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1.
The protonation constants and solubilities of three complexons [ethylenediamine-N,N′-disuccinic acid (EDDS), ethylene glycol bis(2-aminoethyl ether)-N,N,N′,N′-tetraacetic acid (EGTA) and 1,2-cyclohexanediamine-N,N,N′,N′-tetraacetic acid (CDTA)] are reported in aqueous solutions of NaCl with different ionic strength values (0 ≤ I ≤ 4.8 mol·L?1) and, in the case of CDTA, in (CH3)4NCl (0.1 ≤ I ≤ 2.7 mol·L?1). The dependence on ionic strength of the protonation constants of these three complexons and four other complexons that were previously reported (NTA, EDTA, DTPA and TTHA), is analyzed in NaCl solution; the ionic strength influences quite strongly the protonation constants (as an example for CDTA, log10 K 1 = 10.54 and 9.25 at I = 0.1 and 1 mol·L?1, respectively), while the effect of (CH3)4NCl concentration is lower. Based on the total solubility S T and the protonation constant data at different salt concentrations, the solubility of the neutral species S 0 and the solubility products K S0 are obtained. The Setschenow coefficients k m and the solubility values S 0 0 in pure water are also reported (S 0 0  = 0.55, 0.21 and 0.75 mmol·kg?1 for EDDS, EGTA and CDTA, respectively). The dependence of the protonation constants on ionic strength is also interpreted in terms of ion pair formation, and the formation constants of Na+ species are reported.  相似文献   

2.
In this study the binary and ternary complexes of copper(II) with substituted 1,10-phenanthrolines [s-phen: 1,10-phenanthroline (phen), 4,7-dimethyl-1,10-phenanthroline (dmphen) and 5-nitro-1,10-phenanthroline (nphen)] and l-amino acids [aa: l-phenylalanine (phe), l-tyrosine (tyr) and l-tryptophan (trp)] have been investigated using potentiometric methods in 0.1 mol·L?1 KCl aqueous ionic media at 298.2 K. The protonation constants of the ligands and the stability constants of the binary and ternary complexes of Cu(II) with the ligands were calculated from the potentiometric data using the “BEST” software package. It was inferred that the aromatic 1,10-phenanthrolines act as a primary ligand in the ternary complexes, while the oxygen and nitrogen donor-containing amino acids are secondary ligands. The observed values of Δlog10 K indicate that the ternary complexes are more stable than the binary ones, suggesting no interaction takes place between the ligands in the ternary complexes. The magnitudes of the measured stability constants of all of the ternary complexes are in the order [Cu(s-phen)(trp)]+ > [Cu(s-phen)(tyr)]+ > [Cu(s-phen)(phe)]+, which is identical to the sequence found for the binary complexes of Cu(II) with the amino acids. When the substituted 1,10-phenanthroline is changed, the stability constants of the ternary complexes decrease in the following order: [Cu(dmphen)(aa)]+ > [Cu(phen)(aa)]+ > [Cu(nphen)(aa)]+.  相似文献   

3.
The complexation characteristics of thorium–arsenazo III in the range of 1–6 mol·L?1 hydrochloric acid media were investigated by UV–Vis absorption spectroscopy and computational analysis. The chemical equilibrium model of thorium–arsenazo III complexation was established including the species distribution of arsenazo III, the formation of thorium chloride species, and the release of protons from thorium–arsenazo III complexes. In the spectra of thorium–arsenazo III complexes, two characteristic absorption peaks were observed at 610 and 660 nm, and the latter peak showed a tendency to shift about 4 nm to higher wavelength as the acidity of the hydrochloric acid media increased from 1 to 6 mol·L?1. Analysis of the experimental data indicates that the molar absorptivities of both 1:1 and 1:2 complexes (thorium to arsenazo III) steadily increase as the acidity of medium increases. The determined stability constants of 1:1 and 1:2 complexes at various concentrations of hydrochloric acid were extrapolated to zero ionic strength, based on the specific ion interaction theory (SIT) approach. The limiting stability constants were determined to be \( { \log }_{10} \beta_{11}^{\text{o}} \) = 8.56 ± 0.13 and \( {\log}_{10} \beta_{12}^{\text{o}} \) = 15.17 ± 0.18 with ion interaction coefficients of Δε 11 = –0.57 ± 0.02 kg·mol?1 and Δε 12 = –0.60 ± 0.04 kg·mol?1, respectively.  相似文献   

4.
The protonation equilibria of (2Z, 3Z)-2H-benzo[b][1,4]thiazine-2,3(4H)-dionedioxime (BTDH2) together with the equilibria of its bis- binary complexes of Co(II), Ni(II), Cu(II) and Zn(II) were investigated potentiometrically. The investigation was carried out at 25 ± 0.1 °C, in aqueous solution, with a constant ionic strength of 0.100 mol·dm?3 NaCl. The protonation constants of the ligand together with the stability constants of a variety of complexes were determined potentiometrically in 10 % ethanol–water mixed solution using the SUPERQUAD computer program. Theoretical calculations were set up to assist in understanding the protonation sequence in the ligand molecule via the semi-empirical molecule orbital method of parameterized model number 3. Results are discussed in connection to the basicity of the donor atoms and structural arrangement of the ligand. Although BTDH2 has two dissociable protons, four protonation constants can be measured under the experimental conditions presented. These four protonation constants (as log10 βs) are 10.245, 19.397, 22.414 and 25.176.  相似文献   

5.
Protonation constants of methyl/nitro substituted 1,10-phenanthrolines {(m/n-sphen): 4-methyl-phenanthroline (4-mphen), 5-methyl-1,10-phenanthroline (5-mphen), 4,7-dimethyl-1,10-phenanthroline (dmphen), 3,4,7,8-tetramethyl-1,10-phenanthroline (tmphen) and 5-nitro-1,10-phenanthroline (5-nphen)] and the amino acids (aa) l-tyrosine (tyr) and glycine (gly), and their corresponding binary and ternary stability constants with Cu(II), were determined in aqueous 0.1 mol·L?1 KCl ionic media at 298.15 K. The protonation constants of the ligands and the stability constants of the binary and ternary complexes of Cu(II) with the ligands were calculated from the potentiometric data using the “BEST” software package. The species distribution diagrams were obtained using the “SPE” software package under the experimental conditions described. The order of stability of the ternary complexes in terms of the primary ligands is [Cu(tmphen)(aa)]+ > [Cu(dmphen)(aa)]+ > [Cu(4-mphen)(aa)]+ > [Cu(5-mphen)(aa)]+ > [Cu(5-nphen)(aa)]+. The stability constants of the ternary complexes decrease in the following order: [Cu(m/n-sphen)(gly)]+ > [Cu(m/n-sphen)(tyr)]+, which is identical to the sequence found for the binary complexes of Cu(II) with gly and tyr.  相似文献   

6.
BAGHERI GH Azar 《中国化学》2009,27(6):1073-1078
The complexation of zinc(II) with dopamine has been investigated by spectrophotometric measurements in mixed solvent system at an ionic strength of 0.2 mol•dm-3 sodium chloride, employed at at (15±0.1), (25±0.1), (35±0.1) ℃ at inin a pH range of ca. 6 to ca. 7 with a high ratio of ligand to metal. The effect of solvent systems on protonation and complexation are was was discussed. Linear relationships are werewere observed by plotting lg K versus 1/D, where K and D show stability and dielectric constants, respectively.  相似文献   

7.
The stability constants for the Tc(IV) and V(IV) complexation with the polyamino polycarboxylate ligands IDA, NTA, HEDTA and DTPA were determined using liquid–liquid extraction techniques. These stability constants were then used to evaluate the validity of using V(IV) as a chemical analogue for Tc(IV). Results suggest that Tc(IV), as TcOOH+, will form β 1?11 complexes with the selected ligands, while V(IV), as VO2+, will form β 101 complexes. The values for these determined stability constants are (in log10 unit) 10.9 ± 0.1, 11.4 ± 0.1, 14.9 ± 0.1, and 20.1 ± 0.1 for Tc(IV) in 0.5 mol·L?1 NaCl at 25 °C, for IDA, NTA, HEDTA and DTPA, respectively, they are 9.3 ± 0.1, 11.6 ± 0.2, 15.8 ± 0.1, and 20.8 ± 0.1 for V(IV) in 0.5 mol·L?1 NaCl at 25 °C, for the same suite of ligands. The incorporation of a hydroxide into the metal ligand complexes formed by Tc(IV) is proposed as the largest factor differentiating the apparent stability constants of Tc(IV) and V(IV). This work shows that V(IV) is a poor analog for Tc(IV); however, despite the differences in complexation mechanism between V(IV) and Tc(IV), V(IV) still appears to have some use for predicting Tc(IV) complexation behavior.  相似文献   

8.
The properties of diflunisal, a widely used analgesic, were studied in physiologic solutions, 0.15 mol·dm?3 NaCl. Solubility and protonation constants were determined and its behavior as ligand towards Ca(II) and Mg(II) was investigated. Solubility and protonation constants of diflunisal at 25 °C and 0.15 mol·dm?3 were obtained from electromotive force measurements of galvanic cells using coulometric titrations. The experimental data yielded the solubility, s, of –log10 s = 3.86 ± 0.02 and the protonation constants log10 K 1 = 11.98 ± 0.10 and log10 K 2 = 3.86 ± 0.03. Equilibria between diflunisal and Ca(II) and Mg(II) were investigated by means of electromotive force measurements and by comparing solubilities of diflunisal in the presence and absence of Ca(II) or Mg(II), respectively. Experimental data were explained by assuming the formation of 1:1 complexes for Ca(II) and Mg(II) along with evaluating the relative stability constants.  相似文献   

9.
Spectrophotometric and calorimetric titrations were used to determine the equilibrium constants (log10 K 111) and enthalpies of formation (ΔH 111) for aqueous ternary complexes of the form M(La)(Lb) (M = Nd3+, Sm3+, Tb3+, Ho3+, Er3+, or Am3+; La = DTPA5?, DO3A3?, or CDTA4?; Lb = oxalate (Ox), malonate (Mal), or iminodiacetate (IDA)). Inner-sphere ternary complexes were readily formed with the septadentate DO3A (1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid) and hexadentate CDTA (trans-1,2-diaminocyclohexanetetraacetic acid) ligands, whose binary complexes have residual metal-coordinated water molecules that are readily displaced by the smaller secondary ligands. The stability constants for the formation of lanthanide–CDTA complexes with Ox, Mal, and IDA generally increase with decreasing ionic radius when steric hindrance is minimal, with the trend in the M(CDTA)? formation constants overshadowing any size-based reversal in the stepwise ternary complexation constants. Similar ternary complexes with DO3A showed little increase in thermodynamic stability compared to analogous CDTA complexes and no preference for larger Ln cations. The octadentate DTPA (diethylenetriaminepentaacetic acid) ligand proved too large to form ternary complexes to a measurable extent with any of the secondary ligands investigated, despite the presence of one residual inner sphere water molecule.  相似文献   

10.
4-hydroxy-3,5-pyridinedicarboxylic acid (DQ58) and 4-hydroxy-1-methyl-3,5-pyridinedicarboxylic acid (DQ71508) have been synthesized, and their Fe(III), Al(III), Cu(II), and Zn(II) coordination properties have been studied by potentiometry, UV–Vis spectroscopy (in the case of Fe(III), Al(III), Cu(II)), 1H-NMR (for Al(III)) and EPR (for Cu(II)). The thermodynamic results were used to model the extent of the toxic metal ions decorporation (Fe(III) or Al(III)) in the presence of the essential metal ions (Cu(II) or Zn(II)). DQ58 and DQ71508 were demonstrated to interact with human serum albumin (HSA), which is assumed to be the main serum transporter of the chelators, and binding constants have been obtained by ultrafiltration. IC50 values of 5.185 × 10?3 and 1.033 × 10?3 mol·L?1 were collected after 24 and 48 h of treatment with DQ71508 towards human embryonic kidney HEK-293 cells, demonstrating the relatively low cytotoxicity of this compound. According to these results, both DQ58 and DQ71508 seem to be potential candidates for Fe chelation therapy, and DQ58 is a better Fe(III) chelator than DQ71508.  相似文献   

11.
Diethylenetriamine-N,N,N′,N″,N″-pentaacetic acid (DTPA) is an octadentate aminopolycarboxylate complexing agent whose f-element complexes find important practical applications in nuclear medicine and in advanced nuclear fuel reprocessing. This investigation focuses primarily on the latter application, specifically on characterization of lanthanide–DTPA complexes of relevance to the Trivalent Actinide–Lanthanide Separations by Phosphorus reagent Extraction and Aqueous Komplexants (TALSPEAK) process. To function acceptably, the TALSPEAK process requires the presence of moderate concentrations (0.5–2.0 mol·L?1) of a (Na+/H+) lactate (or citrate) buffer. Competition between DTPA, lactate, and the extractant bis(2-ethylhexyl)phosphoric acid (HDEHP) for the lanthanides and trivalent actinides governs the course of the extraction process. To facilitate modeling and to support process improvements, the acid dissociation constants and stability constants for rare earth complexes with DTPA have been determined in 2.0 mol·L?1 ionic strength (NaClO4) media. The acid dissociation constants for DTPA and the stability constant for [Eu(DTPA)]2? also were determined in sodium trifluoromethanesulfonate at 2.0 mol·L?1 ionic strength to evaluate the potential impact of changing the nature of the electrolyte. The thermodynamic data are compared with earlier reports of similar data at lower ionic strength and used to complete calculations exploring the relative stability of lanthanide–DTPA and lactate complexes under TALSPEAK extraction conditions. Lanthanide–DTPA stability trends are discussed in comparison with literature data on a variety of other metal ions.  相似文献   

12.
Glufosinate, an analogue of glutamic acid (also known as phosphinothricin), is an important herbicide. The protonation constants of glufosinate were determined by means of potentiometric titrations at variable temperatures with ionic strength 0.5 mol·L?1 (NaCl solution). The heat effects of the protonation reactions of glufosinate were measured by direct calorimetry. NMR spectroscopies have demonstrated that the first protonation site occurs on the nitrogen atom in the amino group, followed by one of the oxygen atoms in the phosphono group, and finally the carboxyl oxygen atom. This trend is in good agreement with the enthalpy of protonation and crystal structure results. These data will help to predict the speciation of glufosinate in physiological systems.  相似文献   

13.
UV spectroscopic measurements have been used to determine the binding ability of diethylenetriaminepentaacetic acid (DTPA) ligand towards the $ {\text{VO}}_2^+ $ ion at different ionic strengths of sodium chloride (0.11–0.95 mol·dm?3) and at T = 298 K. Dissociation constants of DTPA have been gathered from the literature. Calculations allowed us to identify the formation of three species VO2H3L, VO2H2L? and VO2HL2? in the pH range of about 1.00–2.50. All of these complexes were characterized in terms of their stability constants on the basis of two different thermodynamic models (extended Debye–Hückel type and specific ion interaction theory) for the investigation of the ionic strength dependence of the stability and dissociation constants. Comparison with literature data is also reported.  相似文献   

14.
Seven-coordinate Fe(III) complexes [Fe(dapsox)(H2O)2]+, where [dapsox = 2,6-diacetylpyridine-bis(semioxamazide)] is an equatorial pentadentate ligand with five donor atoms (2O and 3N), were studied with regard to their acid–base properties and complex formation equilibria. Stability constants of the complexes and the pK a values of the ligands were measured by potentiometric titration. The interaction of [Fe(dapsox)(H2O)2]+ with the DNA constituents, imidazole and methylamine·HCl were investigated at 25 °C and ionic strength 0.1 mol·dm?3 NaNO3. The hydrolysis constants of the [Fe(dapsox)(H2O)2]+ cation (pK a1 = 5.94 and pK a2 = 9.04), the induced ionization of the amide bond and the formation constants of the complexes formed in solution were calculated using the nonlinear least-squares program MINIQUAD-75. The stoichiometry and stability constants for the complexes formed are reported. The results show the formation of 1:1 and 1:2 complexes with DNA constituents supporting the hepta-coordination mode of Fe(III). The concentration distributions of the various complex species were evaluated as a function of pH. The thermodynamic parameters ΔH° and ΔS° calculated from the temperature dependence of the equilibrium constants were investigated for interaction of [Fe(dapsox)(H2O)2] with uridine.  相似文献   

15.
Extraction of U(VI), Eu(III) and Am(III) has been performed from acidic aqueous solutions (HNO3, HClO4) into the ionic liquid [C4mim][Tf2N] in which a new extracting task-specific ionic liquid, based on the CMPO unit {namely 1-[3-[2-(octylphenylphosphoryl)acetamido]propyl]-3-methyl-1H-imidazol-3-ium bis(trifluoromethane)sulfonamide, hereafter noted OctPh-CMPO-IL}, was dissolved at low concentration (0.01 mol·L?1). EXAFS and UV–Vis spectroscopy measurements were performed to characterize the extracted species. The extraction of U(VI) is more efficient than the extraction of trivalent Am and Eu using this TSIL, for both acids and their concentration range. We obtained evidence that the metal ions are extracted as a solvate (UO2(OctPh-CMPO-IL)3) by a cation exchange mechanism. Nitrate or perchlorate ions do not play a direct role in the extraction by being part of the extracted complexes, but the replacement of nitric acid for perchloric acid entails a drop in the selectivity between U and Eu. However, our TSIL allows a sequential separation of U(VI) and Eu/Am(III) using the same HNO3 concentration and same nature of the organic phase, just by changing the ligand concentration.  相似文献   

16.
The interaction of diethyltin(IV), DET, with selected bioligands having a variety of model functional groups was investigated at 25 °C and ionic strength 0.1 mol·dm?3 NaCl using the potentiometric technique. The hydrolysis constants of the DET cation and the formation constants of the complexes formed in solution were calculated using the MINIQUAD-75 program. The stoichiometry and stability constants for the complexes formed are reported. The results show the formation of 1:1 and 1:2 complexes with amino acids and DNA constituents. The dicarboxylic acids form 1:1 complexes. The peptides form both 110 complexes and the corresponding deprotonated amide species [Et2Sn(LH?1)] (11-1). The participation of different ligand functional groups in binding to organotin is discussed. The concentration distributions of the various complex species were evaluated as a function of pH. The standard thermodynamic parameters ΔH° and ΔS°, calculated from the temperature dependence of the equilibrium constants, were investigated for the interaction of DET with thymine as a representative example of DNA constituents. The effect of ionic strength and solvent on hydrolysis constants of DET, protonation equilibria of thymine and its complex formation with DET were investigated and discussed.  相似文献   

17.
The thermodynamic properties of 2-mercaptopyridine-N-oxide (pyrithione, PT) were studied potentiometrically in NaCl aqueous solutions at different ionic strengths and temperatures. A set of protonation constants is provided, together with distribution (water/2-methyl-1-propanol) and solubility data. The total and the specific solubility (solubility of neutral species) values of pyrithione were determined and, for example, are 0.0561 and 0.0518 mol·dm?3 at c NaCl = 0.244 mol·dm?3 and T = 298.15 K. By fitting the distribution and solubility results against the ionic strength, the Setschenow coefficient and the activity coefficients of the neutral species were determined. In pure water, the specific solubility is log10 \( S_{m 0}^{0} = \, {-} 1. 20 \, \pm \, 0.0 4 \) . To determine the activity coefficient of the charged species and the protonation constant at infinite dilution, the data were analyzed by different models, namely the Debye–Hückel type equation, the SIT (Specific ion Interaction Theory) and the Pitzer approach. The interaction coefficient of the deprotonated pyrithione species was determined [ε(Na+, PT?) = ?0.105 ± 0.002]. The protonation enthalpy was also determined, is slightly positive, and the protonation process is entropic in nature. At infinite dilution and T = 298.15 K, log10 K H0 = 4.620 ± 0.002, ΔG 0 = –26.4 ± 0.1 kJ·mol?1, ΔH 0 = 2.1 ± 0.5 kJ·mol?1 and TΔS 0 = 28.5 ± 0.5 kJ·mol?1. The electrochemical behavior of pyrithione was studied in NaCl solutions at T = 298.15 K. It was found that voltammetry can be used to study the binding ability of pyrithione towards metal cations. The results of this work are in agreement with literature findings and improve the knowledge of the chemistry of pyrithione in aqueous solutions.  相似文献   

18.
By using spectrophotometric and potentiometric techniques the formation constants of the species formed in the systems H^++ Mo(Ⅵ)+nitrilotriacetic acid and H^+ + nitrilotriacetic acid have been determined in aqueous solutions of propanol at 25 ℃ and constant ionic strength 0.1 molodm^-3 sodium perchlorate. The composition of the complex was determined by the continuous variation method. It was shown that molybdenum(Ⅵ) forms a mononuclear 1 : 1 complex with nitrilotriacetic acid of the type MoO3L^-3 at -lg[H^+] =5.8. The formation constants in various media were analyzed in terms of Kamlet and Taft's parameters. Linear relationships were observed when lg Ks was plotted versusp. Finally, the results were discussed in terms of the effect of solvent on complexation.  相似文献   

19.
The complexation equilibria of Fe(III) with two buffer families, which are ubiquitous in biological system studies, were studied by potentiometric measurements at a constant ionic strength of I = 0.1 mol·dm?3 NaNO3 in aqueous solutions at 298.15 K. The members of TRIS family are tris(hydroxymethyl)aminomethane (TRIS), N-[tris(hydroxymethyl)methyl]-2-aminoethanesulfonic acid (TES), N-[tris(hydroxymethyl)methyl]-3-aminopropanesulfonic acid (TAPS), N-[tris(hydroxymethyl)methyl]-3-amino-2-hydroxypropanesulfonic acid (TAPSO), and N-tris(hydroxymethyl)methyl-4-aminobutanesulfonic acid (TABS) buffers. The members of morpholine family are 4-morpholineethanesulfonic acid (MES), 4-morpholinepropanesulfonic acid (MOPS), 3-morpholino-2-hydroxypropanesulfonic acid (MOPSO), and 4-(N-morpholino) butanesulfonic acid (MOBS) buffers. The overall stability constants were determined from pH-metric data using the least-squares curve-fitting program HYPERQUAD 2008. Based on the best-fit results, the species formed at equilibrium are ML, ML2, ML2H?1, and ML3 in the systems with TRIS family buffers. The complex species ML, ML2, ML2H?1, and MLH?1 are formed in the MOPSO-containing system, while ML, ML2, and ML2H?1 are formed in the systems with MES, MOPS, and MOBS. The stabilities of the complexes fall in the order TABS > TRIS > TAPS > TAPSO > TES and MOBS > MOPS > MOPSO > MES for the TRIS family and morpholine families, respectively.  相似文献   

20.
沈雪松  秦雪莲  刘义  屈松生 《化学学报》2005,63(18):1739-1742
[H+]在0.01~0.70 mol•L-1范围内, 离子强度为1.00 mol•L-1, [Fe(III)]>>[配体]、[H+]>>[配体]的条件下, 研究了Fe(III)与2,3-二羟基苯磺酸钠(Tiron)的配位反应. 发现当[H+]≤3.00×10-2 mol•L-1时, [Fe(III)]2对反应速率有明显的贡献. 求得了相关反应的动力学参数, 从而揭示了FeOH2+和与Tiron配位的解离反应途径及的缔合反应机制, 并提出了该配位反应的可能机理.  相似文献   

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