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.     

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.     

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 \( {\Delta_{\text{f}}^{} H}_{\text{m}}^{\text{o}} ({\text{C}}_{ 6} {\text{H}}_{ 4} {\text{NO}}_{2}^{-} \text{,aq}) = - \left( {603.2 \pm 1.2} \right)\;{\text{kJ}}{\cdot}{\text{mol}}^{-1} \).     

Crystallization study of Se<Subscript>86</Subscript>Sb<Subscript>14</Subscript> glass

The present study concerns with high-accuracy determination of crystallization activation energy (\(E_{\text{c}}\)), the frequency factor (\(k_{0}\)), the kinetic exponent (n) for Se₈₆Sb₁₄ glass. Different three methods have been used to investigate the \(E_{\text{c}} \,{\text{and}}\,k_{0 }\) values. It was found that the deduced value of k ₀ based on Kissinger’s method is too small compared with the others. Therefore, it can’t be used to investigate k ₀ value. Where \(E_{\text{c}} \,{\text{and}}\,k_{0}\) values are already known, the overall reaction rate \(k = k_{0 } { \exp }\left( { - E_{\text{c}} /\left( {R \cdot T} \right)} \right)\) at any temperature can be calculated. Now, Avrami’s equation (\(\chi = 1 - { \exp }\left( { - \left( {kt} \right)^{\text{n}} } \right)\)) contains only one unknown which is the kinetic exponent (n). This method enables us to determine n value without any approximations. The values’ crystallization fraction \((\chi_{\text{th}} )\) that theoretically calculated is the same as that experimentally investigated \((\chi_{{{ \exp } .}} )\).     

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.     

The Study of Solute–Solvent Interactions in 1-Butyl-3-Methylimidazolium Hexafluorophosphate + 2-Pyrrolidone from Volumetric,Acoustic, Optical and Spectral Properties

The density (ρ), speed of sound (u) and refractive index (n_D) of [Bmim][PF₆], 2-pyrrolidone and their binary mixtures were measured over the whole composition range as a function of temperature between (303.15 and 323.15)?K at atmospheric pressure. Experimental values were used to calculate the excess molar volumes \( \left( {V_{m}^{\text{E}} } \right) \), excess partial molar volumes \( \left( {\overline{V}_{m}^{\text{E}} } \right) \), partial molar volumes at infinite dilution \( \left( {\overline{V}_{m}^{{{\text{E}},\infty }} } \right) \), excess values of isentropic compressibility \( \left( {\kappa_{S}^{\text{E}} } \right) \), free length \( \left( {L_{\text{f}}^{\text{E}} } \right) \) and speeds of sound \( \left( {u^{\text{E}} } \right) \) for the binary mixtures. The calculated properties are discussed in terms of molecular interactions between the components of the mixtures. The results reveal that interactions between unlike molecules take place, particularly through intermolecular hydrogen bond formation between the C₂–H of [Bmim][PF₆] and the carbonyl group of pyrrolidin-2-one. An excellent correlation between thermodynamic and IR spectroscopic measurements was observed. The observations were further supported by the Prigogine–Flory–Patterson (PFP) theory of excess molar volume.     

Aromaticity of Bare Iridium Trimers and Ir3M0/+ and $$\rm{Ir}_3M_2^{+/3+}$$ (M = Li,Na, K,and Be,Ca) Bimetallic Clusters

The structural stabilities, bonding nature, electronic properties, and aromaticity of bare iridium trimers \(\rm{Ir}_3^{+/-}\) with different geometries and spin multiplicities are studied at the DFT/B3LYP level of theory. The ground state of the \(\rm{Ir}_3^{+}\) cation is found to be the ³A₂ (C_2v) triplet state and the ground state of the \(\rm{Ir}_3^{-}\) anion the ⁵A₂ (C_2v) quintet state. A detailed molecular orbital (MO) analysis indicates that the ground-state \(\rm{Ir}_3^{+}\) ion (C_2v, ³A₂) possesses double (σ and partial δ) aromaticity as well as the ground-state \(\rm{Ir}_3^{-}\) ion (C_2v, ⁵A₂). The multiple d-orbital aromaticity is responsible for the totally delocalized three-center metal-metal bond of the triangular Ir₃ framework. \(\rm{Ir}_3^{-}\) (C_2v, ¹A₁) structure motif is perfectly preserved in pyramidal Ir₃M^0/+ (C_s, ¹A′) and bipyramidal \(\rm{Ir}_3M_2^{+/3+}\) (C_2v, ¹A₁) (M = Li, Na, K and Be, Ca) bimetallic clusters which also possess the corresponding d-orbital aromatic characters.     

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.     

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.     

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.     

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.     

Transition-metal dichalcogenide heterostructure solar cells: a numerical study

We evaluate the tunneling short-circuit current density \(J_{TU}\) in a p–i–n solar cell in which the transition metal dichalcogenide heterostructure (\(\hbox {MoS}_2/\hbox {WS}_2\) superlattice) is embedded in the intrinsic i region. The effects of varying well and barrier widths, Fermi energy levels and number of quantum wells in the i region on \(J_{TU}\) are examined. A similar analysis is performed for the thermionic current \(J_{TH}\) that arises due to the escape and recapture of charge carriers between adjacent potential wells in the i-region. The interplay between \(J_{TU}\) and \(J_{TH}\) in the temperature range (300–330 K) is examined. The thermionic current is seen to exceed the tunneling current considerably at temperatures beyond 310 K, a desirable attribute in heterostructure solar cells. This work demonstrates the versatility of monolayer transition metal dichalcogenides when utilized as fabrication materials for van der Waals heterostructure solar cells.     

Deposition Morphology and Magnetism of Co,Pt Adatoms and Small CoPt Adclusters on Ni(100) Substrate

Theoretical calculations of Co\(_{n-x}\)Pt\(_x\) (n = 1–3; \(x \le n\)) clusters on Ni(100) surface for their spin and orbital magnetic moments, as well as the magnetic anisotropy energy (MAE), are performed by using the density-functional theory (DFT) method including a self-consistent treatment of spin–orbit coupling (SOC). The results reveal that the ferromagnetic Co atoms in intra Co\(_{n-x}\)Pt\(_x\) adclusters couple ferromagnetically to their underlayer Ni atoms. The predominant inter-interactions between Co adatoms and Ni surface with the partly filled 3d band, together with the secondary intra-interactions between Co adatoms and Pt adatoms with fully filled 5d band, lead to a strongly quenched orbital moment (\(\mu _{\mathrm{{orb}}}^{\mathrm{{Co}}}\) = 0.18–0.14 \(\mu _B\); \(\mu _{\mathrm{{orb}}}^{\mathrm{{Pt}}} \approx \) 0.24–0.19 \(\mu _B\)) but a less quenched spin moment (\(\mu _{\mathrm{{spin}}}^{\mathrm{{Co}}} \approx \) 2.0 \(\mu _B\); \(\mu _{\mathrm{{spin}}}^{\mathrm{{Pt}}} \approx \) 0.35 \( \mu _B\)). The MAEs of CoPt adclusters exhibit a strong dependence on alloying effect rather than size effect, which is direly proportional to SOC strength and orbital moment anisotropy. The oxidations of CoPt clusters always reduce orbital magnetic moments and consequently decrease the corresponding MAEs.     

Measurement and Modeling the Excess Molar Volumes and Refractive Index Deviations of Binary Mixtures of 2-Propanol, 2-Butanol and 2-Pentanol with <Emphasis Type="Italic">N</Emphasis>-Propylamine

The densities, ρ, and refractive indices, n _D, of 2-alkanols (C₃–C₅) with N-propylamine have been measured for the whole range of composition at temperatures from (298.15–328.15) K at 10 K intervals and ambient pressure of 81.5 kPa, using an Anton Paar DMA 4500 oscillating tube densimeter and an Anton Paar Abbemat 500 automatic refractometer. From the experimental data, excess molar volumes \( V_{\text{m}}^{\text{E}} \) partial molar volumes \( \bar{V}_{i} \) apparent molar volumes V _?i and refractive index deviations Δn _D the binary systems consisting of N-propylamine + 2-alkanols (2-propanol, 2-butanol, 2-pentanol) were calculated and \( V_{\text{m}}^{\text{E}} \) and Δn _D values were correlated with the Redlich–Kister polynomial. The effect of temperature and the chain length of the alcohol on the excess molar volumes and refractive index deviations are discussed in terms of molecular interaction between unlike molecules. The excess molar volumes are negative and refractive index deviations are positive over the entire composition range, which indicates strong hydrogen bonding between molecules of the mixtures. A comparative study has been made of the refractive indices obtained experimentally and those calculated by means of the Lorentz–Lorenz, Weiner and Arago–Biot relations. The perturbed chain statistical associating fluid theory (PC-SAFT), simplified PC-SAFT and Prigogine–Flory–Patterson theory were also applied to correlate and predict the density and excess molar volumes of the mixtures.     

Determination of sorption and diffusion parameters of <Superscript>99</Superscript>Tc in crushed granite using through-diffusion experiments

Diffusion and sorption are important processes associated with radionuclides migration in crystalline rock. These processes are studied in the laboratory using borehole core samples. In this study, we obtained distribution coefficients (K _d), apparent diffusion coefficients (D _a) and retardation factor (R _f) using batch and through-diffusion experiments. The \( R_{\text{f}}^{\text{H/Tc}} \) and \( K_{\text{d}}^{\text{H/Tc}} \) values obtained using the accumulative concentration method were lower than those derived in the batch experiments. These findings demonstrate that reliable R _f and K _d values of ⁹⁹Tc can be obtained using through-diffusion experiments with a non-reactive radiotracer, thereby bolstering confidence in the assessment of the long-term performance of disposal repositories.     

Thermochemistry of the Reaction of Solvated Sodium Ion Clusters with Thymine in the Gas Phase: An Example of the Reaction in Microcosmic Environment

The thermochemistry of the reaction of the microsolvated Na⁺ such as [Na(H₂O) _n ; n?=?1?6]⁺, [Na(NH₃) _n ; n?=?1?6]⁺ and [Na(H₂O) _n (NH₃) _m ; n?+?m?=?2?6]⁺ with thymine (Thy), as an example of a reaction in the microcosmic environment, have been studied in this work, theoretically. It was found that the increase of the number of solvent molecules in the structure of microsolvated Na⁺ is accompanied by the decrease of the standard enthalpy (\(\Delta H_{r}^{^\circ }\)) and Gibbs free (\(\Delta G_{r}^{^\circ }\)) energies of the reaction (Thy?+?[Na(X) _n ]⁺→Thy-Na(X) _n ⁺ ; X?=?solvent molecule). Also, the calculations showed that the electronic intermolecular interaction (?E_int) between the Thy and microslovated Na⁺ decreased with the increase of solvent molecules. For the interaction of the [Na(H₂O) _n ; n?=?4, 5 and 6]⁺ ions with the Thy, there was the probability of forming of the hydrogen bond between water molecules in the structure of solvated Na⁺ and the Thy. The gas phase infrared (IR) spectra of the complexes of the microsolvated Na⁺ with the Thy for different values of n were calculated and compared with each other to follow the change in the frequency of the stretching vibration of the interaction path between the C=O group of the Thy and Na (O…Na) with n. Using the calculated values of \(\Delta G_{r}^{^\circ }\) of the reactions, the mole fractions of the complexes of microsolvated Na⁺ ions with the Thy were calculated at different humidity.     

The Partial Molar Isothermal Compressions of the Nucleosides Adenosine,Cytidine, and Uridine in Aqueous Solution at <Emphasis Type="Italic">T</Emphasis> = (288.15 and 313.15) K

Sound speeds have been measured for aqueous solutions of the nucleosides adenosine, cytidine, and uridine at T = (288.15 and 313.15) K and at ambient pressure. The partial molar isentropic compressions at infinite dilution, \( K_{S,2}^{\text{o}} \), were derived from the speed of sound data. The partial molar heat capacities at infinite dilution, \( C_{p,2}^{\text{o}} \), for the three nucleosides at T = (288.15 and 313.15) K were also determined. These \( K_{S,2}^{\text{o}} \) and \( C_{p,2}^{\text{o}} \) results, along with partial molar isobaric expansions at infinite dilution, \( E_{2}^{\text{o}} = \, (\partial V_{2}^{\text{o}} /\partial T)_{p} \), that were derived using data from the literature, were used to evaluate the partial molar isothermal compressions at infinite dilution, \( K_{T,2}^{\text{o}} \{ K_{T,2}^{\text{o}} = - \, (\partial V_{2}^{\text{o}} /\partial p)_{T} \} \), for the nucleosides. The \( K_{T,2}^{\text{o}} \) results were rationalized in terms of nucleoside hydration and its temperature dependence.     

Hierarchical enumeration of Kekulé’s benzenes,Ladenburg’s benzenes,Dewar’s benzenes,and benzvalenes by using combined-permutation representations

The group hierarchy for each skeleton of ligancy 6 is formulated to be: point group (PG \({\varvec{G}}_{\sigma }\)) \(\subseteq \) RS-stereoisomeric group (RS-SIG \({\varvec{G}}_{\sigma \widetilde{\sigma }\widehat{I}}\)) \(\subseteq \) stereoisomeric group (SIG \(\widetilde{{\varvec{G}}}_{\sigma \widetilde{\sigma }\widehat{I}}\)) \(\subseteq \) isoskeletomeric group (ISG \(\widetilde{\widetilde{{\varvec{G}}}}_{\sigma \widetilde{\sigma }\widehat{I}}\) = \({\varvec{S}}^{[6]}_{\sigma \widehat{I}}\)), where we start from the PG \({\varvec{G}}_{\sigma }\) = \({\varvec{D}}_{6h}\) for the Kekulé benzene skeleton, from the PG \({\varvec{G}}_{\sigma }\) = \({\varvec{D}}_{3h}\) for the Ladenburg benzene skeleton, from the PG \({\varvec{G}}_{\sigma }\) = \({\varvec{C}}_{2v}\) for the Dewar benzene skeleton, or from the PG \({\varvec{G}}_{\sigma }\) = \({\varvec{C}}_{2v}\) for the benzvalene skeleton. After these groups are constructed as combined-permutation representations, the calculation of the respective cycle indices with chirality fittingness (CI-CFs) and the introduction of ligand-inventory functions are conducted to give generation functions for 3D-based enumerations (for PGs and RS-SIGs) and 2D-based enumerations (for SIGs and ISGs). The enumeration results are discussed by means of isomer-classification diagrams, in which equivalence classes under enantiomerism (for PGs), RS-stereoisomerism (for RS-SIGs), stereoisomerism (for SIGs), and isoskeletomerism (for ISGs) are illustrated schematically. The implicit connotations of the conventional terms “skeletal isomerism”, “positional isomerism”, and “constitutional isomerism” are discussed, where the effects of the concept of isoskeletomerism are emphasized.     

Base hydrolysis of tris(3-(2-pyridyl)-5,6-bis(4-phenyl sulphonic acid)-1,2,4-triazine)iron(II) in aqueous,SDS and CTAB media: kinetic and mechanistic study

The kinetics and mechanism of base hydrolysis of tris(3-(2-pyridyl)-5,6-bis(4-phenyl sulphonic acid)-1,2,4-triazine)iron(II), \({\text{Fe}}({\text{PDTS}})_{3}^{4 - }\) have been studied in aqueous, sodium dodecyl sulphate (SDS) and cetyltrimethyl ammonium bromide (CTAB) media at 25, 35 and 45 °C under pseudo-first-order conditions, i.e. \(\left[ {\text{OH}^{ - } } \right]\) ? \({\text{Fe}}({\text{PDTS}})_{3}^{4 - }\). The reaction is first order each in \({\text{Fe}}({\text{PDTS}})_{3}^{4 - }\) and hydroxide ion. The rate increases with increasing ionic strength in aqueous and SDS media, whereas this parameter has little effect in CTAB. In SDS medium, the rate-determining step involves the reaction between \(\left[ {\text{OH}^{ - } } \right]\) and \({\text{Fe}}({\text{PDTS}})_{3}^{4 - }\), whereas in CTAB medium, it involves reaction between a neutral ion pair, {\({\text{Fe}}({\text{PDTS}})_{3}^{4 - }\)·4CTA⁺} and \(\left[ {\text{OH}^{ - } } \right]\) ions. The specific rate constants and thermodynamic parameters (E _a, ΔH ^#, ΔS ^# and ΔG _35°C ^# ) have been evaluated in all three media. The near equal values of ΔG _35°C ^# obtained in aqueous and SDS media suggest that these reactions occur essentially by the same mechanism. Slightly lower ΔG _35°C ^# values in CTAB medium can be attributed to a higher concentration of reactants in the Stern layer. The reaction is inhibited in SDS medium but catalysed in CTAB. The former can be attributed to the anionic surfactant creating more repellent space between the reactants. Catalysis in CTAB medium is ascribed to electrophilic and hydrophilic interactions between hydroxide ion/substrate with the cationic Stern layer, resulting in increased local concentrations of both reactants.