Complexation of Eu(III), Am(III) and Cm(III) with Dicarboxylates: Thermodynamics and Structural Aspects of the Binary and Ternary Complexes

The complexation of Eu(III), Am(III) and Cm(III) with dicarboxylate anions with O, N or S donor groups was measured in I=6.60 mol⋅kg⁻¹ (NaClO₄) at temperatures of 0–60 °C by potentiometry and solvent extraction. The complexation thermodynamics of these complexes show that their stability is due to highly favorable complexation entropies because the complexation enthalpies are endothermic. Luminescence studies with Eu(III) and Cm(III) were used to measure the hydration numbers of the complexes. NMR spectra of ¹H and ¹³C were used to determine the binding modes of La(III) with the ligands. The formation of 1:1:1 ternary complexes of M(EDTA)⁻ with the dicarboxylate ligands was studied to determine changes in coordination of the metal cation with formation of the ternary species. The complexation of ternary complexes changes from bidentate to monodentate as the chain length between the binding sites of the dicarboxylates increases from 1 (malonate) to 4 (adipate). DFT computations were used to confirm the structural aspects of the interaction of these complexes.     

Diffusion in polymers dependence on crosslink density

Kinetics of N-methyl pyrrolidone evaporation from swollen photo-crosslinked polyacrylate was monitored thermogravimetrically at temperatures ranging from 323 to 398 K. Crosslink density dependence of evaporation kinetics was investigated in photo-crosslinked polyacrylates with crosslinked density ranging from ≈1.2 × 10² to ≈1.7 × 10⁴ mol m⁻³ and number of main chain atoms between crosslinks ranging from ≈70 atoms to ≈6 atoms, respectively. As was shown, evaporation kinetics was controlled by the solvent diffusion in polymer. Activation energies of evaporation (diffusion) were deduced from the rate measurements at different temperatures. Apparent activation energy of evaporation decreased from 48.7 to 31.1 kJ mol⁻¹ with crosslink density increase. Activation energy of pure N-methyl pyrrolidone evaporation was 50.6 kJ mol⁻¹. Decrease of the rate of solvent diffusion and unexpected decrease of diffusion activation energy with increase of crosslink density of swollen polymer matrix was explained by decrease in polymer chain segments mobility, as indicated by Eyring’s approach to diffusion in polymers.     

Standard molar enthalpies of formation of some methylfuran derivatives

The standard (p ^o = 0.1 MPa) molar enthalpies of formation \Updelta_\textf H_\textm^\texto ( \textl), {{\Updelta}}_{\text{f}} H_{\text{m}}^{\text{o}} ( {\text{l),}} of the liquid 2-methylfuran, 5-methyl-2-acetylfuran and 5-methyl-2-furaldehyde were derived from the standard molar energies of combustion, in oxygen, at T = 298.15 K, measured by static bomb combustion calorimetry. The Calvet high temperature vacuum sublimation technique was used to measure the enthalpies of vaporization of the three compounds. The standard (p ^o = 0.1 MPa) molar enthalpies of formation of the compounds, in the gaseous phase, at T = 298.15 K have been derived from the corresponding standard molar enthalpies of formation in the liquid phase and the standard molar enthalpies of vaporization. The results obtained were −(76.4 ± 1.2), −(253.9 ± 1.9), and −(196.8 ± 1.8) kJ mol⁻¹, for 2-methylfuran, 5-methyl-2-acetylfuran, and 5-methyl-2-furaldehyde, respectively.     

The thermodynamic characteristics of complex formation between Cd<Superscript>2+</Superscript> and iminodisuccinic acid in aqueous solution

The enthalpies of complex formation between iminodisuccinic acid (H₄L) and the Cd²⁺ ion were determined calorimetrically at 298.15 K and ionic strengths 0.5, 1.0, and 1.5 (KNO₃). The thermodynamic characteristics of formation of CdL²⁻ and CdHL⁻ complexes at fixed and zero ionic strength values were calculated.     

Thermodynamic Study on the Interaction of Copper Ion with Human Growth Hormone

A thermodynamic study on the interaction between the Cu²⁺ ion and human growth hormone (hGH) was studied at the temperatures 300.15 and 310.15 K in NaCl solution using isothermal titration calorimetry. The new solvation model was used to reproduce the enthalpies of Cu²⁺+hGH interaction over the whole range of Cu²⁺ concentrations. It was found that there is a set of three identical and non-interacting binding sites for Cu²⁺ ions. The intrinsic dissociation equilibrium constant and the molar enthalpy of binding are 1313.4 μmol⋅L⁻¹ and −16.80 kJ⋅mol⁻¹ at 300.15 K, and 1648.2 μmol⋅L⁻¹ and −16.40 kJ⋅mol⁻¹ and 310.15 K, respectively. The binding parameters recovered from the new equation are attributed to a structural change of hGH and its biological activity due to metal ion interaction.     

An examination of the vaporization enthalpies and vapor pressures of pyrazine, pyrimidine, pyridazine, and 1,3,5-triazine

The vaporization enthalpies and liquid vapor pressures from T = 298.15 K to T = 400 K of 1,3,5-triazine, pyrazine, pyrimidine, and pyridazine using pyridines and pyrazines as standards have been measured by correlation-gas chromatography. The vaporization enthalpies of 1,3,5-triazine (38.8 ± 1.9 kJ mol⁻¹) and pyrazine (40.5 ± 1.7 kJ mol⁻¹) obtained by these correlations are in good agreement with current literature values. The value obtained for pyrimidine (41.0 ± 1.9 kJ mol⁻¹) can be compared with a literature value of 50.0 kJ mol⁻¹. Combined with the condensed phase enthalpy of formation in the literature, this results in a gas-phase enthalpy of formation, Δ_f H _m (g, 298.15 K), of 187.6 ± 2.2 kJ mol⁻¹ for pyrimidine, compared to a value of 195.1 ± 2.1 calculated for pyrazine. Vapor pressures also obtained by correlation are used to predict boiling temperatures (BT). Good agreement with experimental BT (±4.2 K) including results for pyrimidine is observed for most compounds with the exception of the pyridazines. The results suggest that compounds containing one or two nitrogen atoms in the ring are suitable standards for correlating various heterocyclic compounds provided the nitrogen atoms are isolated from each other by carbon. Pyridazines do not appear to be evaluated correctly using pyridines and pyrazines as standards.     

The calorimetric study of some guanidine derivatives involved in living bodies nitrogen metabolism

The energies of combustion of creatine (anhydrous and monohydrate), creatinine, and arginine were measured in a static bomb adiabatic calorimeter, in pure oxygen at 3,040 kPa. The derived standard enthalpies of formation in solid state of the above-mentioned compounds are, respectively, −520.4 ± 4.3, −809.7 ± 1.3, −204.2 ± 7.0, and −634.8 ± 2.3 kJ mol⁻¹ . The data of enthalpy of formation are compared with literature values and with estimated values by means of group additivity. The dehydration of creatine monohydrate and the processes occurring in the three guanidine derivatives at temperatures exceeding 200 °C were investigated by means of DSC.     

Thermodynamic characteristics of the complexation between Pb<Superscript>2+</Superscript> and <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-Bis(carboxymethyl)aspartic acid in aqueous solution

The enthalpies of complexation between N,N-bis(carboxymethyl)aspartic acid (H₄Y) and the Pb²⁺ ion at 298.15 K were determined from calorimetric data for a wide range of the ionic strengths (KNO₃). The thermodynamic characteristics ΔH, ΔG, and ΔS, of formation of the complexes PbHY⁻ and PbY²⁻ were calculated for zero and fixed ionic strengths. The results obtained were interpreted.     

The Dissolution Properties of 2-(1,1-Dinitromethylene)-1,3-diazepentane in N-methyl Pyrrolidone

The dissolution properties of 2-(1,1-dinitromethylene)-1,3-diazepentane in N-methyl pyrrolidone(NMP) were studied with a RD496-2000 Calvet microcalorimeter at three different temperatures. The measured molar enthalpies (Δ_sol H) for 2-(1,1-dinitromethylene)-1,3-diazepentane in NMP at T=(298.15,306.15,311.15) K are (5.02, 5.59, 6.67) kJ⋅mol⁻¹, respectively. The differential molar enthalpies (Δ_dif H), the specific enthalpies (Δ_sol h), and the standard heat effect (Q ^Θ) for 2-(1,1-dinitromethylene)-1,3-diazepentane in NMP were obtained at the same time. The kinetic parameters of activation energy E and pre-exponential factor A are 2.26×10⁴ J⋅mol⁻¹ and 10^2.06 s⁻¹, which indicate that NMP is a good solvent for the title compound.     

Kinetic studies on promazine oxidation by FeIII/CuII in acidic aqueous bromide solutions. Spectroscopic and kinetic non-additivity as evidence for the CuII–Br–FeIII-type heterobimetallic complex formation

The formation of Cu^II–Br–Fe^III-type heterobimetallic complexes was observed spectrophotometrically, given the non-additivity of the spectra from the copper(II) and iron(III) complexes. The kinetics of the oxidation of promazine radical (ptz^+•) to promazine 5-oxide, by iron(III) bromides, copper(II) bromides, and a mixture of these complexes in acidic aqueous solutions, have been studied using UV–Vis spectroscopy at I = 1.0 M (H⁺, Cu²⁺, Fe³⁺, Br⁻) and T = 318 K. Copper(II) inhibits the oxidation of the promazine radical to promazine sulfoxide using iron(III) complexes. A rate retardation effect, characterized by the dependence of the pseudo second-order rate constant (k ^II) on the copper(II) concentration k ^II = a/(1 + b[Cu^II]), can be rationalized as a result of Cu^II–Br–Fe^III-type heterobimetallic complex formation.     

The structure and thermochemistry of 3:4,5:6-dibenzo-2-hydroxymethylene-cyclohepta-3,5-dienenone (1) and some related compounds

Condensed and gas phase enthalpies of formation of 3:4,5:6-dibenzo-2-hydroxymethylene-cyclohepta-3,5-dienenone (1, (−199.1 ± 16.4), (−70.5 ± 20.5) kJ mol⁻¹, respectively) and 3,4,6,7-dibenzobicyclo[3.2.1]nona-3,6-dien-2-one (2, (−79.7 ± 22.9), (20.1 ± 23.1) kJ mol⁻¹) are reported. Sublimation enthalpies at T=298.15 K for these compounds were evaluated by combining the fusion enthalpies at T = 298.15 K (1, (12.5 ± 1.8); 2, (5.3 ± 1.7) kJ mol⁻¹) adjusted from DSC measurements at the melting temperature (1, (T _fus, 357.7 K, 16.9 ± 1.3 kJ mol⁻¹)); 2, (T _fus, 383.3 K, 10.9 ± 0.1) kJ mol⁻¹) with the vaporization enthalpies at T = 298.15 K (1, (116.1 ± 12.1); 2, (94.5 ± 2.2) kJ mol⁻¹) measured by correlation-gas chromatography. The vaporization enthalpies of benzoin ((98.5 ± 12.5) kJ mol⁻¹) and 7-heptadecanone ((94.5 ± 1.8) kJ mol⁻¹) at T = 298.15 K and the fusion enthalpy of phenyl salicylate (T _fus, 312.7 K, 18.4 ± 0.5) kJ mol⁻¹) were also determined for the correlations. The crystal structure of 1 was determined by X-ray crystallography. Compound 1 exists entirely in the enol form and resembles the crystal structure found for benzoylacetone.     

Polarization orientation dependence of the far infrared spectra of oriented single crystals of 1,3,5-trinitro-S-triazine (RDX) using terahertz time–domain spectroscopy

The far infrared spectra of (100), (010), and (001)-oriented RDX single crystals were measured as the crystal was rotated about the axis perpendicular to the polarization plane of the incident radiation. Absorption measurements were taken at temperatures of both 20 K and 295 K for all rotations using terahertz time–domain spectroscopy. A number of discrete absorptions were found ranging from 10–100 cm⁻¹ (0.3–3 THz). The absorptions are highly dependent on the orientation of the terahertz polarization with respect to crystallographic axes.     

Enthalpic characterization of activated carbons obtained from <Emphasis Type="Italic">Mucuna Mutisiana</Emphasis> with different burn-offs

Immersion enthalpies of activated carbon samples obtained by activation with steam at temperatures between 600 and 900 °C and activation times between 1 and 10 h were determined. The calorimetric liquids of immersion are CCl₄, water, NaOH, and HCl 2 M solutions, and the values of the immersion enthalpies are related to other properties of the activated carbons such as the surface area B.E.T., the micropore volume, the content of acid, and basic surface groups. The highest values for the immersion enthalpies take place for the polar solvent CCl₄ and for HCl solution, with values between 4.0 and 75.2 J g⁻¹ and 9.15 and 48.3 J g⁻¹, respectively.     

CO2 adsorption in LiY and NaY at high temperature: molecular simulations compared to experiments

Grand Canonical Monte Carlo simulations combined with adsorption measurements have been carried out to gain further insight into the CO₂ adsorption process at the microscopic scale in both LiY and NaY faujasites at various temperatures. A new Li⁺−CO₂ force field derived by ab initio calculations was validated by a reasonable agreement between the simulated isotherms and those obtained by experiments in a wide range of temperature (from 323 K to 473 K). In addition, the microscopic mechanisms of CO₂ adsorption in both systems, consistent with the trends observed for the simulated differential enthalpies of adsorption as a function of the loading, were proposed. It was observed that two different types of adsorption behaviour exist for NaY and LiY at 323 K and 373 K, mainly caused by the significant more exposed position of the SII Na⁺ from the six-ring plane of the supercage compared to those occupied by the SII Li⁺, whereas at higher temperature, both faujasites exhibit the same flat profile for the differential enthalpy of adsorption as a function of loading.     

Spectrophotometric and Calorimetric Studies of Np(V) Complexation with Acetate at Various Temperatures from <Emphasis Type="Italic">T</Emphasis>=283 to 343 K

Spectrophotometric titrations were performed to identify the Np(V)/acetate complex and determine the equilibrium constants at various temperatures (T=283 to 343 K) and at the ionic strength 1.05 mol⋅kg⁻¹. The enthalpies of complexation at the corresponding temperatures were determined by microcalorimetric titrations. Results show that the complexation of Np(V) with acetate is weak but strengthens as the temperature increases. The complexation reaction is endothermic and entropy driven. The enhancement of complexation at higher temperatures is primarily due to the increasingly larger entropy gain when the solvent molecules are released from the highly-ordered solvation spheres of NpO₂⁺\mathrm{NpO}_{2}^{+} and acetate to the bulk solvent where the degree of disorder is higher at higher temperatures.     

Thermal and spectroscopic properties of light lanthanides (III) and sodium complexes of 2,5-pyridinedicarboxylic acid

Pyridine-2,5-dicarboxylic acid, known as isocinchomeric acid is one of six isomers containing two carboxylic groups. Light lanthanide (III) complexes with pyridine-2,5-dicarboxylic acid with general formula Ln₂L₃·nH₂O, where n = 8, 9, were obtained. Their thermal and spectroscopic properties were studied. Sodium salt was obtained as Na₂L·H₂O. Hydrated complexes of La(III), Ce(III), Pr(III), Nd(III), Sm(III), Eu(III) and Gd(III) are stable to 313–333 K, whereas Na₂L·H₂O is stable to about 333 K. Dehydration process for all compounds runs in one stage, next they decompose into appropriate lanthanide oxalates, oxocarbonates carbonates and finally to metal oxides. Bands of νCOOH vibrations at 1736 and 1728 cm⁻¹ disappear on complex spectra and ν_as and ν_s of COO⁻ groups appear thus indicating that complexation process took place.     

Cholesterol complexes with some proton acceptors in benzene and toluene solutions

Abstract  

Cholesterol complexes with tri-n-butyl phosphate, tri-n-octylamine, N,N-dimethylacetamide, and cyclohexanone in benzene and toluene solutions were studied using conventional IR spectroscopy. The spectra were recorded in the region of fundamental OH stretching (3,700–3,100 cm⁻¹) at 298 K. The experimental spectra were resolved into bands corresponding to the cholesterol monomer and particular oligomeric and complex species. The formation constants of complexes were determined from the-least squares plots of the linearized expressions of Bjerrum’s formation function. The stoichiometry of complexes was also identified in this way. The identification of the particular resolved bands was performed from their location, and from the dependence of their intensity on the cholesterol monomer and free base concentration.     

Interactions between AuCl<Subscript>4</Subscript><Superscript>−</Superscript> and CTA<Superscript>+</Superscript> ions in water

The solubility of hexadecyltrimethylammonium tetrachloroaurate (CTA·AuCl₄) in water was measured at different temperatures of 288.2, 293.2, 298.2, 303.2, and 308.2 K. The enthalpy change associated with the formation of the CTA·AuCl₄ precipitate was estimated on the basis of the van’t Hoff equation and was found to be −42.5 ± 2.8 kJ mol⁻¹ at 298.2 K. The calorimetric enthalpy change for the CTA·AuCl₄ precipitate formation was directly determined by isothermal titration calorimetry performed at 298.2 K and was found to agree well with that estimated from the van’t Hoff equation.     

Thermodynamic properties of Eu-Sn melts

Partial and integral mixing enthalpies of melts of the Eu-Sn system were determined by calorimetry at 1300 (1250) K in the concentration intervals 0 < x _Sn < 0.16 and 0.7 < x _Sn < 1. It was found that the first partial mixing enthalpies of Sn and Eu were −215.6 ± 10.6 and −161.2 ± 7.6 kJ/mol, respectively. The thermodynamic properties of the Eu-Sn alloys were modeled using the theory of ideal associated solutions over a wide interval of concentrations and temperatures. In was found that the activities of components exhibit strong negative deviations from Raoult’s law. At minimum, the calculated integral Gibbs energies of mixing reach −43.4 kJ/mol at x _Sn = 0.48; ΔG ^ex = −36 kJ/mol, ΔS ^ex = −22 J/(mol K).