{m,1}}^{ \circ } \) and \( \bar{V}_{\text{m,2}}^{ \circ } \), partial molar isentropic compressibilities, \( \bar{K}_{\text{s,m,1}}^{ \circ } \) and \( \bar{K}_{\text{s,m,2}}^{ \circ } \), excess partial molar volumes, \( \bar{V}_{\text{m,1}}^{{ \circ {\text{E}}}} \) and \( \bar{V}_{{{\text{m}},2}}^{{ \circ {\text{E}}}} \), and excess partial molar isentropic compressibilities, \( \bar{K}_{\text{s,m,1}}^{{ \circ {\text{E}}}} \) and \( \bar{K}_{\text{s,m,2}}^{{ \circ {\text{E}}}} \), of the components at infinite dilution have also been calculated from the analytically obtained Redlich–Kister polynomials. The excess molar volume V^E results are analyzed using the Prigogine–Flory–Patterson theory. Analysis of each of the three contributions viz. interactional V^E(int.), free volume V^E(fv.) and characteristic pressure p* to V^E showed that the interactional contributions are positive for all systems while the free volume and characteristic pressure p* contributions are negative for all the binary mixtures. The results are analyzed in terms of attractive forces between 2-methylaniline and carboxylic acids molecules. Good agreement is obtained between excess quantities and spectroscopic data.     

Measurement and Calculation the Excess Molar Properties of Binary Mixtures Containing Isobutanol, 1-Amino-2-Propanol,and 1-Propanol at Temperatures of (293.15 to 333.15) K

Densities, ρ, and viscosities, η, of pure isobutanol, 1-amino-2-propanol, and 1-propanol, along with their binary mixtures of {x ₁isobutanol + x ₂1-propanol}, {x ₁1-amino-2-propanol + x ₂1-propanol}, and {x ₁1-amino-2-propanol + x ₂isobutanol} were measured over the entire composition range and at temperatures (293.15–333.15) K at ambient pressure (81.5 kPa). Excess molar properties such as the excess molar volume, V _m ^E , partial molar volumes, \( \bar{V}_{1} \) and \( \bar{V}_{2} \), excess partial molar volumes, \( \bar{V}_{1}^{\text{E}} \) and \( \bar{V}_{2}^{\text{E}} \), thermal expansion coefficient, α, excess thermal expansion coefficient, α ^E, viscosity deviation, Δη, and the excess Gibbs energy of activation, ?G ^E*, for the binary mixtures were calculated from the experimental values of densities and viscosities. The excess values of the binary mixtures are negative in the entire composition range and at all temperatures, and increase with increasing temperature. Viscosity deviations, Δη, are negative over the entire composition range and decrease with increasing temperature. The viscosities of the mixtures were correlated by the models of McAllister, Heric, Hind, Katti, and Nissan. The obtained data were correlated by Redlich–Kister equation and the fitting parameters and standard deviations were determined.     

Volumetric,Acoustic and Transport Properties of Metformin Hydrochloride Drug in Aqueous <Emphasis Type="SmallCaps">d</Emphasis>-Glucose Solutions at <Emphasis Type="Italic">T</Emphasis> = (298.15–318.15) K

Apparent molar volumes, apparent molar adiabatic compressibilities and viscosity B-coefficients for metformin hydrochloride in aqueous d-glucose solutions were determined from solution densities, sound velocities and viscosities measured at T = (298.15–318.15) K and at pressure p = 101 kPa as a function of the metformin hydrochloride concentrations. The standard partial molar volumes (\( \phi_{V}^{0} \)) and slopes (\( S_{V}^{*} \)) obtained from the Masson equation were interpreted in terms of solute–solvent and solute–solute interactions, respectively. Solution viscosities were analyzed using the Jones–Dole equation and the viscosity A and B coefficients discussed in terms of solute–solute and solute–solvent interactions, respectively. Adiabatic compressibility (\( \beta_{s} \)) and apparent molar adiabatic compressibility (\( \phi_{\kappa }^{{}} \)), limiting apparent molar adiabatic compressibility (\( \phi_{\kappa }^{0} \)) and experimental slopes (\( S_{\kappa }^{*} \)) were determined from sound velocity data. The standard volume of transfer (\( \Delta_{t} \phi_{V}^{0} \)), viscosity B-coefficients of transfer (\( \Delta_{t} B \)) and limiting apparent molar adiabatic compressibility of transfer (\( \Delta_{t} \phi_{\kappa }^{0} \)) of metformin hydrochloride from water to aqueous glucose solutions were derived to understand various interactions in the ternary solutions. The activation parameters of viscous flow for the studied solutions were calculated using transition state theory. Hepler’s coefficient \( (d\phi /dT)_{p} \) indicated the structure making ability of metformin hydrochloride in the ternary solutions.     

The Study of Intermolecular Interactions for <Emphasis Type="SmallCaps">dl</Emphasis>-Alanine and Glycine in Aqueous <Emphasis Type="SmallCaps">l</Emphasis>(+)-Arabinose Solutions at Different Temperatures and Ambient Pressure,Using the Volumetric Approach

Density measurements are used to calculate the apparent molar volumes V_φ, limiting apparent molar volumes \(V_{\varphi }^{0}\), limiting apparent molar volumes of transfer, \(\Delta_{\text{t}} V_{\varphi }^{0}\), limiting apparent molar expansibilities, \(E_{\varphi }^{0}\), and hydration numbers n_H, for dl-alanine and glycine in aqueous solutions of l(+)-arabinose at T?=?293.15 to 313.15 K. To obtain the limiting apparent molar volume, the V_φ values are extrapolated to zero molality using the linear form of the Redlich–Meyer equation. Also, the limiting apparent molar volumes of transfer, \(\Delta_{\text{t}} V_{\varphi }^{0}\), for the amino acids, from water to aqueous l(+)-arabinose solutions, are calculated from the \(V_{\varphi }^{0}\) values. The limiting apparent molar expansibility, \(E_{\varphi }^{0}\), values have been obtained from the first derivative of limiting apparent molar volumes with respect to temperature. Also the hydration number, n_H, for both amino acids in the ternary solutions are estimated. Possible solute–solvent interactions in the studied ternary systems are discussed.     

Additional Aspects of Complexation of Gold(I) with Thiomalate

Some equilibria involving gold(I) thiomalate (mercaptosuccinate, TM) complexes have been studied in the aqueous solution at 25 °C and I?=?0.2 mol·L^?1 (NaCl). In the acidic region, the oxidation of TM by \( {\text{AuCl}}_{4}^{ - } \) proceeds with the formation of sulfinic acid, and gold(III) is reduced to gold(I). The interaction of gold(I) with TM at n_TM/n_Au?≤?1 leads to the formation of highly stable cyclic polymeric complexes \( {\text{Au}}_{m} \left( {\text{TM}} \right)_{m}^{*} \) with various degrees of protonation depending on pH. In general, the results agree with the tetrameric form of this complex proposed in the literature. At n_TM/n_Au?>?1, the processes of opening the cyclic structure, depolymerization and the formation of \( {\text{Au}}\left( {\text{TM}} \right)_{2}^{*} \) occur: \( {\text{Au}}_{4} ( {\text{TM)}}_{4}^{8 - } + {\text{TM}}^{3 - } \rightleftharpoons {\text{Au}}_{ 4} ( {\text{TM)}}_{5}^{11 - } \), log₁₀ K₄₅?=?10.1?±?0.5; 0.25 \( {\text{Au}}_{4} ( {\text{TM)}}_{4}^{8 - } + {\text{TM}}^{3 - } \rightleftharpoons {\text{Au(TM)}}_{2}^{5 - } \), log₁₀ K₁₂?=?4.9?±?0.2. The standard potential of \( {\text{Au(TM)}}_{2}^{5 - } \) is \( E_{1/0}^{ \circ } = -0. 2 5 5\pm 0.0 30{\text{ V}} \). The numerous protonation processes of complexes at pH?<?7 were described with the use of effective functions.     

Lego-like spheres and tori

Given a connected surface \({\mathbb {F}}^2\) with Euler characteristic \(\chi \) and three integers \(b>a\ge 1<k\), an \((\{a,b\};k)\)-\({\mathbb {F}}^2\) is a \({\mathbb {F}}^2\)-embedded graph, having vertices of degree only k and only a- and b-gonal faces. The main case are (geometric) fullerenes (5, 6; 3)-\({\mathbb {S}}^2\). By \(p_a\), \(p_b\) we denote the number of a-gonal, b-gonal faces. Call an \((\{a,b\};k)\)-map lego-admissible if either \(\frac{p_b}{p_a}\), or \(\frac{p_a}{p_b}\) is integer. Call it lego-like if it is either \(ab^f\)-lego map, or \(a^fb\)-lego map, i.e., the face-set is partitioned into \(\min (p_a,p_b)\) isomorphic clusters, legos, consisting either one a-gon and \(f=\frac{p_b}{p_a}\,b\)-gons, or, respectively, \(f=\frac{p_a}{p_b}\,a\)-gons and one b-gon; the case \(f=1\) we denote also by ab. Call a \((\{a,b\};k)\)-map elliptic, parabolic or hyperbolic if the curvature \(\kappa _b=1+\frac{b}{k}-\frac{b}{2}\) of b-gons is positive, zero or negative, respectively. There are 14 lego-like elliptic \((\{a,b\};k)\)-\({\mathbb {S}}^2\) with \((a,b)\ne (1,2)\). No \((\{1,3\};6)\)-\({\mathbb {S}}^2\) is lego-admissible. For other 7 families of parabolic \((\{a,b\};k)\)-\({\mathbb {S}}^2\), each lego-admissible sphere with \(p_a\le p_b\) is \(a^fb\) and an infinity (by Goldberg–Coxeter operation) of \(ab^f\)-spheres exist. The number of hyperbolic \(ab^f\,(\{a,b\};k)\)-\({\mathbb {S}}^2\) with \((a,b)\ne (1,3)\) is finite. Such \(a^f b\)-spheres with \(a\ge 3\) have \((a,k)=(3,4),(3,5),(4,3),(5,3)\) or (3, 3); their number is finite for each b, but infinite for each of 5 cases (a, k). Any lego-admissible \((\{a,b\};k)\)-\({\mathbb {S}}^2\) with \(p_b=2\le a\) is \(a^f b\). We list, explicitly or by parameters, lego-admissible \((\{a,b\};k)\)-maps among: hyperbolic spheres, spheres with \(a\in \{1,2\}\), spheres with \(p_b\in \{2,\frac{p_a}{2}\}\), Goldberg–Coxeter’s spheres and \((\{a,b\};k)\)-tori. We present extensive computer search of lego-like spheres: 7 parabolic (\(p_b\)-dependent) families, basic examples of all 5 hyperbolic \(a^fb\) (b-dependent) families with \(a\ge 3\), and lego-like \((\{a,b\};3)\)-tori.     

Interaction between oxygen and polycrystalline palladium at O<Subscript>2</Subscript> pressures of 10<Superscript>−6</Superscript>–10 Pa

The interaction between oxygen and polycrystalline palladium (Pd(poly)) at \(P_{O_2 } \) = 2.6 × 10^?6–10 Pa and T = 300–1300 K was studied by the thermal desorption (TD) method. The interaction between O₂ and Pd(poly) is governed by the O₂ pressure and the sample temperature. At low pressures of \(P_{O_2 } \) (≤1.3 × 10^?5 Pa), O₂ is chemisorbed dissociatively on the Pd(poly) surface. During chemisorption, the O_ads-surface bond energy and the O₂ sticking coefficient gradually decrease as the surface coverage θ increases. At \(P_{O_2 } \) ≥ 10^?2 Pa and T ≤ 500 K, after the saturation of the O_ads layer (θ ～ 0.5), O_ads atoms penetrate under the surface layer of the metal to form surface palladium oxide. At \(P_{O_2 } \) ≥ 1 Pa and T > 500 K, after the saturation of the surface oxide film 2 ML in thickness (n ～ 2), O_ads atoms penetrate into the oxide film and then into the subsurface palladium layer and diffuse deep into the metal bulk. As a result, the oxygen uptake at 700 K is n ～ 50. Upon heating, the surface oxides decompose, desorbing O₂, which gives rise to a low-temperature TD peak with T _max = 715 K. The release of oxygen inserted in the subsurface layers of palladium shows itself as a distinct high-temperature TD peak with T _max ≥ 750 K.     

High-pressure defect phase Nd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Cu<Subscript>3</Subscript>V<Subscript>4</Subscript>O<Subscript>12</Subscript>

A perovskite-like oxide Nd _x Cu₃V₄O₁₂ (space group Im \(\bar 3\) Z = 2, a = 7.278–7.322 Å) with cationic vacancies was prepared for the first time under triaxial compression of p = 6.0–9.0 GPa at 700–1300°C. The compound has a metal-type conductivity, paramagnetic properties, and a phase transition.     

Synthesis,crystal structure,and thermodynamics of a high-nitrogen copper complex with <Emphasis Type="Italic">N</Emphasis>, <Emphasis Type="Italic">N</Emphasis>-bis-(1(2)H-tetrazol-5-yl) amine

A new high-nitrogen complex [Cu(Hbta)₂]·4H₂O (H₂bta = N,N-bis-(1(2)H-tetrazol-5-yl) amine) was synthesized and characterized by elemental analysis, single crystal X-ray diffraction and thermogravimetric analyses. X-ray structural analyses revealed that the crystal was monoclinic, space group P2(1)/c with lattice parameters a = 14.695(3) Å, b = 6.975(2) Å, c = 18.807(3) Å, β = 126.603(1)°, Z = 4, D _c = 1.888 g cm^?3, and F(000) = 892. The complex exhibits a 3D supermolecular structure which is built up from 1D zigzag chains. The enthalpy change of the reaction of formation for the complex was determined by an RD496–III microcalorimeter at 25 °C with the value of ?47.905 ± 0.021 kJ mol^?1. In addition, the thermodynamics of the reaction of formation of the complex was investigated and the fundamental parameters k, E, n, \( \Updelta S_{ \ne }^{{{\uptheta}}} \), \( \Updelta H_{ \ne }^{{{\uptheta}}} \), and \( \Updelta G_{ \ne }^{{{\uptheta}}} \) were obtained. The effects of the complex on the thermal decomposition behaviors of the main component of solid propellant (HMX and RDX) indicated that the complex possessed good performance for HMX and RDX.     

Densities and Speeds of Sound of Binary Liquid Mixtures of 1,4-Butanediol with 2-Methoxyethanol and 2-Propoxyethanol at <Emphasis Type="Italic">T</Emphasis> = (303.15, 308.15, 313.15 and 318.15) K

Densities, ρ, and speeds of sound, u, for the binary liquid mixtures of 1,4-butanediol (1,4-BD) + 2-alkoxyethanols {2-methoxyethanol (2-ME), or 2-propoxyethanol (2-PE)} over the whole composition range have been measured at T = (303.15, 308.15, 313.15 and 318.15) K, and at atmospheric pressure (p = 0.1 kPa). Experimental data for the densities and speeds of sound have been used to derive the quantities like excess molar volume, \( V_{\text{m}}^{\text{E}} \), excess isentropic compressibility, \( \kappa_{S}^{\text{E}} \), excess molar isentropic compressibility, \( K_{{S,{\text{m}}}}^{\text{E}} \), excess speed of sound, \( u^{\text{E}} \), and excess isobaric thermal expansion \( \alpha_{p}^{\text{E}} \). These excess parameters were correlated by Redlich–Kister polynomials. Excess partial molar volumes (\( \bar{V}_{\text{m,1}}^{\text{E}} \) and \( \bar{V}_{\text{m,2}}^{\text{E}} \)) and their limiting values at infinite dilution (\( \bar{V}_{\text{m,1}}^{{ 0 {\text{E}}}} \) and \( {\bar{\text{V}}}_{\text{m,2}}^{{ 0 {\text{E}}}} \)) have been calculated from the experimental density measurements and were analytically obtained using the Redlich–Kister polynomials. The results are discussed in terms of intermolecular interactions and their dependence on composition and temperature.     

Crystal structure of CsNbMoO<Subscript>6</Subscript>

Single crystals of CsNbMoO₆ were grown from solution in melt, and their crystal structure was solved by X-ray diffraction (R[I > 2σ(I)]₁ = 0.0386). Crystals were cubic, а = 10.41039(8) Å, Z = 8, space group \(F\bar 43m\). The synthesized crystals were shown to exhibit the second harmonic generation effect, which confirmed the absence of an inversion center in the structure. The structure was built of MO₆ (M = Nb, Mo) octahedra, which share all vertices to form a three-dimensional framework where niobium and molybdenum atoms are randomly distributed. Framework interstices accommodate cesium ions. Crystals of CsNbMoO6 can be considered as pseudo-symmetric with respect to space group \(Fd\bar 3m\) due to a small shift of some oxygen atoms relative to the regular system of points in this group.