Conductance Studies on Complex Formation Between Aza-18-Crown-6 with Ag+, Hg2+ and Pb2+ Cations in DMSO–H2O Binary Solutions

The complexation reactions between Ag⁺, Hg²⁺ and Pb²⁺ metal cations with aza-18-crown-6 (A18C6) were studied in dimethylsulfoxide (DMSO)–water (H₂O) binary mixtures at different temperatures using the conductometric method. The conductance data show that the stoichiometry of the complexes in most cases is 1:1(ML), but in some cases 1:2 (ML₂) complexes are formed in solutions. A non-linear behaviour was observed for the variation of log K _f of the complexes vs. the composition of the binary mixed solvents. Selectivity of A18C6 for Ag⁺, Hg²⁺ and Pb²⁺ cations is sensitive to the solvent composition and in some cases and in certain compositions of the mixed solvent systems, the selectivity order is changed. The values of thermodynamic parameters (ΔH _c^o, ΔS _c^o) for formation of A18C6–Ag⁺, A18C6–Hg²⁺ and A18C6–Pb²⁺ complexes in DMSO–H₂O binary systems were obtained from temperature dependence of stability constants and the results show that the thermodynamics of complexation reactions is affected by the nature and composition of the mixed solvents.     

Complexation of 4′-Nitrobenzo-15-crown-5 with Zn<Superscript>2+</Superscript>, Mn<Superscript>2+</Superscript>, Cr<Superscript>3+</Superscript> and Sn<Superscript>4+</Superscript> Cations in Acetonitrile–Ethanol Binary Mixtures

The complexation reactions of 4′-nitrobenzo-15-crown-5 (4′NB15C5) with Zn²⁺, Mn²⁺, Cr³⁺ and Sn⁴⁺ cations were studied in acetonitrile–ethanol (AN–EtOH) binary solvent mixtures at different temperatures by the electrical conductometry method. The stability constants of the resulting 1:1 complexes were determined from computer fitting of the conductance versus mole ratio data. The results show that the selectivity order of 4′NB15C5 for the metal cations in the AN–EtOH (mol-%AN=76) binary solvent at 298.15 K is: Cr³⁺>Mn²⁺≈Zn²⁺>Sn⁴⁺, but the selectivity order changes with the composition of the mixed solvents. A nonlinear relationship was observed between the stability constants (log ₁₀ K _f) of these complexes and the composition of the AN–EtOH binary solvents. The corresponding thermodynamic parameters (DH_c^o, DS_c^o)(\Delta H_{\mathrm{c}}^{\mathrm{o}}, \Delta S_{\mathrm{c}}^{\mathrm{o}}) were obtained from the temperature dependence of the stability constants using van’t Hoff plots. The results show that the values and also the sign of these parameters are influenced by the nature and composition of the mixed solvents.     

Study of Complex Formation between N-Phenylaza-15-Crown-5 with Mg2+, Ca2+, Ag+ and Cd2+ Metal Cations in Some Binary Mixed Aqueous and Non-aqueous Solvents using the Conductometric Method

The complexation reactions between Mg²⁺, Ca²⁺, Ag⁺ and Cd²⁺ metal cations with N-phenylaza-15-crown-5 (Ph-N15C5) were studied in acetonitrile (AN)–methanol (MeOH), methanol (MeOH)–water (H₂O) and propanol (PrOH)–water (H₂O) binary mixtures at different temperatures using the conductometric method. The conductance data show that the stochiometry of all of the complexes with Mg²⁺, Ca²⁺, Ag⁺ and Cd²⁺ cations is 1:1 (L:M). The stability of the complexes is sensitive to the solvent composition and a non-linear behaviour was observed for variation of log K _f of the complexes versus the composition of the binary mixed solvents. The selectivity order of Ph-N15C5 for the metal cations in neat MeOH is Ag⁺>Cd²⁺>Ca²⁺>Mg²⁺, but in the case of neat AN is Ca²⁺>Cd²⁺>Mg²⁺>Ag⁺. The values of thermodynamic parameters (ΔH _c ^o , ΔS _c ^o ) for formation of Ph-N15C5–Mg²⁺, Ph-N15C5–Ca²⁺, Ph-N15C5–Ag⁺ and Ph-N15C5–Cd²⁺ complexes were obtained from temperature dependence of stability constants and the results show that the thermodynamics of complexation reactions is affected by the nature and composition of the mixed solvents.     

Thermodynamic characteristics of the acid dissociation of dopamine hydrochloride in water-ethanol solutions

Enthalpies of the interaction of protonated dopamine with a hydroxide ion in water-ethanol mixtures in the concentration range of 0–0.8 EtOH mole fractions are measured calorimetrically. The neutralization process of dopamine hydrochloride is shown to occur endothermally in solvents with an ethanol concentration of ≥0.5 mole fractions. Standard thermodynamic characteristics (Δ_r H ^○, Δ_r G ^○, and Δ_r S ^○) of the first-step acid dissociation of dopamine hydrochloride in solutions are calculated with regard to the autoprotolysis enthalpy of binary solvents. It is found that dissociation enthalpies vary within 9.1–64.8 kJ/mol, depending on the water-ethanol solvent composition.     

Structural and electrochemical behavior of Mn–V oxide synthesized by a novel precipitation method

Manganese–vanadium oxide had been synthesized by a novel simple precipitation technique. Scanning electron microscopy, X-ray diffraction, Brunauer–Emmett–Teller, thermogravimetric analysis/differential scanning calorimetry, and X-ray photoelectron spectroscopy were used to characterize Mn–V binary oxide and δ-MnO₂. Electrochemical capacitive behavior of the synthesized Mn–V binary oxide and δ-MnO₂ was investigated by cyclic voltammetry, galvanostic charge–discharge curve, and electrochemical impedance spectroscope methods. The results showed that, by introducing V into δ-MnO₂, the specific surface area of the mixed oxide increased due to a formation of small grain size. The specific capacitance increased from 166 F g⁻¹ estimated for MnO₂ to 251 F g⁻¹ for Mn–V binary oxide, and the applied potential window extended to −0.2–1.0 V (vs. saturated calomel electrode). Through analysis, it is suggested that the capacitance performance of Mn–V binary oxide materials may be improved by changing the following three factors: (1) small grain and particle size and large activity surface area, (2) appropriate amount of lattice water, and (3) chemical state on the surface of MnO₂ material.     

Solvent effect on distribution of phenyl groups for C<Subscript>6</Subscript>H<Subscript>5</Subscript>SiO<Subscript>3/2</Subscript>–SiO<Subscript>2</Subscript> coatings prepared on polycarbonate substrate

Phenyltriethoxysilane (PhTES) and tetraethoxysilane (TEOS) coatings [xPhTES·(100 − x)TEOS (mol%)] (x = 0–80) were prepared using methanol (Film A) or 1-propanol (Film B) as a solvent on polycarbonate (PC) substrate, and the effect of alcohol solvents on both the adhesion and distribution of phenyl groups were studied. The alcohol evaporation rates for Films A and B were monitored by using quartz crystal microbalance (QCM). QCM measurements revealed that the migration of phenyl group to the PC substrate side was strongly related with the alcohol solvent. Transmission fourier transform infrared measurements for these films suggest that a phase-separation between SiO₂ and PhSiO_3/2 networks occur during the alcohol evaporation.     

Complexes of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) with 4-chloro-2-methoxybenzoic acid anion

The complexes of 4-chloro-2-methoxybenzoic acid anion with Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺ and Zn²⁺ were obtained as polycrystalline solids with general formula M(C₈H₆ClO₃)₂·nH₂O and colours typical for M(II) ions (Mn – slightly pink, Co – pink, Ni – slightly green, Cu – turquoise and Zn – white). The results of elemental, thermal and spectral analyses suggest that compounds of Mn(II), Cu(II) and Zn(II) are tetrahydrates whereas those of Co(II) and Ni(II) are pentahydrates. The carboxylate groups in these complexes are monodentate. The hydrates of 4-chloro-2-methoxybenzoates of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) heated in air to 1273 K are dehydrated in one step in the range of 323–411 K and form anhydrous salts which next in the range of 433–1212 K are decomposed to the following oxides: Mn₃O₄, CoO, NiO and ZnO. The final products of decomposition of Cu(II) complex are CuO and Cu. The solubility value in water at 293 K for all complexes is in the order of 10^–3 mol dm^–3. The plots of χ_M vs. temperature of 4-chloro-2-methoxybenzoates of Mn(II), Co(II), Ni(II) and Cu(II) follow the Curie–Weiss law. The magnetic moment values of Mn²⁺, Co²⁺, Ni²⁺ and Cu²⁺ ions in these complexes were determined in the range of 76−303 K and they change from: 5.88–6.04 μ_B for Mn(C₈H₆ClO₃)₂·4H₂O, 3.96–4.75 μ_B for Co(C₈H₆ClO₃)₂·5H₂O, 2.32–3.02 μ_B for Ni(C₈H₆ClO₃)₂·5H₂O and 1.77–1.94 μ_B for Cu(C₈H₆ClO₃)₂·4H₂O.     

Conformational Analysis,Infrared, and Fluorescence Spectra of 1-Phenyl-1,2-propandione 1-oxime and Related Tautomers: Experimental and Theoretical Study

Summary. Conformational analysis and frequency calculation were achieved for 1-phenyl-1,2-propandione 1-oxime and its four tautomers: 1-nitroso-1-phenyl-1-propen-2-ol, 1-nitroso-1-phenyl-2-propanone, 2-hydroxy-1-phenyl-propenone oxime, and 3-nitroso-3-phenyl-propen-2-ol. Calculations were carried out at the Hartree–Fock (HF), Density Functional Theory (B3LYP), and the second-order M?ller–Plesset perturbation (MP2) levels of theory using 6-31G^* and 6-311G^** basis sets. Five conformers with no imaginary vibrational frequency were obtained by free rotations around three single bonds of 1-phenyl-1,2-propandione-1-oxime: Ph–C(NOH)C(O)CH₃, PhC(NOH)–C(O)CH₃, and PhC(N–OH)C(O)CH₃. Similarly, eight structures with no imaginary vibrational frequency were encountered upon rotations around three single bonds of 1-nitroso-1-phenyl-1-propen-2-ol: Ph–C(NO)C(OH)CH₃, PhC(N–O)C(OH)CH₃, and PhC(NO)C(–OH)CH₃. In the same manner, six minima were found through rotations around three single bonds of 1-nitroso-1-phenyl-2-propanone: Ph–CH(NO)C(O)CH₃, PhCH(–NO)C(O)CH₃, and PhCH(NO)–C(O)CH₃. Also, two minima were found through rotations around four single bonds of 2-hydroxy-1-phenyl-propenone oxime: Ph–C(NOH)C(OH)CH₂, PhC(N–OH)C(OH)CH₂, PhC(NOH)–C(OH)CH₂, and Ph-C(NOH)C(–OH)CH₂. Finally, two minima were found through rotations around four single bonds of 3-nitroso-3-phenyl-propen-2-ol: Ph–CH(NO)C(OH)CH₂, PhCH(–NO)C(OH)CH₂, PhCH(NO)–C(OH)CH₂, and PhCH(NO)C(–OH)CH₂. Interconversions within the above sets of conformers were probed through scanning (one and/or two dimensional), and/or QST3 techniques. The order of the stability of global minima encountered was: 1,2-propandione-1-oxime > 1-nitroso-1-phenyl-2-propanone > 1-nitroso-1-phenyl-1-propen-2-ol > 2-hydroxy-1-phenyl-propenone oxime > 3-nitroso-3-phenyl-propen-2-ol. Hydrogen bonding appears significant in tautomers of 1-nitroso-1-phenyl-1-propen-2-ol and 2-hydroxy-1-phenyl-propenone oxime. The CIS simulated λ_max for the first excited singlet state (S₁) of 1-phenyl-1,2-propandione 1-oxime is 300.4 nm, which was comparable to its experimental λ_max of 312.0 nm. The calculated IR spectra of 1-phenyl-1,2-propandione 1-oxime and its tautomers were compared to the experimental spectra.     

Microwave saturation of EPR spectra of oxidised coal

Microwave saturation of multi-component EPR spectra of oxidized lignite Mequinenza (Spain) with a carbon content of 65.1 wt % and with a high sulphur content of 10.3 wt % was studied. The coal was oxidized with nitric acid (NHO₃), peroxyacetic acid (PAA), and in O₂/Na₂CO₃ system. Three different groups of paramagnetic centres exist in the coal samples analyzed. The EPR spectrum of the demineralised coal was a superposition of broad Gauss (ΔB _pp = 0.75 mT), broad Lorentz 1 (ΔB _pp = 0.42 mT) and narrow Lorentz 3 lines (ΔB _pp = 0.08 mT). The three EPR components with linewidths: 0.58–0.77 mT (Gauss line), 0.30–0.39 mT (Lorentz 1 line) and 0.05–0.06 mT (Lorentz 3 line) were recorded for the oxidized coal. The g-values were obtained for the samples studied in the ranges 2.0043–2.0046 (Gauss lines), 2.0035–2.0038 (Lorentz 1 lines) and 2.0032–2.0034 (Lorentz 3 lines). The broad Gauss and Lorentz 1 lines saturate at low microwave powers. The narrow Lorentz 3 lines of demineralised coal were not saturated at microwave power from the range considered. After the coal oxidation with HNO₃, PAA and in O₂/Na₂CO₃ system, the microwave saturation of the narrow Lorentz 3 lines was also observed, which indicated a degradation of the multi-ring aromatic structures upon oxidation.      

Conformational Analysis, Infrared, and Fluorescence Spectra of 1-Phenyl-1,2-propandione 1-oxime and Related Tautomers: Experimental and Theoretical Study

Conformational analysis and frequency calculation were achieved for 1-phenyl-1,2-propandione 1-oxime and its four tautomers: 1-nitroso-1-phenyl-1-propen-2-ol, 1-nitroso-1-phenyl-2-propanone, 2-hydroxy-1-phenyl-propenone oxime, and 3-nitroso-3-phenyl-propen-2-ol. Calculations were carried out at the Hartree–Fock (HF), Density Functional Theory (B3LYP), and the second-order M?ller–Plesset perturbation (MP2) levels of theory using 6-31G^* and 6-311G^** basis sets. Five conformers with no imaginary vibrational frequency were obtained by free rotations around three single bonds of 1-phenyl-1,2-propandione-1-oxime: Ph–C(NOH)C(O)CH₃, PhC(NOH)–C(O)CH₃, and PhC(N–OH)C(O)CH₃. Similarly, eight structures with no imaginary vibrational frequency were encountered upon rotations around three single bonds of 1-nitroso-1-phenyl-1-propen-2-ol: Ph–C(NO)C(OH)CH₃, PhC(N–O)C(OH)CH₃, and PhC(NO)C(–OH)CH₃. In the same manner, six minima were found through rotations around three single bonds of 1-nitroso-1-phenyl-2-propanone: Ph–CH(NO)C(O)CH₃, PhCH(–NO)C(O)CH₃, and PhCH(NO)–C(O)CH₃. Also, two minima were found through rotations around four single bonds of 2-hydroxy-1-phenyl-propenone oxime: Ph–C(NOH)C(OH)CH₂, PhC(N–OH)C(OH)CH₂, PhC(NOH)–C(OH)CH₂, and Ph-C(NOH)C(–OH)CH₂. Finally, two minima were found through rotations around four single bonds of 3-nitroso-3-phenyl-propen-2-ol: Ph–CH(NO)C(OH)CH₂, PhCH(–NO)C(OH)CH₂, PhCH(NO)–C(OH)CH₂, and PhCH(NO)C(–OH)CH₂. Interconversions within the above sets of conformers were probed through scanning (one and/or two dimensional), and/or QST3 techniques. The order of the stability of global minima encountered was: 1,2-propandione-1-oxime > 1-nitroso-1-phenyl-2-propanone > 1-nitroso-1-phenyl-1-propen-2-ol > 2-hydroxy-1-phenyl-propenone oxime > 3-nitroso-3-phenyl-propen-2-ol. Hydrogen bonding appears significant in tautomers of 1-nitroso-1-phenyl-1-propen-2-ol and 2-hydroxy-1-phenyl-propenone oxime. The CIS simulated λ_max for the first excited singlet state (S₁) of 1-phenyl-1,2-propandione 1-oxime is 300.4 nm, which was comparable to its experimental λ_max of 312.0 nm. The calculated IR spectra of 1-phenyl-1,2-propandione 1-oxime and its tautomers were compared to the experimental spectra.     

Speciation of BCxNy films grown by PECVD with trimethylborazine precursor

Films of BC _x N _y were produced in a plasma-enhanced chemical vapor deposition process using trimethylborazine as precursor and with H₂, He, N₂, and NH₃, respectively, as auxiliary gas. These films deposited on Si(100) wafers or fused quartz glass substrates were characterized chemically by X-ray photoelectron spectroscopy and by synchrotron radiation-based total-reflection X-ray fluorescence combined with near-edge X-ray absorption fine structure. Independent of the auxiliary gas, the B–N bonds are dominating. Furthermore, B–C and N–C bonds were identified. Oxygen, present in the bulk (in contrast to the surface layer of some nanometers, where molecular oxygen and/or water are absorbed) as an impurity, is bonded to boron or to carbon, respectively. The relation of boron and nitrogen changes with the character of the auxiliary gas: c _B/c _N ≈ 4:3 (for H₂ and He) and c _B/c _N ≈ 1 (for N₂ or NH₃). Furthermore, physical properties such as the refractive index and the optical band-gap energy were determined.     

Glycol modified titanosiloxane as molecular precursor for homogenous titania–silica material: synthesis and characterization

Ti(OPrⁱ)₄ reacts with HOSi(O^tBu)₃ in anhydrous benzene in 1:1 and 1:2 molar ratios to afford alkoxy titanosiloxane precursors, [Ti(OPrⁱ)₃{OSi(O^tBu)₃}] (A) and [Ti(OPrⁱ)₂{OSi(O^tBu)₃}₂] (B), respectively. Further reactions of (A) or (B) with glycols in 1:1 molar ratio afforded six complexes of the types [Ti(OPrⁱ)(O–G–O){OSi(O^tBu)₃}] (1A–3A) and [Ti(O–G–O){OSi(O^tBu)₃}₂] (1B–3B), respectively [where G = (CH₂)₂ (1A, 1B); (CH₂)₃ (2A, 2B) and {CH₂CH₂CH(CH₃)} (3A, 3B)]. Both (A) and (B) are liquids while all the other products are viscous liquids which get solidified on ageing. Cryoscopic molecular weight measurements of the fresh products indicate their monomeric nature. FAB mass studies of (A) and (B) also indicate monomeric nature. However, FAB mass spectra of the two representative solids (1A) and (2B) suggest dimeric behavior of the glycolato derivatives. (A) distills at 85 °C/5 mm while other products get decomposed even under reduced pressure. TG analyses of (A), (B), (1A), and (1B) suggest formation of titania–silica materials at 200 °C for (A) and (B) and 350 °C for (1A) and (1B). The products have been characterized by elemental analyses, FTIR and ¹H, ¹³C & ²⁹Si-NMR techniques. All these products are soluble in common organic solvents indicating a homogenous distribution of the components on the molecular scale. The Si/Ti ratio of the oxide may be controlled easily by the composition of the starting precursors. Hydrolysis of the glycol modified derivative, (1A) by the Sol–Gel technique affords the desired homogenous titania–silica material, TiO₂·SiO₂ in nano-size while, the precursor (A) yields a non-stiochiometric silica doped titania material. However, pyrolysis of (A) yields nano-sized crystallites of TiO₂·SiO₂. All these materials were characterized by FTIR, powder XRD patterns, SEM images, and EDX analyses.     

Formation and multinuclear magnetic resonance investigation of silylammonium tetracarbonylcobaltate contact ion pairs

Silylcobalt tetracarbonyls were reacted with various amines (B) in non-polar solvents to form silylammonium tetracarbonylcobaltate contact ion pairs formulated as [BSiR ₃ ⁺ , ⁻Co(CO)₄]. The compounds were characterized by IR and multinuclear magnetic resonance spectroscopy both in solution and in solid state. Their properties are analogous to the known ion pairs [BH⁺, ⁻Co(CO)₄] and to amine adducts of halosilanes as well.     

Solvatochromic parameters for binary mixtures of an ionic liquid with various protic molecular solvents

Abstract  Solvatochromic parameters (E _T ^N, normalized polarity parameter; π*, dipolarity/polarizability; β, hydrogen-bond acceptor basicity; α, hydrogen-bond donor acidity) have been determined for binary mixtures of propan-2-ol, propan-1-ol, ethanol, methanol and water with recently synthesized ionic liquid (IL; 2-hydroxyethylammonium formate) at 25 °C. In all solutions except aqueous solution, E _T ^N values of the media increase abruptly with the ILs mole fraction and then increase gradually to the value of pure IL. A synergistic behavior is observed for the α parameter in all solutions. The behavior of π* and β are nearly ideal for all solutions except for solutions of methanol with the IL. The applicability of nearly ideal combined binary solvent/Redlich–Kister equation was proved for the correlation of various solvatochromic parameters with solvent composition. The correlation between the calculated and the experimental values of various parameters was in accordance with this model. Solute–solvent and solvent–solvent interactions were applied to interpret the results. Graphical Abstract  Predicted values of solvatochromic parameters (SP) (E _T ^N, normalized polarity parameter; π*, dipolarity/polarizability; β, hydrogen-bond acceptor basicity; α, hydrogen-bond donor acidity) from the correlation equations versus its experimental values for binary mixtures of 2-hydroxyethylammonium formate with water, methanol, ethanol, propan-1-ol and propan-2-ol.      

Growth Pattern, Electronic Structures and Magnetic Moments of Small Lutetium Clusters

The lowest-energy configurations, electronic structures and magnetic moments of small Lu _n (n = 2–20) clusters have been investigated within the framework of density functional theory. The results show that Lu _n (n = 4, 8, 13, and 18) clusters are more stable than their respective neighbors, and structural transformation reveals at n = 16. As the number of atoms increases, the magnetic moments increase in an alternating fashion until they reach a maximum of 4.00 μ_B for Lu₈ clusters, followed by even–odd oscillation between 0.00 and 1.00 μ_B over the range n = 9–20.     

Complexation of 4′-nitrobenzo-15-crown-5 with Mg<Superscript>2+</Superscript>, Ca<Superscript>2+</Superscript>, Sr<Superscript>2+</Superscript> and Ba<Superscript>2+</Superscript> metal cations in acetonitrile-methanol binary solutions

The complex formation reactions between Mg²⁺, Ca²⁺, Sr²⁺ and Ba²⁺ metal cations with macrocyclic ligand, 4′-nitrobenzo-15C5, were studied in acetonitrile (AN)-methanol (MeOH) binary mixtures at different temperatures using conductometric method. The results show that 4′-nitrobenzo-15C5 forms 1:1 [ML] complexes with Mg²⁺, Ca²⁺ and Sr²⁺ metal cations in solutions. But in the case of Ba²⁺ cation a 1:2 [ML₂] complex is formed in these solvent systems. The stability of the complexes is sensitive to the solvent composition and a non-linear behavior was observed for variation of logK _f of the complexes versus the composition of the binary mixed solvents. The stability constants of complexes decrease suddenly with increasing the concentration of methanol in this binary system. The values of thermodynamic parameters (ΔH _c^° and ΔS _c^°) for formation of (4′-nitrobenzo-15C5.Mg)²⁺, (4′-nitrobenzo-15C5.Ca)²⁺ and (4′-nitrobenzo-15C5.Sr)²⁺ complexes were obtained from temperature dependence of the stability constants and the results show that these parameters are affected by the nature and composition of the mixed solvents. A non-linear behavior is observed between the ΔS _c^° and the composition of the mixed solvents.     

Quasi-thermodynamics of Viscous Flow of Electrolyte Solutions in Aqueous, Non-aqueous and Mixed Aqueous Solvents

Viscosity B-coefficients for cesium chloride and lithium sulfate in methanol + water mixtures at 25 and 35 °C are reported. A general treatment of the quasi-thermodynamics of viscous flow of electrolyte solutions is described. ΔG ₃ ^Θ (1→1′), the contribution made to the Gibbs energy of activation of the solution by the influence of the solute on the solvent, is a function of solute–solvent interactions only; but, ΔH ₃ ^Θ (1→1′) and ΔS ₃ ^Θ (1→1′) also reflect the solvent–solvent interactions. In aqueous solution all alkali-metal ions except Li⁺ are sterically unsaturated, having solvent co-ordination numbers n<n _max, the maximum allowed sterically. Such complexes exchange molecules with the solvent more readily than saturated ones and have energy–reaction co-ordinate diagrams in forms that explain the negative B or ΔG ₃ ^Θ (1→1′) values found in aqueous solution. Saturated complexes are the norm in non-aqueous solvents, and the ΔG ₃ ^Θ (1→1′) values are determined mainly by the secondary solvation. Behavior in mixed solvents reflects the transition from aqueous to non-aqueous behavior across the range of solvent composition.     

Thermokinetic study on the phase evolution of mechanically alloyed Ni–B powders

A combination of differential thermal analysis and detailed X-ray diffraction (XRD) analyses were used for the thermokinetic study of phase evolution during heating–cooling of the mechanically alloyed (MA-ed) Ni–15 wt% B. According to the results obtained, different phase transition sequences led to the formation of nanocrystalline Ni–B alloys comprising of Ni₂B + o-Ni₄B₃ and Ni₂B + m-Ni₄B₃ + B. Using the XRD studies, it was found that the Ni₂B is the most stable intermetallic compound in the Ni–B binary phase diagram, and its nanocrystalline nature retained unchanged even after annealing up to temperatures near the melting point. In addition, average enthalpy as well as activation energy of occurred reactions was calculated; the latter was estimated using two well-known Kissinger and Augis & Bennett methods.     

Analysis of Solvent–Solvent Interactions in Mixed Isosteric Solvents by Inverse Gas Chromatography

The Flory–Huggins interaction parameter, χ ₂₃, characterizing the interaction between solvents in a mixed stationary phase has been calculated using inverse gas chromatography (IGC). The χ ₂₃ parameters for four mixed solvent systems formed by mixing a non-polar branched alkane, 19, 24-dioctadecyldotetracontane (C78), with four different polar solvents are analysed as a function of temperature. Two of the polar solvents are formed by replacing one of the –CH₃ groups of C78 by –OH (POH) group and –CN (PCN) group and the other two polar solvents are formed by replacing all the four –CH₃ groups of C78 by four –CF₃ (TTF) groups and four –OCH₃ (TMO) groups. The five solvents have similar structures and nearly the same molar volume and in mixtures, they form regular solutions. For the mixture, C78 + POH, χ ₂₃ was calculated at two compositions and for the remaining three mixtures χ ₂₃ was calculated at equimolar composition. Eight solute probes representing all possible chemical structures and polarity were used under conditions approaching infinite dilution. The effects of temperature, concentration of the mixed solvent and probe solute on χ ₂₃ are presented and discussed. The probe-independent χ ₂₃ values were also calculated by linear regression analysis using the retention data of all the solute probes. In all the mixed solvents considered here the χ ₂₃ values are probe-dependent and decrease with increase of temperature.     

Structural, spectroscopic, electrochemical and computational studies of C,C′-diaryl-ortho-carboranes, 1-(4-XC6H4)-2-Ph-1,2-C2B10H10 (X = H, F, OMe, NMe2, NH2, OH and O−)

The influence of aryl ring substituents X (F, OMe, NMe₂, NH₂, OH and O⁻) on the physical and electronic structure of the ortho-carborane cage in a series of C,C′-diaryl-ortho-carboranes, 1-(4-XC₆H₄)-2-Ph-1,2-C₂B₁₀H₁₀ has been investigated by crystallographic, spectroscopic [nuclear magnetic resonance (NMR), UV–vis], electrochemical and computational methods. The cage C1–C2 bond lengths in this carborane series show small variations with the electron-donating strength of the substituent X, but there is no evidence of a fully evolved quinoid form within the aryl substituents in the ground state. In the ¹¹B and ¹³C NMR spectra, the ‘antipodal’ shift at B12, and the C1 shift correlates with the Hammett σ _p value of the substituent X. The UV–visible absorption spectra of the cluster compounds show marked differences when compared with the spectra of the analogous substituted benzenes. These spectroscopic differences are attributed to variation in contributions from the cage orbitals to the unoccupied/virtual orbitals involved in the transitions responsible for the observed absorption bands. Electrochemical studies (cyclic and square-wave voltammetry) carried out on the diarylcarborane series reveal that one-electron reduction takes place at the cage in every case with the voltage required for reduction of the cage influenced by the electron-donating strength of the substituent X, affording a series of carborane radicals with formal [2n + 3] electron counts. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.