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1.
The formation of complexes between iron(II) and tartrate ion (L) has been studied at 25° C in 1m-NaClO4, by using a glass electrode. The e.m.f. data are explained with the following equilibria: $$\begin{gathered} Fe^{2 + } + L \rightleftarrows FeL log \beta _1 = 1,43 \pm 0,05 \hfill \\ Fe^{2 + } + 2L \rightleftarrows FeL_2 log \beta _2 = 2,50 \pm 0,05 \hfill \\\end{gathered} $$ The protonation constants of the tartaric acid have been determinated: $$\begin{gathered} H^ + + L \rightleftarrows HL logk_1 = 3,84 \pm 0,03 \hfill \\ 2H^ + + L \rightleftarrows H_2 L logk_2 = 6,43 \pm 0,02 \hfill \\\end{gathered}$$ .  相似文献   

2.
The temperature dependencies of europium carbonate stability constants were examined at 15, 25, and 35°C in 0.68 molal Na+(ClO 4 ? , HCO 3 ? ) using a tributyl phosphate solvent extration technique. Our distribution data can be explained by the equilibria $$\begin{gathered} Eu^{3 + } + H_2 O + CO_2 (g)_ \leftarrow ^ \to EuCO_3^ + + 2H^ + \hfill \\ - log\beta _{12} = 9.607 + 496(t + 273.16)^{ - 1} \hfill \\ Eu^{3 + } + 2H_2 O + 2CO_2 (g)_ \leftarrow ^ \to Eu(CO_3 )_2^ - + 4H^ + \hfill \\ - log\beta _{24} = 21.951 + 670(t + 273.16)^{ - 1} \hfill \\ Eu^{3 + } + H_2 O + CO_2 (g)_ \leftarrow ^ \to EuHCO_3^{2 + } + H^ + \hfill \\ - log\beta _{11} = 1.688 + 1397(t + 273.16)^{ - 1} \hfill \\ \end{gathered}$$   相似文献   

3.
The equilibrium of distribution of Yb(III) and Lu(III) between chloroform and the aqueous phase in the presence of cupferron (the ammonium salt of N-nitrosophenylhydroxylamine) were studied as apH function of the aqueous phase and the concentration of N-nitrosophenylhydroxylamine (HL). The stability constants for theLnL n 3–n ) complexes (n=1÷3) being formed in the aqueous phase were established, as well as the equilibrium constants of the extraction reaction $$Ln(H_2 O)_m^{3 + } + 3HL_{(O)} \mathop \rightleftharpoons \limits^{K_{ex} } LnL_{3(O)} + 3H^ + + mH_2 O(Ln^{3 + } = Yb,Lu),$$ two-phase stability constants for theLnL 3 complexes,pH 0.5 and the separation factor Lu(III) from Yb(III).  相似文献   

4.
The complex formation between Cu(II) and 8-hydroxyquinolinat (Ox) was studied with the liquid-liquid distribution method, between 1M-Na(ClO4) and CHCl3 at 25°C. The experimental data were explained by the equilibria: $$\begin{gathered} \operatorname{Cu} ^{2 + } + Ox \rightleftharpoons \operatorname{Cu} Ox \log \beta _1 = 12.38 \pm 0.13 \hfill \\ \operatorname{Cu} ^{2 + } + 2 Ox \rightleftharpoons \operatorname{Cu} Ox_2 \log \beta _2 = 23.80 \pm 0.10 \hfill \\ \operatorname{Cu} Ox_{2aq} \rightleftharpoons \operatorname{Cu} Ox_{2\operatorname{org} } \log \lambda = 2.06 \pm 0.08 \hfill \\ \end{gathered} $$ The equilibria between Cu(II) and o-aminophenolate (AF) were studied potentiometrically with a glass electrode at 25°C and in 1M-Na(ClO4). The experimental data were explained by the equilibria: $$\begin{gathered} \operatorname{Cu} ^{2 + } + AF \rightleftharpoons \operatorname{Cu} AF \log \beta _1 = 8.08 \pm 0.08 \hfill \\ \operatorname{Cu} ^{2 + } + 2AF \rightleftharpoons \operatorname{Cu} AF_2 \log \beta _2 = 14.60 \pm 0.06 \hfill \\ \end{gathered} $$ The protonation constants ofAF and the distribution constants between CHCl3?H2O and (C2H5)2O?H2O were also determined.  相似文献   

5.
Prior to this study there were no thermodynamic data for isosaccharinate (ISA) complexes of Fe(III) in the environmental range of pH (>~4.5). This study was undertaken to obtain such data in order to predict Fe(III) behavior in the presence of ISA. The solubility of Fe(OH)3(2-line ferrihydrite), referred to as Fe(OH)3(s), was studied at 22?±?2?°C in: (1) very acidic (0.01?mol·dm?3 H+) to highly alkaline conditions (3?mol·dm?3 NaOH) as a function of time (11?C421?days), and fixed concentrations of 0.01 or 0.001?mol·dm?3 NaISA; and (2) as a function of NaISA concentrations ranging from approximately 0.0001 to 0.256?mol·dm?3 and at fixed pH values of approximately 4.5 and 11.6 to determine the ISA complexes of Fe(III). The data were interpreted using the SIT model that included previously reported stability constants for $ {{\text{Fe(ISA}})_{n}}^{3 - n} $ (with n varying from 1 to 4) and Fe(III)?COH complexes, and the solubility product for Fe(OH)3(s) along with the values for two additional complexes (Fe(OH)2(ISA)(aq) and $ {\text{Fe(OH)}}_{ 3} ( {{\text{ISA}})_{2}}^{2 - } $ ) determined in this study. These extensive data provided a log10 K 0 value of 1.55?±?0.38 for the reaction $ ({\text{Fe}}^{ 3+ } + {\text{ISA}}^{-} + 2 {\text{H}}_{ 2} {\text{O}} \rightleftarrows {\text{Fe(OH}})_{ 2} {\text{ISA(aq}}) + 2 {\text{H}}^{ + } ) $ and a value of ?3.27?±?0.32 for the reaction $ ({\text{Fe}}^{ 3+ } + 2 {\text{ISA}}^{-} + 3 {\text{H}}_{ 2} {\text{O}} \rightleftarrows {\text{Fe(OH)}}_{ 3} ( {\text{ISA}})_{2}^{2 - } + 3 {\text{H}}^{ + } ) $ and show that ISA forms strong complexes with Fe(III) which significantly increase the Fe(OH)3(s) solubility at pH?<~12. Thermodynamic calculations show that competition of Fe(III) with tetravalent ions for ISA does not significantly affect the solubilities of tetravalent hydrous oxides (e.g., Th and Np(IV)) in ISA solutions.  相似文献   

6.
The pK 2 * for the dissociation of sulfurous acid from I=0.5 to 6.0 molal at 25°C has been determined from emf measurements in NaCl solutions with added concentrations of NiCl2, CoCl2, McCl2 and CdCl2 (m=0.1). These experimental results have been treated using both the ion pairing and Pitzer's specific ion-interaction models. The Pitzer parameters for the interaction of M2+ with SO 3 2? yielded $$\begin{gathered} \beta _{NiSO_3 }^{(0)} = - 5.5, \beta _{NiSO_3 }^{(1)} = 5.8, and \beta _{NiSO_3 }^{(2)} = - 138 \hfill \\ \beta _{CoSO_3 }^{(0)} = - 12.3, \beta _{CoSO_3 }^{(1)} = 31.6, and \beta _{CoSO_3 }^{(2)} = - 562 \hfill \\ \beta _{MnSO_3 }^{(0)} = - 8.9, \beta _{MnSO_3 }^{(1)} = 18.7, and \beta _{MnSO_3 }^{(2)} = - 353 \hfill \\ \beta _{CdSO_3 }^{(0)} = - 7.2, \beta _{CdSO_3 }^{(1)} = 13.8, and \beta _{CdSO_3 }^{(2)} = - 489 \hfill \\ \end{gathered} $$ The calculated values of pK 2 * using Pitzer's equations reproduce the measured values to within ±0.01 pK units. The ion pairing model yielded $$\begin{gathered} logK_{NiSO_3 } = 2.88 and log\gamma _{NiSO_3 } = 0.111 \hfill \\ logK_{CoSO_3 } = 3.08 and log\gamma _{CoSO_3 } = 0.051 \hfill \\ logK_{MnSO_3 } = 3.00 and log\gamma _{MnSO_3 } = 0.041 \hfill \\ logK_{CdSO_3 } = 3.29 and log\gamma _{CdSO_3 } = 0.171 \hfill \\ \end{gathered} $$ for the formation of the complex MSO3. The stability constants for the formation of MSO3 complexes were found to correlate with the literature values for the formation of MSO4 complexes.  相似文献   

7.
The kinetics of oxidation of cis-[CrIII(gly)2(H2O)2]+ (gly = glycinate) by $ {\text{IO}}_{ 4}^{ - } $ has been studied in aqueous solutions. The reaction is first order in the chromium(III) complex concentration. The pseudo-first-order rate constant, k obs, showed a small change with increasing $ \left[ {{\text{IO}}_{ 4}^{ - } } \right] $ . The pseudo-first-order rate constant, k obs, increased with increasing pH, indicating that the hydroxo form of the chromium(III) complex is the reactive species. The reaction has been found to obey the following rate law: $ {\text{Rate}} = 2k^{\text{et}} K_{ 3} K_{ 4} \left[ {{\text{Cr}}\left( {\text{III}} \right)} \right]_{t} \left[ {{\text{IO}}_{ 4}^{ - } } \right]/\left\{ {\left[ {{\text{H}}^{ + } } \right] + K_{ 3} + K_{ 3} K_{ 4} \left[ {{\text{IO}}_{ 4}^{ - } } \right]} \right\} $ . Values of the intramolecular electron transfer constant, k et, the first deprotonation constant of cis-[CrIII(gly)2(H2O)2]+, K 3 and the equilibrium formation constant between cis-[CrIII(gly)2(H2O)(OH)] and $ {\text{IO}}_{ 4}^{ - } $ , K 4, have been determined. An inner-sphere mechanism has been proposed for the oxidation process. The thermodynamic activation parameters of the processes involved are reported.  相似文献   

8.
Complex formation between lead(II) and ethylenedithio diacetic acid (H2 L) has been studied at 25°C in aqueous 0.5M sodium perchlorate medium. Measurements have been carried out with a glass electrode and with a lead amalgam electrode. In acidic medium and in the investigated concentration range experimental data can be explained by assuming the following equilibria: $$\begin{gathered} Pb^{2 + } + L^{2 - } \rightleftharpoons PbL log\beta _{101} = 3.62 \pm 0.03 \hfill \\ Pb^{2 + } + H^ + + L^{2 - } \rightleftharpoons PbHL^ - log\beta _{111} = 6.30 \pm 0.07 \hfill \\ \end{gathered} $$   相似文献   

9.
Solvent extraction of microamounts of trivalent europium and americium into nitrobenzene by using a synergistic mixture of hydrogen dicarbollylcobaltate (H+B?) and magnesium ionophore III (L) was studied. The equilibrium data were explained assuming that the species HL+, \( \text{HL}_{2}^{ + } , \) \( {\text{ML}}_{2}^{3 + } , \) and \( {\text{ML}}_{3}^{3 + } \) (M3+ = Eu3+, Am3+; L = magnesium ionophore III) are extracted into the nitrobenzene phase. The values of extraction and stability constants of the cationic complex species in nitrobenzene saturated with water were determined and discussed.  相似文献   

10.
The solvent extraction of Yb(III) and Ho(III) by 1-(2-pyridylazo)-2-naphthol (PAN or HL) in carbon tetrachloride from aqueous-methanol phase has been studied as a function ofpH × and the concentration ofPAN or methanol (MeOH) in the organic phase. When the aqueous phase contains above ~25%v/v of methanol the synergistic effect was increased. The equation for the extraction reaction has been suggested as: $$\begin{gathered} Ln(H_2 0)_{m(p)}^{3 + } + 3 HL_{(o)} + t MeOH_{(o)} \mathop \rightleftharpoons \limits^{K_{ex} } \hfill \\ LnL_3 (MeOH)_{t(o)} + 3 H_{(p)}^ + + m H_2 0 \hfill \\ \end{gathered} $$ where:Ln 3+=Yb, Ho; $$\begin{gathered} t = 3 for C_{MeOH in.} \varepsilon \left( { \sim 25 - 50} \right)\% {\upsilon \mathord{\left/ {\vphantom {\upsilon \upsilon }} \right. \kern-\nulldelimiterspace} \upsilon }; \hfill \\ t = 0 for C_{MeOH in.} \varepsilon \left( { \sim 5 - 25} \right)\% {\upsilon \mathord{\left/ {\vphantom {\upsilon \upsilon }} \right. \kern-\nulldelimiterspace} \upsilon } \hfill \\ \end{gathered} $$ . The extraction equilibrium constants (K ex ) and the two-phase stability constants (β 3 × ) for theLnL 3(MeOH)3 complexes have been evaluated.  相似文献   

11.
Extraction of microamounts of europium and americium by a nitrobenzene solution of hydrogen dicarbollylcobaltate (H+B?) in the presence of bis(diphenylphosphino)methane dioxide (DPPMDO, L) has been investigated. The equilibrium data have been explained assuming that the species $ {\text{HL}}^{ + } $ , $ {\text{HL}}_{2}^{ + } $ , $ {\text{ML}}_{2}^{3 + } $ , $ {\text{ML}}_{3}^{3 + } $ and $ {\text{ML}}_{4}^{3 + } $ (M3+ = Eu3+, Am3+) are extracted into the organic phase. The values of extraction and stability constants of the species in nitrobenzene saturated with water have been determined. It was found that the stability constants of the corresponding complexes $ {\text{EuL}}_{n}^{3 + } $ and $ {\text{AmL}}_{n}^{3 + } $ , where n = 2, 3 and L is DPPMDO, in water–saturated nitrobenzene are comparable, whereas in this medium the stability of the cationic species $ {\text{AmL}}_{4}^{3 + } $ (L = DPPMDO) is somewhat higher than that of $ {\text{EuL}}_{4}^{3 + } $ with the same ligand L.  相似文献   

12.
The reaction of mucic acid (H6 Mu) with Cobalt(II) and Nickel(II) ions has been studied in 1.0M-Na+(NO 3 ? ) ionic medium at 25° C using a glass electrode. The e.m.f. data in the range 8≦?log [H+]≦10 are explained by assuming $$\begin{gathered} Me^{2 + } + H_4 Mu^{2 - } \rightleftharpoons MeH_3 Mu^ - + H^ + \beta ''_1 \hfill \\ Me^{2 + } + H_4 Mu^{2 - } \rightleftharpoons MeH_2 Mu^{2 - } + 2 H^ + \beta ''_2 \hfill \\ \end{gathered}$$ with equilibrium constants log β′1 = — 9.36; — 9.34; log β′2 = — 18.11; — 18.08 for Co(II) and Ni(II) resp.  相似文献   

13.
The equilibrium constants and thermodynamic parameters for complex formation of 18-crown-6(18C6) with Zn2+, Tl+, Hg2+ and $ {\text{UO}}^{{{\text{2 + }}}}_{{\text{2}}} $ cations have been determined by conductivity measurements in acetonitrile(AN)-dimethylformamide(DMF) binary solutions. 18-crown-6 forms 1:1 complexes [M:L] with Zn2+, Hg2+ and $ {\text{UO}}^{{{\text{2 + }}}}_{{\text{2}}} $ cations, but in the case of Tl+ cation, a 1:2 [M:L2] complex is formed in most binary solutions. The thermodynamic parameters ( $ \Delta {\text{H}}^{ \circ }_{{\text{c}}} $ and $ \Delta {\text{S}}^{ \circ }_{{\text{c}}} $ ) which were obtained from temperature dependence of the equilibrium constants show that in most cases, the complexes are enthalpy destabilized but entropy stabilized and a non-monotonic behaviour is observed for variations of standard enthalpy and entropy changes versus the composition of AN/DMF binary mixed solvents. The obtained results show that the order of selectivity of 18C6 ligand for these cations changes with the composition of the mixed solvent. A non-linear relationship was observed between the stability constants (logKf) of these complexes with the composition of AN/DMF binary solutions. The influence of the $ {\text{ClO}}^{ - }_{{\text{4}}} $ , $ {\text{NO}}^{ - }_{{\text{3}}} $ and $ {\text{Cl}}^{ - } $ anions on the stability constant of (18C6-Na+) complex in methanol (MeOH) solutions was also studied by potentiometry method. The results show that the stability of (18C6-Na+) complex in the presence of the anions increases in order: $ {\text{ClO}}^{ - }_{{\text{4}}} $  >  $ {\text{NO}}^{ - }_{{\text{3}}} $  >  $ {\text{Cl}}^{ - } $ .  相似文献   

14.
From extraction experiments and γ-activity measurements, the exchange extraction constants corresponding to the general equilibrium $ {\text{M}}^{ + } \left( {\text{aq}} \right) \, + {\mathbf{1}}\cdot{\text{Na}}^{ + } \left( {\text{nb}} \right) \Leftrightarrow {\mathbf{1}}\cdot{\text{M}}^{ + } \left( {\text{nb}} \right) \, + {\text{Na}}^{ + } \left( {\text{aq}} \right) $ taking place in the two-phase water–nitrobenzene system $ \begin{gathered} ({\text{M}}^{ + } = {\text{ Li}}^{ + } ,{\text{ K}}^{ + } ,{\text{ Rb}}^{ + } ,{\text{ Cs}}^{ + } ,{\text{ H}}_{ 3} {\text{O}}^{ + } ,{\text{NH}}_{4}^{ + }, {\text{ Ag}}^{ + } ,{\text{ Tl}}^{ + } ;{\mathbf{1}} \\ = {\text{ nonactin}};{\text{ aq }} = {\text{ aqueous phase}},{\text{ nb }} = {\text{nitrobenzene phase}}) \\ \end{gathered} $ were determined. Moreover, the stability constants of the M+ complexes in water-saturated nitrobenzene were calculated; they were found to increase in the series of $ {\text{Cs}}^{ + } < {\text{ Rb}}^{ + } < {\text{ H}}_{ 3} {\text{O}}^{ + } ,{\text{ Ag}}^{ + } < {\text{ Tl}}^{ + } < {\text{ Li}}^{ + } < {\text{ K}}^{ + } < {\text{NH}}_{4}^{ + } $ .  相似文献   

15.
Extraction of microamounts of europium and americium by a nitrobenzene solution of hydrogen dicarbollylcobaltate (H+B?) in the presence of 1,3-bis(diphenylphosphino)propane dioxide (DPPPrDO, L) has been investigated. The equilibrium data have been explained assuming that the species $ {\text{HL}}^{ + } ,\,{\text{HL}}_{2}^{ + } ,\,{\text{ML}}^{3 + } \,{\text{and}}\,{\text{ML}}_{3}^{3 + } $ HL + , HL 2 + , ML 3 + and ML 3 3 + (M3+ = Eu3+, Am3+) are extracted into the organic phase. The values of extraction and stability constants of the complex species in nitrobenzene saturated with water have been determined. It was found that the stability constants of the corresponding complexes $ {\text{EuL}}_{n}^{ 3+ } \,{\text{and}}\,{\text{AmL}}_{n}^{ 3+ } , $ EuL n 3 + and AmL n 3 + , where n = 1, 3 and L is DPPPrDO, in water-saturated nitrobenzene are comparable.  相似文献   

16.
The stability constants of 1:1 (M:L) complexes of benzo-15-crown-5 (B15C5) with Li+, Na+, K+ and NH4 + cations, the Gibbs standard free energies ( $ \Updelta {\text{G}}_{\text{c}}^{ \circ } $ ), the standard enthalpy changes ( $ \Updelta {\text{H}}_{\text{c}}^{ \circ } $ ) and standard entropy changes ( $ \Updelta {\text{S}}_{\text{c}}^{ \circ } $ ) for formation of these complexes in acetonitrile–methanol (AN–MeOH) binary mixtures have been determined conductometrically. The conductance data show that the stoichiometry of the complexes formed between the macrocyclic ligand and the studied cations is 1:1 (M:L). In most cases, addition of B15C5 to solutions of these cations, causes a continuous increase in the molar conductivities which indicates that the mobility of complexed cations is more than the uncomplexed ones. The stability constants of the complexes were obtained from fitting of molar conductivity curves using a computer program, GENPLOT. The results show that the selectivity order of B15C5 for the metal cations changes with the nature and composition of the binary mixed solvent. The values of standard enthalpy changes ( $ \Updelta {\text{H}}_{\text{c}}^{ \circ } $ ) for complexation reactions were obtained from the slope of the van’t Hoff plots and the changes in standard entropy ( $ \Updelta {\text{S}}_{\text{c}}^{ \circ } $ ) were calculated from the relationship $ \Updelta {\text{G}}_{{{\text{c}},298.15}}^{ \circ } = \Updelta {\text{H}}_{\text{c}}^{ \circ } - 298.15\Updelta {\text{S}}_{\text{c}}^{ \circ } $ . A non-linear behavior was observed between the stability constants (log Kf) of the complexes and the composition of the acetonitrile–methanol (AN–MeOH) binary solution. The results obtained in this study, show that in most cases, the complexes formed between B15C5 and Li+, Na+, K+ and NH4 + cations are both enthalpy and entropy stabilized and the values of these thermodynamic quantities change with the composition of the binary solution.  相似文献   

17.
Extraction of lutetium(III) and erbium(III) with 1-(2-pyridylazo)-2-naphthol (PAN or HL) in carbon tetrachloride from aqueous solutions was examined. The composition of the complex extracted was determined and it was found that the extraction process can be described by the following equation (Ln 3+=Lu, Er): $$Ln(H_2 O)_m^{3 + } + 3 HL_{(0)} \mathop \rightleftharpoons \limits^{K_{ex} } LnL_{3(0)} + 3 H^ + + mH_2 O$$ The extraction constants (K ex ) and two-phase stability constants (β 3 x ) forLnL 3 complexes have been evaluated.  相似文献   

18.
Binary and mixed-ligand complexes of Ni2+ and Co2+ involving L-norvaline (Nva) and ferulic acid (FA) have been investigated in aqueous solutions by pH potentiometry and UV?Cvisible spectrophotometric techniques, at 298.15 K and fixed ionic strength (0.15?mol?dm?3, NaNO3). The overall stability constants of the Ni2+ and Co2+ complexes with the ligands studied were obtained by the HYPERQUAD2008 program from the pH-potentiometric data. As a result of the numerical treatment, a model composed of seven species NiNva+, NiNva2, NiNvaH?1, $\mathrm{NiNva}_{ - 2}^{ -}$ , NiFA, $\mathrm{NiFAH}_{ - 1}^{ -}$ and NiNvaFA? was obtained for the Ni2++Nva+FA system, whereas for the Co2++Nva+FA system the complexes CoNva+, CoNva2, CoNvaH?1, $\mathrm{CoNvaH}_{ - 2}^{ -}$ , CoFA, $\mathrm{CoFAH}_{ - 1}^{ -}$ , and CoNvaFA? were obtained. The complex species distributions in certain pH ranges were calculated by the HySS2009 simulation program. Spectroscopic UV?Cvisible measurements were carried out to give qualitative information about the complexes formed in these solutions.  相似文献   

19.
Complex formation between Cd(II) and oxalate has been studied before the precipitation at 25°C and 1M-NaClO4, by means of glass- and cadmium amalgam electrodes. The e.m.f. data are explained with the following equilibrium: $$Cd^{2 + } + C_2 O_4^{2 - } \rightleftharpoons CdC_2 O_4 \log {\text{ }}\beta _1 = 2.75 \pm 0.05$$   相似文献   

20.
The solvent extraction of Er(III), Yb(III) and Lu(III) by 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 (HPMBP or HL) in carbon tetrachloride has been studied as a function of thepH of the aqueous phase and the concentration of the extractant in the organic phase. The equation for the extraction reaction has been suggested as: $$Ln^{3 + } + 3HL_{(0)} \rightleftharpoons LnL_{3(0)} + 3H^ + \left( {Ln^{3 + } = Er,Yb, Lu} \right)$$ The extraction equilibrium constants (K ex ) and two-phase stability constants (β 3 x ) for theLnL 3 complexes have been evaluated.  相似文献   

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