Standard Gibbs energies of transfer of rubidium tetraphenylborate from water to straight-chain n-alkanols

Solubilities of ribidium tetraphenylborate in water,methanol,ethanol,1-propanol,1-butanol,l-pentanol,1-hexanol and 1-octanol at 288.15,298.15,308.15,318.15,328.15 K have been determined by spectrophotometry.The standard Gibbs energy of transfer of ribidium tetraphenylborate from water to straight-chain n-alkanols and the primary medium effect of rubidium tetraphenylborate from 288.15 to 328.15 K have been calculated.Furthermore,the contribution of microscopic interactions to the standard Gibbs energy of transfer of rubidium tetraphenylborate is calculated and discussed.     

液/液界面电子转移研究苯甲酰吡啶-缩氨基硫脲的亲脂性

The ion transfer reaction of 2-benzoylpyridine-thiosemicarbazone (HL), which has antimicrobial and antifungal properties and anticancer activity, has been studied to determine its lipophilicity by cyclic voltammetry at the water/1,2-dichloroethane (1,2-DCE) interface. The physicochemical parameters such as standard partition coefficient (IgP1) and the standard Gibbs energy of transfer (△G0,w→otr,I) of the protonated form of the ligand were measured as a function of pH in aqueous phase. The protonated form of the ligand exhibited reversible or quasi-reversible voltammograms at the 1,2-DCE in the range of pH 1-5. The protonation constants of the ligand, pKal, and pK? were determined spectrophotometrically and were found to be 12.14 and 3.24, respectively. The standard Gibbs energy of transfer (△G0,w→otr,N) and the partition coefficient of neutral species (IgPN) were also determined by the shake-flask method. The standard Gibbs energy of transfer of this compound across the water/1,2-DCE interface was evaluated as the quantitative measure of its lipophilicity. The difference between lgP1 and lgPN was related to the degree of charge delocalization and was used to evaluate qualitatively the lipophilicity of the ligand.     

四苯硼钠在活性炭表面吸附过程的疏水相互作用

In this paper, the adsorption characteristics of sodium tetraphenylborate(NaBPh4) on activated carbon at 298.2,303.2,308.2,313..2 and 323.2 K was studied.The results show that the adsorption isotherm of NaBPh4 on activated carbon at different temperatures could be described using Langrnuir equation. Furthermore, the standard Gibbs energy, enthalpy, entropy and hydrophobic interaction Gibbs energy for the adsorption of NaBPh4 on activated carbon were studied, and the result shows that the hydrophobic interaction of BPh4^- ion plays the most important role for the transfer of NaBPh4 from water to activated carbon surface.     

ION TRANSFER OF BROMOCRESOL PURPLE ACROSS THE LIQUID/LIQUID INTERFACES

In this paper, the ion transfer process of bromocresol purple(BCP) across the liquid/liquid interface has been described. The effects of the supporting eletrolyte in two phases and solvent on the transfer behavior of bromocresol purple have been investigated in detail and the relationship between the ion transfer and concentration of electrolytes in the organic phase is explained in terms of the dissociation of TBA~+ anti TPB~- in the organic phase. The proposed transfer mechanism for BCP has been proved to be reasonable by UV-spectroscopy of the products of the electrolysis in aqueous phase. The standard potential differences △_0~wφ~0 and standard Gibbs energies △_0~WG~0 of BCP transfer from water to some organic solvents are calculated. The dissociation constants of BCP obtained are in agreement with the literature values.     

Theoretical Study on Intermolecular Interactions and Thermodynamic Properties of Nitroamine Dimers

Ab initio self-consistent field(SCF) and Mφller-Plesset correlation correction methods employing 6-31G^** basis set have been applied to the optimizations of nitroamine dimers.The binding energies have been corrected for the basis set superposition error (BSSE) and the zero-point energy.Theree optimized dimers have been obtained.The BSSE corrected binding energy of the most stable dimer is predicted to be -31.85kJ/mol at the MP4/6-31G^**//MP2/6-31G^** level.The energy barriers of the Walden conversion for -NH2 group are 19.7kJ/mol and 18.3kJ/mol for monomer and the most stable dimer,respectively.The molecular interaction makes the internal rotation around N1-N2 even more difficult.The thermodynamic properties of nitroamine and its dimers at different temperatures have been calculated on the basis of vibrational analyses.The change of the Gibbs free energy for the aggregation from monomer to the most stable dimer at standard pressure and 298.2 K is predicted to be 14.05kJ/mol.     

Studies of Structural and Thermodynamic Properties for Polychlorinated Thianthrenes by Density Functional Theory

The structural and thermodynamic （PCTAs） in the ideal gas state at 298.15 K and 1.013 properties of 75 polychlorinated thianthrenes ×10^5 Pa have been calculated at the B3LYP/6- 31G＊ level using Gaussian 98 program. Based on the output data of Gaussian, the isodesmic reactions were designed to calculate standard enthalpy of formation （△fH^θ） and standard free energy of formation （△fH^θ） of PCTAs congeners. The relations of these thermodynamic parameters with the number and position of C1 atom substitution （Npcs） were discussed, and it was found that there exists high correlation between thermodynamic parameters （total energy （TE）, zero-point vibrational energy （ZPE）, thermal correction to energy （Eth）, heat capacity at constant volume （Cv^θ）, entropy （S^θ）, enthalpy （H^θ）, free energy （G^θ）, standard enthalpies of formation （△fH^θ） and standard Gibbs energies of formation （△fG^θ）） and Npcs. On the basis of the relative magnitude of their △fG^θ, the order of relative stability of PCTA congeners was theoretically proposed. In addition, the correlations between structural parameters and Npcs were also discussed. The good correlations were found between molecular average polarizability （α）, energy of the highest occupied molecular orbital （EHOMO）, molecular volume （Vm） and Npcs, and all R^2 values are larger than 0.95. Moreover, it was supposed that the isomer groups with higher toxicity should be Tri-CTA and TCTA.     

Kinetics of hydrate formation using gas bubble suspended in water

An innovative experimental technique, which was devised to study the effects of temperature and pressure on the rate of hydrate formation at the surface of a gas bubble suspended in a stagnant water phase, was adapted in this work. Under such conditions, the hydrate-growth process is free from dynamic mass transfer factors. The rate of hydrate formation of methane and carbon dioxide has been systematically studied. The measured hydrate-growth data were correlated by using the molar Gibbs free energy as driving force. In the course of the experiments, some interesting surface phenomena were observed.     

α-氨基酸在水-乙醇中羧基质子化热力学

Enthalpy changes for the protonation of carboxyl group of four α-amino acids(glycine,L-α-alanine,L-valine and L-serine) were measured in water-ethanol mixtures (10－ 70wt％) at 298.15K using LKB-2277 Bioactivity Monitor.The corresponding entropy and Gibbs energy changes were also calculated.The results show that both enthalpy changes and entropy changes are favorable to the protonation of carboxyl groups of the investigated amino acids in water-ethanol mixtures.However,the influence of the composition of ethanol in the mixed solvents on the enthalpy change and entropy changes is complicated.Both sδ and sδ ,the differences of enthalpy changes and entropy changes in mixed solvents and in pure water respectively,show a minimum approximately at xEtOH=0.1.The effects of side chains on the enthalpy change and entropy changes were also investigated using the proton transfer process between glycine and the other three amino acids.The results demonstrate that the proton transfer processes for alanine and valine are spontaneous but not for serine,which could be interpreted in terms of the electrostatic interaction between amino group and carboxyl group within the molecule and the interaction between carboxyl group and the solvent.     

Studies of Thermodynamic Properties and Relative Stability of Polybrominated Xanthones by Density Functional Theory

The thermodynamic properties of xanthone(XTH) and 135 polybrominated xanthones(PBXTHs) in the standard state have been calculated at the B3LYP/6-31G* level using Gaussian 03 program.The isodesmic reactions were designed to calculate the standard enthalpy of formation(△fHθ) and standard free energy of formation(△fGθ) of PBXTH congeners.The relations of these thermodynamic parameters with the number and position of Br atom substitution(NPBS) were discussed,and it was found that there exist high correlation between thermodynamic parameters(entropy(Sθ),△fHθ and △fGθ) and NPBS.According to the relative magnitude of their △fGθ,the relative stability order of PBXTH congeners was theoretically proposed.The relative rate constants of formation reactions of PBXTH congeners were calculated,Moreover,the values of molar heat capacity at constant pressure(Cp,m) from 200 to 1000 K for PBXTH congeners were also calculated,and the temperature dependence relation of them was obtained,suggesting very good relationships between Cp,m and temperature(T,T-1 and T-2) for almost all PBXTH congeners.     

Theoretical Study on the Adsorption and Hydrogenation Mechanism of 2-Methylthiophene over the Pt(111) Catalyst

The adsorption process and hydrogenation mechanisms of 2-methylthiophene on the Pt(111) surface have been elucidated using density functional theory(DFT). The optimal adsorption sites of reactants, intermediates, and products as well as the activation energy and reaction energy of each elementary reactions were investigated. The results turned out that the 2-methylthiophene tilt to the Pt(111) catalyst with the C_1–C_2 double bond at the top site was the most stable. During the hydrogenation process, the heat of reaction almost located at the negative side, so dropping the temperature is good for the occurrence of hydrogenation process. The hydrogenation steps of mechanism take place along C_2→C_3→C_1→C_4→S→C_1 to generate the product of pentane-2-thiol, in which the first step with the highest energy barrier is the rate-determining step.     

Transfer free energies of some ions from water to dimethylsulfoxide-water and urea-water mixtures

The standard free energies of transfer (G _t ^o ) of some electrolytes from water to aqueous mixtures of dimethylsulfoxide (DMSO) and of urea have been split into the contribution from individual ions by use of the reference electrolyte Ph ₄ AsBPh ₄ (RE), where Ph=phenyl. For each of the solvents, G _t ^o (Ph ₄ AsBPh ₄ ) was determined from the solubility products of the salts KBPh ₄ , Ph ₄ AsPi, and KPi, where Pi=picrate ion. The observed G _t ^o (i) values for the individual ions are strikingly different from the corresponding values obtained by the simultaneous extrapolation (SE) procedure reported earlier.     

Temperature and salt addition effects on the solubility behaviour of some phenolic compounds in water

Solubility-temperature dependence data for six phenolic compounds (PhC), contained in olive mill wastewater (OMWW), in water and in some chloride salts (KCl, NaCl, and LiCl) aqueous solutions have been presented and solution standard molar enthalpies (Δ_solH^∘) were determined using Van’t Hoff plots. The temperature was varied from 293.15 K to 318.15 K. Solubility data were estimated using a thermostated reactor and HPLC analysis. It has been observed that solubility, in pure water and in aqueous chloride solutions, increases with increasing temperature. The salting-out LiCl > NaCl > KCl order obtained at 298.15 K is confirmed. Results were interpreted in terms of the salt hydration shells and the ability of the solute to form hydrogen-bond with water. The standard molar Gibbs free energies of transfer of PhC (Δ_trG^∘) from pure water to aqueous solutions of the chloride salts have been calculated from the solubility data. In order to estimate the contribution of enthalpic and entropic terms, standard molar enthalpies (Δ_trH^∘) and entropies (Δ_trS^∘) of transfer have also been calculated. The decrease in solubility is correlated to the positive Δ_trG^∘ value which is mainly of enthalpic origin.     

New Insights into Buffer-Ionic Salt Interactions: Solubilities,Transfer Gibbs Energies,and Transfer Molar Volumes of TAPS and TAPSO from Water to Aqueous Electrolyte Solutions

The solubilities of N-[tris(hydroxymethyl)methyl]-3-aminopropanesulfonic acid (TAPS) or N-[tris(hydroxymethyl)methyl]-3-amino-2-hydroxypropanesulfonic acid (TAPSO) in water and in aqueous solutions of CH₃COOK (KAc), KBr, KCl, or NaCl were determined from density measurements at 298.15 K. The solubilities of TAPS in aqueous solution decrease with increasing concentration of the salts (salting-out effect), whereas those of TAPSO increase with increasing concentration of the salts (salting-in effect). The solubility and density data were further used to calculate the apparent transfer Gibbs energies, Δ_tr G, and transfer molar volumes, D_trV_f^o\Delta_{\mathrm{tr}}V_{\phi}^{\mathrm{o}}, of these buffers from water to aqueous electrolyte solutions at 298.15 K. The contributions of various functional groups of TAPS, TAPSO, and the related buffers (tris(hydroxymethyl)aminomethane, TRIS, and N-tris[hydroxymethyl]-4-amino-butanesulfonic acid, TABS) to the transfer properties were systematically estimated from the calculated Δ_tr G and D_trV_f^o\Delta_{\mathrm{tr}}V_{\phi}^{\mathrm{o}}.     

Acoustical and excess thermodynamic studies of mixtures of 2-pyrrolidone with 1,3-propanediol and water as well as 1,3-propanediol with water at 308.15 K

The density (ρ), viscosity (η) and ultrasonic velocity (u) of three mixtures consisting of 2- pyrrolidone with 1,3-propanediol (PD) and water and also of PD and water have been measured as a function of mole fraction at 308.15 K. The experimentally collected data has been used to calculate the excess molar volume (V^E), deviation in viscosity (Δη), deviation in ultrasonic velocity (Δu), isentropic compressibility (κ_s), deviation in isentropic compressibility (Δκ_s) and excess Gibbs free energy of activation (ΔG*^E). The Redlich–Kister polynomial equation has been used to fit the derived parameters. The variation in excessive thermodynamic properties as a consequence of possible molecular interactions is discussed.     

Non-isothermal Kinetics of the First-stage Decomposition Reaction of the Complex of Terbium p-Methylbenzoate with 1,10-Phenanthroline

The thermal behavior of Tb₂ (p‐MBA)₆(phen)₂ (p‐MBA=p‐methylbenzoate; phen=1,10‐phenanthroline) in a static air atmosphere was investigated by TG‐DTG, SEM and IR techniques. The thermal decomposition of the Tb₂(p‐MBA)₆(phen)₂ occurred in three consecutive stages at T_P of 354, 457 and 595 °C. By Malek method, RO (n<1) was defined as kinetic model for the first‐step thermal decomposition. The activation energy (E) of this step is 170.21 kJ·mol^‐1, the enthalpy of activation (ΔH^≠) 164.98 kJ·mol^‐1, the Gibbs free energy of activation (ΔG^≠) 145.04 kJ·mol^‐1, the entropy of activation (ΔS^≠) 31.77 J·mol^‐1·K^‐1, and the pre‐exponential factor (A) 10^15.21 s^‐1.     

Solvation of ions. XXVII. Comparison of methods to calculate single ion free energies of transfer in mixed solvents

Free energies of transfer of ions from water to mixtures of water with acetonitrile (AN), with dimethylformamide (DMF), with dimethylsulfoxide (DMSO), and with ethylene glycol have been determined using both the tetraphenylarsonium tetraphenylboride [TATB] and the negligible liquid junction potential [E _j ] assumptions. By making use of ΔG _tr (Ag⁺)[TATB]=12 kJ-mol^?1 for transfer from DMSO to AN and by assuming negligible liquid junction potential in the cell $${\text{Ag|AgNO}}_{\text{3}} {\text{(0}}{\text{.01}}M{\text{),S}}\parallel {\text{Et}}_{\text{4}} {\text{NPic(0}}{\text{.1}}M{\text{),AN}}\parallel {\text{AgNO}}_{\text{3}} {\text{(0}}{\text{.01}}M{\text{),AN|Ag}}$$ single ion free energies of transfer of silver ion ΔG _tr (Ag⁺)[E _j ] from DMSO to 35 pure and mixed solvents show a standard deviation of only 2 kJ-mol^?1 when compared with ΔG _tr (Ag⁺) calculated from the TATB assumption that ΔG _tr (Ph ₄ As⁺)=ΔG _tr (Ph ₄ B^?). The ferrocene assumption [Fc] also gives acceptable agreement with ΔG _tr (Ag⁺)[TATB] provided that the solvents are not highly aqueous. Other cells with other junctions give less acceptable agreement between the E _j and TATB assumptions. It is essential that the salt bridge is always tetraethylammonium picrate in AN, if the E _j assumption is assumed. Because of the ease of making potentiometric measurements compared with the difficulty of measurements required for the TATB assumption, the negligible liquid junction potential method in the cell shown is recommended for estimating transfer free energies of single ions. The ferrocene assumption is acceptable only for non-structured aprotic solvents.     

Thermodynamic and acoustical properties of mixtures <Emphasis Type="Italic">p</Emphasis>-anisaldehyde—alkanols (C<Subscript>1</Subscript>–C<Subscript>4</Subscript>)—2-methyl-1-propanol at 303.15 K

The density, viscosity and speed of sound of pure p-anisaldehyde and some alkanols, for example, methanol, ethanol, propan-1-ol, propan-2-ol, butan-1-ol, butan-2-ol, 2-methylpropan-1-ol, and the binary mixtures of p-anisaldehyde with these alkanols were measured over the entire composition range at 303.15 K. From the experimental data, various thermodynamic parameters such as excess molar volume (V^E), excess Gibbs free energy of activation (ΔG*^E), and deviation parameters like viscosity (Δη), speed of sound (Δu), isentropic compressibility (Δκ_s), are calculated. The excess as well as deviation parameters are fitted to Redlich—Kister equation. Additionally, the viscosity data for the systems has been used to correlate the application of empirical relation given by Grunberg and Nissan, Katti and Chaudhari, and Hind et al. The results are discussed in terms of specific interactions present in the mixtures.     

Thermodynamics of formation for the 18-crown-6-triglycine molecular complex in water-dimethylsulfoxide solvents

The effect of a water-dimethylsulfoxide (DMSO) solvent on the formation of a molecular complex of 18-crown-6 (18C6) with triglycine (diglycylglycine, 3Gly) is studied via calorimetric titration. It is found that switching from water to an H₂O-DMSO mixture with DMSO mole fraction of 0.30 is accompanied by a monotonic increase in the stability of [3Gly18C6] complex, from logK ^° = 1.10 to logK ^° = 2.44, and an increase in the exothermicity of the reaction of its formation, from ?5.9 to ?16.9 kJ/mol. It is shown that the [3Gly18C6] complex exhibits enthalpy stabilization with negative values of enthalpy and entropy over the investigated range of H₂O-DMSO solvents. Analysis of the reagents’ solvation characteristics reveals that the increase in the reaction’s exothermicity of transfer is due to differences in the solvation of [3Gly18C6] and 18C6 with a small solvation contribution from 3Gly. It is concluded that the change in the Gibbs energy of the reaction 3Gly_solv + 18C6_solv ? [3Gly18C6]_solv is due to differences in the change in the solvation state of the complex and the peptide (Δ_tr G ^°([3Gly18C6])-Δ_tr G ^°(3Gly)).     

The kinetics of the solvolysis of chloropentacyanocobaltate(III) ions in water containing 2-methoxyethanol or diethylene glycol: A contrast with the effect of more hydrophobic cosolvents

The kinetics of the solvolysis of [Co(CN)₅Cl]^3– have been investigated in water +2-methoxyethanol and water + diethylene glycol mixtures. Although the addition of these linear hydrophilic cosolvent molecules to water produces curvature in the variation of log(rate constant) with the reciprocal of the dielectric constant, their effect on the enthalpy and entropy of activation is minimal, unlike the effect of hydrophobic cosolvents. The application of a Gibbs energy cycle to the solvolysis in water and in the mixtures using either solvent-sorting or TATB values for the Gibbs energy of transfer of the chloride ion between water and the mixture shows that the relative stability of the emergent solvated Co(III) ion in the transition state compared to that of Co(CN)₅Cl^3– in the initial state increases with increasing content of cosolvent in the mixture. By comparing the effects of other cosolvents on the solvolysis, this differential increase in the relative stabilities of the two species increases with the degree of hydrophobicity of the cosolvent.List of Symbols v₂ partial molar volume of the cosolvent in water + cosolvent mixtures - V ₂ ^o molar volume of the pure cosolvent - H _mix ^E excess enthalpy of mixing water and cosolvent - S _mix ^E excess entropy of mixing water and cosolvent - G _t ^o (i)_n the Gibbs energy of transfer of speciesi from water into the water + cosolvent mixture excluding electrostatic contributions - k _s first order rate constant for the solvolysis in water + cosolvent mixtures - D _s dielectric constant of the water + cosolvent mixture - H ^* the enthalpy of activation for the solvolysis - S ^* the entropy of activation for the solvolysis - G ^* the Gibbs energy of activation for the solvolysis - V ^* the volume of activation for the solvolysis - i ^* speciesi in the transition state for the solvolysis - H _o Hammett Acidity Function - TATB method for estimating the Gibbs energy of transfer for single ions assuming those for Ph₄As⁺ and BPh ₄ ^– are equal     

Solubility of some phenolic compounds in aqueous alkali metal nitrate solutions from (293.15 to 318.15) K

This paper is continuation of the study concerning the solubility-temperature dependence data for some phenolic compounds (PhC), contained in olive mill wastewater (OMWW), in two nitrate salts (KNO₃ and NaNO₃) aqueous solutions. The solubilities of PhC were determined in the temperature ranging from (293.15 to 318.15) K. It has been observed that the solubility, in aqueous nitrate solutions, increases with increasing temperature. Results showed that alkali metal nitrate has a salting-out effect on the solubility of PhC. The effect of the anion of the electrolyte on the solubility of PhC is observed by comparing these results with values reported in the previous papers for the effect of LiCl, NaCl and KCl. For each cation, the solubilites of the phenolic compounds are higher with nitrate anion than with chloride anion. Results were interpreted in terms of the salt hydration shells and the ability of the solute to form hydrogen-bond with water. The solubility data were accurately correlated by a semi empirical equation. The standard molar Gibbs free energies of transfer of PhC (Δ_trG^°) from pure water to aqueous solutions of the nitrate salts have been calculated from the solubility data. The decrease in solubility is correlated to the positive Δ_trG^° value which is mainly of enthalpic origin.