Heat capacity and thermodynamic functions of ferrocenemethanol

The heat capacity (C _{p, m}) of ferrocenemethanol (FM) C₅H₅FeC₅H₄CH₂OH have been measured by the low-temperature adiabatic calorimetry method in the range 6–371 K. The triple point temperature, the enthalpy of fusion, and the purity of the substance under consideration have been determined. The ideal gas thermodynamic functions of FM—absolute entropy S _m(g) ⁰ and change in the enthalpy Δ ₀ ^T H _m at 298.15 K—have been derived from the heat capacity data and the known values of the saturation vapor pressure and enthalpy of sublimation. The ideal gas thermodynamic functions C _{p, m} ⁰ and S _m(g) ⁰ and the enthalpy of formation of FM have been calculated by the empirical difference method at T = 298.15 K. The experimental and calculated values of the thermodynamic functions are consistent within error limits, which proves their reliability.     

Thermal deformation thermodynamics of a smectite mineral

A method has been purposed to calculate some of the thermodynamic quantities for the thermal deformation of a smectite without using any basic thermodynamic data. The Hanç?l? (Keskin, Ankara, Turkey) bentonite containing a smectite of 88% by volume was taken as material. Thermogravimetric (TG) and differential thermal analysis (DTA) curves of the sample were obtained. Bentonite samples were heated at various temperatures between 25–900°C for the sufficient time (2 h) until to establish the thermal deformation equilibrium.Cation-exchange capacity (CEC) of heated samples was determined by using the methylene blue standard method. The CEC was used as a variable of the equilibrium. An arbitrary equilibrium constant (K _a) was defined similar to chemical equilibrium constant and calculated for each temperature by using the corresponding CEC-value. The arbitrary changes in Gibbs energy (ΔG _a ⁰ ) were calculated from K _a-values. The real change in enthalpy (ΔH ⁰) and entropy (ΔS ⁰) was calculated from the slopes of the lnK vs. 1/T and ΔG vs. T plots, respectively. The real changes in Gibbs energy (ΔG ⁰) and real equilibrium constant (K) were calculated by using the ΔH ⁰ and ΔS ⁰ values. The results at the two different temperature intervals are summarized as below: ΔG ₁ ⁰ =ΔH ₁ ⁰ ?ΔS ₁ ⁰ T=?RTlnK ₁=47000?53t, (200–450°C), and ΔG ₂ ⁰ =ΔH ₂ ⁰ -ΔS ₂ ⁰ T=?RTlnK ₂=132000?164T, (500–800°C).     

Synthesis,structure, physicochemical properties,and solid-phase thermolysis of Co<Subscript>2</Subscript>Sm(Piv)<Subscript>7</Subscript>(2,4-Lut)<Subscript>2</Subscript>

Heterometallic pivalate Co₂Sm(Piv)₇(2,4-Lut)₂ (1) was prepared for the first time and structurally characterized at 293 and 160 K. Antiferromagnetic exchange interactions are dominant in complex 1. This compound experiences a first-order phase transition within 210–260 K. A set of thermodynamic functions was obtained for this complex (C _p , H _T ⁰ - H ₁₈₀ ⁰ , and S _T ⁰ ), and parameters were determined for solid-phase thermolysis where samarium cobaltate SmCoO₃ is the only product.     

Solution Thermodynamics of <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis><Superscript>/</Superscript>-Ethylenebis-(salicylideneiminato)-diaquochromium(III) Chloride in Aqueous Dimethylsulphoxide

The densities, viscosities and refractive indices of N,N ^/-ethylene-bis(salicylideneiminato)-diaquochromium(III) chloride, [Cr(salen)(H₂O)₂]Cl, in aqueous dimethylsulfoxide (DMSO) with different mass fractions (w ₂ = 0.20, 0.40, 0.60, 0.80 and 1.00) of DMSO were determined at 298.15, 308.15 and 318.15 K under atmospheric pressure. From measured densities, viscosities and refractive indices the apparent molar volumes (V _φ ), standard partial molar volume (V _φ ⁰ ), the slope (S _V ^* ), standard isobaric partial molar expansibility (φ _E ⁰ ) and its temperature dependence (?φ _E ⁰ /?T) _p , the viscosity B-coefficient, its temperature dependence (?B/?T), solvation number (S _n ) and apparent molar refractivity (R _D ^φ ), etc., were calculated and discussed on the basis of ion–ion and ion–solvent interactions. These results revealed that the solutions are characterized by ion–solvent interactions rather than by ion–ion interactions and the complex behaves as a long range structure maker. Thermodynamics of viscous flow was discussed in terms of transition state theory.     

Electronic Structure and Relative Stabilities of 10- and 12-Vertex. <Emphasis Type="Italic">Closo</Emphasis>and <Emphasis Type="Italic">Nido</Emphasis>-Heteroborane Clusters of Ga,Ge, and As Elements

A DFT method with the B3LYP functional and the 6-311++G(d,p) diffuse basis set is used to predict geometries, relative stabilities, electronic structures, and the bonding of closo- and nido-Ga_mB_n–mH _n ^2? , Ge_mB_n–mH _n ^m?2 , and As_mB_n–mH _n ^{2 m?2} (n = 10, 12 and m = 1, 2) Clusters are obtained by replacing BH with isolobal GaH, GeH⁺, and AsH²⁺ fragments, keeping the same skeleton electron pairs (SEP). Based on the polyhedral skeletal electron pairs theory (PSEPT), closo and nido structures are predicted and can be of significant interest for experimentalists working in the field of heteroboranes. Different cluster stabilities are studied according to Gimarc′s and Williams′ rules, where our calculations show that the monosubstituted clusters deviate from these rules, giving rise to open structures. As₂B₈H _n ²⁺ as 10-vertex structures lead to nido-type clusters, however, Ge_mB_n–mH _n ^m?2 (n = 10, 12 and m = 1, 2) give rise to closo isomers with close energies. All optimized structures exhibit large HOMO–LUMO gaps suggesting a good kinetic stability, thus predicting their isolation and characterization.     

Stability of diammine and chloroammine gold(I) complexes in aqueous solution

The substitution equilibria AuCl ₂ ^? + iNH ₄ ⁺ = Au(NH₃)_iCl_{2 ? i} + iCl^? + iH⁺, β _i ^* . were studied pH-metrically at 25°C and I = 1 mol/L (NaCl) in aqueous solution. It was found that logβ ₁ ^* = ?5.10±0.15 and logβ ₂ ^* = ?10.25±0.10. For equilibrium AuNH₃Cl_solid = AuNH₃Cl, log K _s = ?3.1±0.3. Taking into account the protonation constants of ammonia (log K _H = 9.40), the obtained results show that for equilibria AuCl ₂ ^? + iNH₃ = Au(NH₃)_iCl_{2 ? i} + iCl^?, logβ₁ = 4.3±0.2, and logβ₂ = 8.55±0.15. The standard potentials E ₀ ^1/0 of AuNH₃Cl⁰ and Au(NH₃) ₂ ⁺ species are equal to 0.90±0.02 and 0.64±0.01 V, respectively.     

Solute–solvent interactions in 2,4-dihydroxyacetophenone isonicotinoylhydrazone solutions in N,N-dimethylformamide and dimethyl sulfoxide at 298–313 K on ultrasonic and viscometric data

The speed of sound (u), density (ρ), and viscosity (η) of 2,4-dihydroxyacetophenone isonicotinoylhydrazone (DHAIH) have been measured in N,N-dimethyl formamide and dimethyl sulfoxide at equidistance temperatures 298.15, 303.15, 308.15, and 313.15 K. These data were used to calculate some important ultrasonic and thermodynamic parameters such as apparent molar volume (V _{? s} ^st ), apparent molar compressibility (K _?), partial molar volume (V _? ⁰ ) and partial molar compressibility (K _? ⁰ ), were estimated by using the values of (V _? ⁰ ) and (K _?), at infinite dilution. Partial molar expansion at infinite dilution, (? _E ⁰ ) has also been calculated from temperature dependence of partial molar volume V _? ⁰ . The viscosity data have been analyzed using the Jones–Dole equation, and the viscosity, B coefficients are calculated. The activation free energy has been calculated from B coefficients and partial molar volume data. The results have been discussed in the term of solute–solvent interaction occurring in solutions and it was found that DHAIH acts as a structure maker in present systems.     

Prediction of changes in the heat capacity of the liquid–vapor phase transition based on modified Randič indices. Alkanes and oxygen-containing compounds

The work proposes a method to predict changes in the heat capacity of the liquid—vapor phase transition Δ _l ^g Ср ⁰ (298.2) based on modified Randi? indices for alkanes and acyclic oxygen-containing compounds: alcohols, aldehydes, ketones, ethers, and esters. Based on the obtained Δ _l ^g Ср ⁰ (298.2) values heat capacities in the liquid phase Cp _liq ⁰ (298.2) are calculated for the compounds under study.     

Stability of <Emphasis Type="Italic">s</Emphasis>-, <Emphasis Type="Italic">p</Emphasis>-, and <Emphasis Type="Italic">d</Emphasis>-element diphosphates in water

The mean atomic Gibbs energies of formation of (Δ _f ? _at ⁰ ) of s-, p-, and d-element diphosphates have been calculated using ion increments of the Gibbs energy (Δ _f G ⁰). The diphosphate hydrolysis kinetics is considered, and a correlation between the Δ _f ? _at ⁰ values and the hydrolysis rate constants is presented.     

New method for calculating the moments of thermally averaged densities of distribution of internuclear distances in polyatomic molecules using the Bloch integral equation

A convenient method is suggested for calculating thermally averaged powers of the normal vibrational coordinates Q _i by iteratively solving the Bloch integral equation with an anharmonic function of potential energy using multidimensional Hermite polynomials. Analytical formulas of the first approximation regarding anharmonicity constant have been obtained for the following moments of thermally averaged density: 〈Q ₁〉, 〈 Q ₁ ² 〉, 〈Q ₁ Q ₂〉, 〈Q ₁ ³ 〉 〈Q ₁ ³ 〉, 〈Q ₁ Q ₂ Q ₃〉, 〈Q ₁ ⁴ 〉, 〈Q ₁ ² Q ₂ ² 〉, 〈Q ₁ Q _2/3〉, 〈Q ₁ Q ₂ Q ₃ ² 〉, 〈 Q 1 Q ₂ Q ₃ Q ₄〉.     

The dynamics of nonadiabatic transitions in collisions between the I<Subscript>2</Subscript>(<Emphasis Type="Italic">E</Emphasis>) and I<Subscript>2</Subscript>(<Emphasis Type="Italic">X</Emphasis>) molecules

The paper presents the results of a theoretical study of the dynamics of nonadiabatic transitions between the ion-pair states E0 _g ⁺ and D0 _u ⁺ of the I₂ molecule induced by collisions with the I₂ molecule in the ground electronic state X0 _g ⁺ . The potential energy surfaces and diabatic coupling matrix elements of electronic states were obtained using a model based on the diatomics-in-molecule approximation. Special perturbation theory for intermolecular interaction was used to show that the large transition dipole moment between the E0 _g ⁺ and D0 _u ⁺ states caused the appearance of additional long-range corrections, an electrostatic dipole-quadrupole correction to the diabatic coupling matrix elements and induction dipole-dipole correction to the potential energy surface. The influence of these corrections on nonadiabatic dynamics was studied at the level of the semiclassical approximation. The electrostatic correction was found to sharply increase the contribution of resonance (accompanied by minimum kinetic energy changes) vibronic transitions at large distances between the colliding molecules. The induction correction had the opposite effect because of the high transition probability at short distances. The results obtained were in qualitative agreement with experimental data. The conclusion was drawn that obtaining quantitative agreement required a more balanced inclusion of interactions at short and long distances.     

Thermal properties of dimethylgold(III) 8-hydroxyquinolinate and 8-mercaptoquinolinate

Dimethylgold(III) complexes with 8-hydroxyquinoline Me₂Au(Ox) (I) and 8-mercaptoquinoline Me₂Au(Tox) (II) were synthesized and studied. Complex II obtained for the first time was identified from the elemental analysis, IR, ¹H NMR, and mass spectrometry data. The thermal properties of complexes I, II in condensed state were investigated by thermography. The temperature dependences of the saturated vapor pressure over crystals were measured by the Knudsen effusion method with mass spectrometric recording of the gas phase composition and the thermodynamic characteristics of the sublimation process were determined: for I, log P[Torr] = (14.6 ± 0.3) ? (6.34 ± 0.10) × 10³/(T, K), Δ H _subl ^o = 121.2 ± 1.9 kJ^?1, Δ S _subl ^o = 224.1 ± 4.6 J mol^?1 K^?1 (the temperature interval under study 80–115°C); for II, log P [Torr] = (13.3 ± 0.2) ? (6.30 ± 0.09) × 10³/(T, K), Δ H _subl ^o = 120.5 ± 1.7 kJmol^?1, ΔS _subl ^o = 199.3 ± 3.0 J mol^?1 K^?1 (86–145°C).     

Dissolution kinetics of silver metal nanoparticles in their reaction with nitric acid in an reverse micelle solution of AOT

The dissolution of silver nanoparticles in their reaction with aqueous HNO₃ solubilized to an reverse micelle solution of sodium bis(2-ethylhexyl)sulfosuccinate in decane is studied spectrophotometrically. A physicochemical model is advanced for quantifying the process kinetics on th basis of the following autocatalytic scheme: Ag⁰ + H⁺ + NO ₃ ^? → Ag⁺ + products (k ₁), and Ag⁰ + Ag⁺ + NO ₃ ^? → 2Ag⁺ + products (k ₂). The effective rate constant k ₂ decreases with decreasing solubilization capacity V _S/V _O (where V _S is the volume of the solubilized dispersed aqueous phase and V _O is the volume of the micelle solution); the solubilization capacity determines the size of the micelle cavities in which the reaction between Ag⁰ and HNO₃ occurs: k ₂ = 74 (V _S/V _O) · 100% ≈ 3.8%), 41 (2.9), and 35 (2.0) L/(mol s). The effective constant k ₁ is determined with a high uncertainty; the effect of V _S/V _O on k ₁ has the opposite tendency.     

Thermodynamic properties of lanthanum and lanthanide halides: IV. Enthalpies of atomization of LnCl,LnCl<Superscript>+</Superscript>, LnF,LnF<Superscript>+</Superscript>, and LnF<Subscript>2</Subscript>

The results of measurement of equilibrium constants of 30 reactions involving lanthanum and lanthanide fluorides (LnF, LnF₂, and LnF₃) and 14 reactions involving lanthanum and lanthanide monochlorides (Ln = La-Lu) have been summarized. These constants have been used for calculating the enthalpies of reactions by the second and third laws, from which the enthalpies of atomization Δ_at H ₀ ⁰ of LnCl, LnF, and LnF₂ have been determined. Comparison of the calculation results shows that the thermodynamic functions of LnCl and LnF (Ln = Ce-Yb) in which the electronic excitation contribution has been calculated from the excitation energies of Ln⁺ ions allow one to adequately determined the Δ_at H ₀ ⁰ values from experimental data. Using the trends in the change in Δ_at H ₀ ⁰ as a function of the atomic number of a lanthanide, the enthalpies of atomization of compounds for which experimental data are lacking have been estimated. The Δ_at H ₀ ⁰ values for LnCl⁺ ions have been calculated. The reliability of the Δ_at H ₀ ⁰ values for LnF⁺ ions have been assessed.     

Vapor pressure and heat capacities of perfluoro-<Emphasis Type="Italic">N</Emphasis>-(4-methylcyclohexyl)piperidine

Heat capacities of perfluoro-N-(4-methylcyclohexyl)piperidine (PMCP) have been measured by low-temperature adiabatic calorimetry. The purity of the compound, its triple-point temperature, and its enthalpy and entropy of fusion have been determined. The saturated vapor pressure was determined by comparative ebulliometry as a function of temperature in the 6.2–101.6 kPa pressure range and 374.2–460.9 K temperature range. The calorimetric enthalpy of vaporization at T = 298.15 K has been measured. The following thermodynamic properties were calculated for PMCP: normal boiling temperature, enthalpy of vaporization Δ_vap H _m ⁰ (T) as a function of temperature, and critical parameters. The enthalpies of vaporization at 298.15 K obtained experimentally and by calculation methods match within their error limits, which validates their adequacy and the adequacy of the Δ_vap H _m ⁰ = f(T) equation as an extrapolation.     

Stability of 3<Emphasis Type="Italic">d</Emphasis>-element cyclotetraphosphates in water

The hydrolysis kinetics of the anion in 3d-element cyclotetraphosphates is considered. The thermodynamic functions of formation (Δ _f H ⁰, Δ _f G ⁰, and Δ _f ? _at ⁰ ) of the cyclotetraphosphates are calculated using the ion increment method. A linear correlation is established between and log K Δ _f ? _at ⁰ for these compounds.     

Surface disordering of classic and superionic crystals: A description in the framework of the stern model

The surface potential (φ_S) in ionic crystals: binary compounds of the type NaCl and superionic oxygen conductors of the type M _{1 ? c} ^IV Me _c ^III O_{2 ? c/2} are calculated with the aid of the Stern model. Effect of the energy of formation of defects, concentration of accessible sites (N _S), and concentration of admixtures on the temperature dependences of φ_S(T) is studied. Instances of high and low potentials are analyzed. It is demonstrated that the surface potential increases proportionally to the difference between the adsorption energies of individual defects, provided the absolute value of |ΔG _i| (ΔG _i < 0) and concentration N _S are sufficiently large. Values of isoelectric temperatures in NaCl crystals doped with admixtures of other valence are calculated. An attempt is undertaken to describe experimental data for silver halides with the aid of the model. Calculations of the surface potential in superionic oxygen conductors show that increasing concentration of surface vacancies is accompanied by segregation of the admixture cations in the surface layer.     

Investigation of Chloride Ion Substitution Equilibria in AuCl<Stack><Subscript>4</Subscript><Superscript>−</Superscript></Stack> with Ethylenediamine and 1,3-Diaminopropane Using Capillary Zone Electrophoresis

Substitution of chloride ions in AuCl ₄ ^? with ethylenediamine (en) and propylenediamine (tn) is studied by capillary zone electrophoresis at I = 0.05 M and T = 25°C. The substitution constants are determined: AuenCl ₂ ⁺ + en = Auen ₂ ³⁺ + 2Cl^–, logK₂ = 10.4; AuCl ₄ ^? + tn = AutnCl ₂ ⁺ + 2Cl^–, logK₁ = 16.1; AutnCl ₂ ⁺ + tn = Autn³⁺₂ + 2Cl^–, logK₂ = 12.0.     

Reduction kinetics of glycinate complexes of palladium(II) on a dropping-mercury electrode in acid perchlorate solutions

Polarograms for the reduction of glycinate complexes of palladium(II) (5 × 10^?5 M) are obtained in equilibrium solutions of pH 0.8–3.0 with different protonated-glycine concentrations c _Hgly (supporting electrolyte, 0.5 M NaClO₄). It is established that the irreversible wave of reduction of complexes Pd(gly)₂ corresponds to the diffusion limiting current I _d ⁽²⁾ . A similar wave at pH 1.5 and c _Hgly = 0.005 M, as well as at pH 1.0 and c _Hgly = 0.05–0.5 M is preceded by the diffusion limiting current I _d ⁽¹⁾ . Values of the I _d ⁽²⁾ /I _d ⁽¹⁾ ratio are close to the ratio between equilibrium concentrations of Pd(gly)₂] and [Pdgly⁺], calculated using the step stability constant for Pd(gly)₂. This fact testifies to the reduction of complexes Pdgly⁺ in the vicinity of I _d ⁽¹⁾ and complexes Pd(gly)₂, in the vicinity of I _d ⁽²⁾ . At pH 0.8–1.2 and [H₂gly⁺] = 1 × 10^?4 to 5 × 10^?3 there is observed the diffusion-kinetic limiting current of the first wave I ₁ ⁽¹⁾ , which increases with increasing [H⁺] and decreasing [H₂gly⁺]. The nature of the slow preceding chemical stage that occurs during the reduction of complexes Pdgly⁺ is discussed.