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1.
The protonation equilibria for 20 standard α-amino acids in solutions have been studied pH-potentiometrically. The dissociation constants (pKa) of 20 amino acids and the thermodynamic functions (ΔG, ΔH, ΔS, and δ) for the successive and overall protonation processes of amino acids have been derived at different temperatures in water and in three different mixtures of water and dioxane (mole fractions of dioxane were 0.083, 0.174, and 0.33). Titrations were also carried out in water ionic strengths of (0.15, 0.20, and 0.25) mol · dm−3 NaNO3, and the resulting dissociation constants are reported. A detailed thermodynamic analysis of the effects of organic solvent (dioxane), temperature and ionic strength influencing the protonation processes of amino acids is presented and discussed to determine the factors which control these processes.  相似文献   

2.
The dissociation constants, pKa, of monoethanolamine (MEA), N-methyldiethanolamine (MDEA), 2-amino-2-methyl-1-propanol (AMP), 2(2-aminoethyl)etanolamine (AEEA), and piperazine (Pz) were measured by potentiometric titration over the temperature range (298.15 to 363.15) K. Enthalpies of protonation, ΔHp, were measured calorimetrically at temperatures from (298.15 to 393.15) K for MEA, MDEA, and AMP, and from (298.15 to 353.15) K for AEEA and Pz. In addition, the effect of the ionic strength of the solutions on the protonation of MDEA was studied using NaCl as background salt {(0 to 5.5) mol/kg-H2O)}. Correlations for the reaction equilibrium constants for proton dissociation are proposed for the studied amines based on the experimental data from literature and from this work. Both experimental enthalpy data and dissociation constants were used for fitting. The results from this work may be used for thermodynamic modeling of CO2 capture processes using amines.  相似文献   

3.
The acid–base properties of four aminophenol derivatives, namely m-aminophenol (L1), 4-amino-2-hydroxytoluene (L2), 2-amino-5-ethylphenol (L3) and 5-amino-4-chloro-o-cresol (L4), are studied by potentiometric and titration calorimetric measurements in NaCl(aq) (0 ? I ? 3 mol · kg?1) at T = 298.15 K. The dependence of the protonation constants on ionic strength is modelled by the Debye–Hückel, SIT (Specific ion Interaction Theory) and Pitzer equations. Therefore, the values of protonation constants at infinite dilution and the relative interaction coefficients are calculated. The dependence of protonation enthalpies on ionic strength is also determined. Distribution (2-methyl-1-propanol/aqueous solution) measurements allowed us to determine the Setschenow coefficients and the activity coefficients of neutral species. Experimental results show that these compounds behave in a very similar way, and common class parameters are reported, in particular for the dependence on ionic strength of both protonation constants and protonation enthalpies.  相似文献   

4.
The interaction between the zwitterionic buffers (3-[N-bis(2-hydroxyethyl)amino]-2-hydroxy propane sulfonic acid, N-(2-actamido)-2-aminoethane sulfonic acid, and 3-[(1,1-dimethyl-2-hydroxyethyl)amino]-2-hydroxy propane sulfonic acid) with some divalent transition metal ions (CuII, NiII, CoII, ZnII, and MnII) were studied at different temperatures (298.15 to 328.15) K at ionic strength I = 0.1 mol · dm−3 NaNO3 and in the presence of 10%, 30%, and 50% (w/w) dioxene by using potentiometry. The thermodynamic stability constants were calculated as well as the free energy change for the 1:1 binary complexation. The protonation constants of the zwitterionic buffers were also determined potentiometrically under the above conditions.  相似文献   

5.
At a constant ionic strength corresponding to human urine (Ic =  0.300 mol · dm  3), the solubilities of xanthine were measured as a function of   lg{c (H + ) / co} (co =  1 mol · dm  3) at the temperatures T =  298.15 K and T =  310.15 K, respectively. Highly reproducible solubility and dissociation constants were obtained. Also, for the first time, the dissolution enthalpy of xanthine was determined calorimetrically. The values of this quantity obtained from both calorimetric determination and temperature dependence of solubility equilibrium constants are thermodynamically consistent.  相似文献   

6.
《Comptes Rendus Chimie》2007,10(7):568-572
A series of new ligands derived from N,N′-O-phenylenebis(salicylideneimine) have been synthesized and characterized by spectrometric methods. Their protonation constants and the stability constants of their complexes with Mn2+, Co2+, Ni2+ et Cu2+ have been determined by potentiometric methods in a water–ethanol (90:10 v/v) mixture at a 0.2 mol l−1 ionic strength (NaCl) and at 25.0 ± 0.1 °C. The Sirko program was used to determine the protonation constants as well as the binding constants of both species [M(HL)]+ and [ML]. The stability order obtained is in agreement with Irving–Williams series.  相似文献   

7.
The equilibrium constants of the 1:1 NpO2+/benzoate complex were determined by spectrophotometric titrations at variable temperatures (T = 283 to 343 K) and the ionic strength of 1.05 mol · kg−1. The enthalpy of complexation at T = 298 K was determined by microcalorimetric titrations. Similar to other monocarboxylates, benzoate forms a weak complex with NpO2+ and the complexation is strengthened as the temperature is increased. The complexation is endothermic and is entropy-driven. The enhancement of the complexation at elevated temperatures is primarily attributed to the increasingly larger entropy gain when the water molecules are released from the highly-ordered solvation spheres of NpO2+ and benzoate to the bulk solvent where the degree of disorder is higher at higher temperatures. The spectroscopic features of the Np(V)/benzoate system, including the effect of temperature on the absorption bands, are discussed in terms of ligand field splitting and a thermal expansion mechanism.  相似文献   

8.
The equilibrium solubility of sodium 2-naphthalenesulfonate in binary (sodium chloride + water), (sodium sulfate + water), and (ethanol + water) solvent mixtures was measured at elevated temperatures from (278.15 to 323.15) K using a steady-state method. With increasing temperatures, the solubility increases in aqueous solvent mixtures. The results of these results were regressed by a modified Apelblat equation. The dissolution entropy and enthalpy determined using the method of the least-squares and the change of Gibbs free energy calculated with the values of ΔdiffSo and ΔdiffHo at T = 278.15 K.  相似文献   

9.
Potentiometric and microcalorimetric titration techniques were applied for the determination of the Gibbs free energies and enthalpies of the protonation and U(VI) complexation of some carboxylic acids (formic, acetic, glycolic, and propionic acids) in 1.0 M NaClO4 solution at 25 °C. By using the values of ΔG determined by potentiometric titrations, the results of calorimetric titrations were analyzed to give the values of ΔH and ΔS. These enthalpy values indicated that the protonation and uranyl(VI) complexation of these carboxylates were mainly entropy-driven, that is, ∣–TΔS  ∣ΔH∣ in ΔG = ΔH  TΔS. The comparison of TΔSm values for uranyl acetate and glycolate complexation with those for europium(III) complexation revealed that the complexation of U(VI) was accompanied by larger entropy changes due to the limited space in its coordination sphere caused by the steric hindrance of two oxygens in the linear dioxo structure of uranyl ion.  相似文献   

10.
An extensive study of the tin(II)/phytate (Phy) system was carried out in NaNO3(aq), at different ionic strengths (0.10  I/mol · L−1  1.00) and temperatures (278.15  T/K  328.15), by potentiometric and voltammetric techniques. The stability and formation enthalpy changes of six SnHqPhy species were determined. To better characterise this system, some potentiometric titrations were also carried out in mixed ionic media (NaNO3(aq) + NaCl(aq) and NaNO3(aq) + NaF(aq)) at total ionic strength I = 1.00 mol · L−1. The formation of some ternary mixed SnHqPhyCl and SnHqPhyF species (charges omitted for simplicity) was found. The formation enthalpies of the complex species were calculated, at I = 0.40 mol · L−1 in NaNO3(aq), by the dependence of stability constants on temperature obtained by potentiometric titrations, in the range 278.15  T/K  328.15. The complex formation process is endothermic, and the main contribution to tin(II) complexation by phytate is entropic in nature. For example, for the SnPhy species we have, at T = 298.15 K and I = 0.40 mol · L−1 in NaNO3(aq): ΔH = 57.7 ± 2.8 kJ mol · L−1, ΔG = −99.9 ± 1.7 kJ mol · L−1, and TΔS = 158 ± 3 kJ mol · L−1. The ionic strength dependence of the formation constants of the simple tin(II)/phytate species, was modelled by the Debye–Hückel and the SIT approaches. The sequestering ability of phytate towards tin(II) was evaluated by calculating the pL0.5 values (i.e., the total ligand concentration necessary to bind 50% of cation present in trace) at different ionic strengths, ionic media, and pH. The sequestering ability increases with increasing the pH, whilst it decreases with increasing the ionic strength (the same behaviour shown by the stability constants). Moreover, taking into account the different sequestering ability of phytate towards tin(II) in the different ionic media, the trend: pL0.5 = 5.70 (in NaNO3(aq) + NaF(aq)) > pL0.5 = 5.16 (in NaNO3(aq) + NaCl(aq)) > pL0.5 = 4.86 (in NaNO3(aq)) was observed at pH 8.1 and I = 1.00 mol · L−1. This is due to the presence of a second ligand (Cl or F) that stabilizes the complex species with the formation of ternary complex species. Some empirical relationships were also found.  相似文献   

11.
The solubility of hydrogen sulphide in three ionic liquids, viz. 1-hexyl-3-methylilmidazolium hexafluorophosphate ([hmim][PF6]), 1-hexyl-3-methylimidazolium tetrafluoroborate ([hmim][BF4]), and 1-hexyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([hmim][Tf2N]), at temperatures ranging from 303.15 K to 343.15 K and pressures up to 1.1 MPa were determined. The solubility values were correlated using the Krichevsky–Kasarnovsky equation and Henry’s constants were obtained at different temperatures. Partial molar thermodynamic functions of solvation such as standard Gibbs free energy, enthalpy, and entropy were calculated from the solubility results. Comparison of the values obtained show that the solubility of H2S in these three ionic liquids was in the sequence: [hmim][BF4] > [hmim][PF6]  [hmim][Tf2N].  相似文献   

12.
Molar calorimetric enthalpy changes ΔrHm(cal) have been measured for the biochemical reactions {cAMP(aq) + H2O(l)=AMP(aq)} and {PEP(aq) + H2O(l)=pyruvate(aq) + phosphate(aq)}. The reactions were catalyzed, respectively, by phosphodiesterase 3,5-cyclic nucleotide and by alkaline phosphatase. The results were analyzed by using a chemical equilibrium model to obtain values of standard molar enthalpies of reaction ΔrHm for the respective reference reactions {cAMP(aq) + H2O(l)=HAMP(aq)} and {PEP3−(aq) + H2O(l)=pyruvate(aq) + HPO2−4(aq)}. Literature values of the apparent equilibrium constants K for the reactions {ATP(aq)=cAMP(aq) + pyrophosphate(aq)}, {ATP(aq) + pyruvate(aq)=ADP(aq) + PEP(aq)}, and {ATP(aq) + pyruvate(aq) + phosphate(aq)=AMP(aq) + PEP(aq) + pyrophosphate(aq)} were also analyzed by using the chemical equilibrium model. These calculations yielded values of the equilibrium constants K and standard molar Gibbs free energy changes ΔrGm for ionic reference reactions that correspond to the overall biochemical reactions. Combination of the standard molar reaction property values (K, ΔrHm, and ΔrGm) with the standard molar formation properties of the AMP, ADP, ATP, pyrophosphate, and pyruvate species led to values of the standard molar enthalpy ΔfHm and Gibbs free energy of formation ΔfGm and the standard partial molar entropy Sm of the cAMP and PEP species. The thermochemical network appears to be reasonably well reinforced and thus lends some confidence to the accuracy of the calculated property values of the variety of species involved in the several reactions considered herein.  相似文献   

13.
A new amino acid ionic liquid (AAIL) [C3mim][Val] (1-propyl-3-methylimidazolium valine) was prepared by the neutralization method. Using the solution-reaction isoperibol calorimeter, molar solution enthalpies of the ionic liquid [C3mim][Val] with known amounts of water and with different concentrations in molality were measured at T = 298.15 K. In terms of standard addition method (SAM) and Archer’s method, the standard molar enthalpy of solution for [C3mim][Val] without water, ΔsHm = (−55.7 ± 0.4) kJ · mol−1, was obtained. The hydration enthalpy of the cation [C3mim]+, ΔH+ ([C3mim]+) = −226 kJ · mol−1, was estimated in terms of Glasser’s theory. Using the RD496-III heat conduction microcalorimeter, the molar enthalpies of dilution, ΔDHm(mi  mf), of aqueous [C3mim][Val] with various values of molality were measured. The values of ΔDHm(mi  mf) were fitted to Pitzer’s ion-interaction model and the values of apparent relative molar enthalpy, φL, calculated using Pitzer’s ion-interaction model.  相似文献   

14.
The solubility of carbon dioxide in a series of 1-(2-hydroxyethyl)-3-methylimidazolium ([hemim]+) based ionic liquids (ILs) with different anions, viz. hexafluorophosphate ([PF6]?), trifluoromethanesulfonate ([OTf]?), and bis-(trifluoromethyl)sulfonylimide ([Tf2N]?) at temperatures ranging from 303.15 K to 353.15 K and pressures up to 1.3 MPa were determined. The solubility data were correlated using the Krichevsky–Kasarnovsky equation and Henry’s law constants were obtained at different temperatures. Using the solubility data, the partial molar thermodynamic functions of solution such as Gibbs free energy, enthalpy, and entropy were calculated. Comparison showed that the solubility of CO2 in the ILs studied follows the same behaviour as the corresponding conventional 1-ethyl-3-methylimidazolium ([emim]+) based ILs with the same anions, i.e. [hemim][NTf2] > [hemim][OTf] > [hemim][PF6] > [hemim][BF4].  相似文献   

15.
Effect of 100 keV proton radiation on the structure and tensile properties of PTFE film was investigated. The change in structure before and after proton radiation was mainly evaluated by means of differential scanning calorimetry. The experimental results show that under radiation of 100 keV protons for the fluence less than 7×1015 p/cm2, the DSC characteristics including the phase enthalpy of transformations at room temperature ΔHrt1 and ΔHrt2, the melting enthalpy ΔHm1 and ΔHm2, the crystallization exothermal enthalpy ΔHc, and Tg II were decreased, while the melting temperature was increased a little with the fluence increase. The change in crystallization enthalpy ΔHc indicated the increase of molecular weight of the PTFE film, but for 150 keV when the fluence exceeded the fluence of 1016/cm2, the molecular weight decreased gradually. With increasing proton fluence, the thermal gravity loss was decreased, while the initial decomposition temperature increased, demonstrating that crosslinking of molecular chains occurred. With the increase of the proton fluence, for proton with energy less than 150 keV, the tensile fracture strength increased at first, but when the fluence exceeded 1016/cm2, the tensile fracture strength showed a decreasing trend. While for the proton of 170 keV, the tensile fracture strength σf increased abruptly at the fluence of 2×1013/cm2, with the fluence increasing further, the tensile fracture strength σf decreased gradually. The change of tensile properties could be related with the competition of branching crosslinking and the scission degradation.  相似文献   

16.
The kinetics of Os(VIII) catalysed oxidation of l-lysine by diperiodatoargentate(III) (DPA) in alkaline medium at T = 298 K and a constant ionic strength of 0.50 mol · dm?3 was studied spectrophotometrically. The oxidation products are aldehyde (5-aminopentanal) and Ag(I). The stoichiometry is i.e. [l-lysine]:[DPA] = 1:1. The reaction is of first order in [Os(VIII)] and [DPA] and is less than unit order in both [l-lys] and [alkali]. Addition of periodate has no effect on the reaction. Effect of added products, ionic strength, and dielectric constant of the reaction medium have been investigated. The oxidation reaction in alkaline medium has been shown to proceed via a Os(VIII)-l-lysine complex, which further reacts with one molecule of deprotonated DPA in a rate determining step followed by other fast steps to give the products. The main products were identified by spot test, IR, and GC-MS. The reaction constants involved in the different steps of the mechanism are calculated at different temperatures. The catalytic constant (KC) was also calculated at different temperatures. From the plots of lg KC versus 1/T, values of activation parameters with respect to the catalyst have been evaluated. The activation parameters with respect to slow step of the mechanism are computed and discussed and thermodynamic quantities are also determined. The active species of catalyst and oxidant have been identified.  相似文献   

17.
Standard thermodynamic functions of transfer of naphthalene and 2-naphthoic acid from water to (water + ethanol) mixtures at T=298.15 K have been determined from solubility measurements at different temperatures. Standard free energies of transfer of both naphthalene and 2-naphthoic acid showed decreasing tendency with the increasing x(EtOH), and the standard entropy and enthalpy of transfer exhibited a change of double peaks with x(EtOH). The ΔtrG0 of 2-naphthoic acid decreased more rapidly than that of naphthalene when x(EtOH) < 0.746 and lower than that of naphthalene when x(EtOH) >0.746 at T=298.15 K. The double peaks in the curves of standard entropy and enthalpy of transfer illustrated that the microstructure of the series of mixed solvents of (water + ethanol) underwent a variable process from ordered to disordered and then from disordered to ordered. The results mean that there is a relatively ordered structure near x(EtOH)=0.13 in the (water + ethanol) solutions besides the existence of a clathrate structure in the water-rich region.  相似文献   

18.
The TALSPEAK process (Trivalent Actinide Lanthanide Separations by Phosphorus-reagent Extraction from Aqueous Komplexes) has been demonstrated in several pilot-scale operations to be effective at separating trivalent actinides (An3+) from trivalent lanthanides (Ln3+). However, fundamental studies have revealed undesired aspects of TALSPEAK, such as the significant partitioning of Na+, lactic acid, and water into the organic phase, thermodynamically unpredictable pH dependence, and the slow extraction kinetics. In the modified TALSPEAK process, the combination of the aqueous holdback complexant HEDTA (N-(2-hydroxyethyl)ethylenediamine-N,N′,N′-triacetic acid) with the extractant HEH[EHP] (2-ethyl(hexyl) phosphonic acid mono-2-ethylhexyl ester) in the organic phase has been found to exhibit a nearly flat pH dependence between 2.5 and 4.5 and more rapid phase transfer kinetics for the heavier lanthanides. To help understand the speciation of Ln3+ and An3+ in the modified TALSPEAK, systematic studies are underway on the thermodynamics of major reactions in the HEDTA system under conditions relevant to the process (e.g., higher temperatures). Thermodynamics of the protonation and complexation of HEDTA with Ln3+ were studied at variable temperatures. Equilibrium constants and enthalpies were determined by a combination of techniques including potentiometry and calorimetry. This paper presents the protonation constants of HEDTA at T = (25 to 70) °C. The potentiometric titrations have demonstrated that, stepwise, the first two protonation constants decrease and the third one slightly increases with the increase of temperature. This trend is in good agreement with the enthalpy of protonation directly determined by calorimetry. The results of NMR analysis further confirm that the first two protonation reactions occur on the diamine nitrogen atoms, while the third protonation reaction occurs on the oxygen of a carboxylate group. These data, in conjunction with the thermodynamic parameters of Ln3+/An3+ complexes with HEDTA at different temperatures, will help to predict the speciation and temperature-dependent behavior of Ln3+/An3+ in the modified TALSPEAK process.  相似文献   

19.
We present a study on the effect of the alkyl chain length of the imidazolium ring in 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquids, [C1CnIm][NTf2] (n = 2 to 10), on the mixing properties of (ionic liquid + alcohol) mixtures (enthalpy and volume). We have measured small excess molar volumes with highly asymmetric curves as a function of mole fraction composition (S-shape) with more negative values in the alcohol-rich regions. The excess molar volumes increase with the increase of the alkyl-chain length of the imidazolium cation of the ionic liquid. The values of the partial molar excess enthalpy and the enthalpy of mixing are positive and, for the case of methanol, do not vary monotonously with the length of the alkyl side-chain of the cation on the ionic liquid – increasing from n = 2 to 6 and then decreasing from n = 8. This non-monotonous variation is explained by a more favourable interaction of methanol with the cation head group of the ionic liquid for alkyl chains longer than eight carbon atoms. It is also observed that the mixing is less favourable for the smaller alcohols, the enthalpy of mixing decreasing to less positive values as the alkyl chain of the alcohol increases. Based on the data from this work and on the knowledge of the vapour pressure of {[C1CnIm][NTf2] + alcohol} binary mixtures at T = 298 K reported in the literature, the excess Gibbs free energy, excess enthalpy and excess entropy could be then calculated and it was observed that these mixtures behave like the ones constituted by a non-associating and a non-polar component, with its solution behaviour being determined by the enthalpy.  相似文献   

20.
In the present work, density and viscosity of two binary mixtures of N-methyldiethanolamine (MDEA) and diethanolamine (DEA) with 1-butyl-3-methylimidazolium acetate ([bmim][acetate]) are measured. The experiments were carried out at atmospheric pressure and at T = (293.15 to 343.15) K for density and from 293.15 K to 353.15 K for viscosity over the whole range of mole fraction. Using the density and viscosity results, several physical and thermodynamic properties such as excess molar volumes (VE), coefficients of thermal expansions (α), viscosity deviation (Δη),molar activation entropy (ΔS), molar activation enthalpy (ΔH) and molar activation Gibbs free energy (ΔG) for these binary mixtures are calculated.The experimental results of the density and viscosity for the pure systems as well as the binary systems show a decrease with increasing temperature as expected. The results of density measurements show that over all ranges of temperatures investigated the density of the pure components show the following trend: DEA > [bmim][acetate] > MDEA. Therefore, in the binary mixtures of the (MDEA + [bmim][acetate]), the density of the mixture reduces with decreasing concentration of the ionic liquid and for the (DEA + [bmim][acetate]) mixture the density of the blend enhances to reduce the concentration of the ionic liquid. Moreover, the calculated excess molar volumes show a positive deviation from ideality for the two binary mixtures. The behaviour of change of viscosity against concentration for the (MDEA + [bmim][acetate]) system is different from the (DEA + [bmim][acetate]) mixture so that for the first system the value of the viscosity rises with increasing [bmim][acetate] mole fraction, but in the second system there is a minimum viscosity point in the DEA-rich region.  相似文献   

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