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1.
The stoichiometries, kinetics and mechanism of the reduction of tetraoxoiodate(VII) ion, IO4
− to the corresponding trioxoiodate(V) ion, IO3
− by n-(2-hydroxylethyl)ethylenediaminetriacetatocobaltate(II) ion, [CoHEDTAOH2]− have been studied in aqueous media at 28 °C, I = 0.50 mol dm−3 (NaClO4) and [H+] = 7.0 × 10−3 mol dm−3. The reaction is first order in [Oxidant] and [Reductant], and the rate is inversely dependent on H+ concentration in the range 5.00 × 10−3 ≤ H+≤ 20.00 × 10−3 mol dm−3 studied. A plot of acid rate constant versus [H+]−1 was linear with intercept. The rate law for the reaction is:
- \frac[ \textCoHEDTAOH2 - ]\textdt = ( a + b[ \textH + ] - 1 )[ \textCoHEDTAOH2 - ][ \textIO4 - ] - {\frac{{\left[ {{\text{CoHEDTAOH}}_{2}^{ - } } \right]}}{{{\text{d}}t}}} = \left( {a + b\left[ {{\text{H}}^{ + } } \right]^{ - 1} } \right)\left[ {{\text{CoHEDTAOH}}_{2}^{ - } } \right]\left[ {{\text{IO}}_{4}^{ - } } \right] 相似文献
2.
[
\textTp\textMe2 {\text{Tp}}^{{{\text{Me}}_{2} }} ]M (M = K, Tl) reacts with “GaI” to give a series of compounds that feature Ga–Ga bonds, namely [
\textTp\textMe2 {\text{Tp}}^{{{\text{Me}}_{2} }} ]Ga→GaI3, [
\textTp\textMe2 {\text{Tp}}^{{{\text{Me}}_{2} }} ]GaGaI2GaI2(
\textHpz\textMe2 {\text{Hpz}}^{{{\text{Me}}_{2} }} ) and [
\textTp\textMe2 {\text{Tp}}^{{{\text{Me}}_{2} }} ]Ga(GaI2)2Ga[
\textTp\textMe2 {\text{Tp}}^{{{\text{Me}}_{2} }} ], in addition to the cationic, mononuclear Ga(III) complex {[
\textTp\textMe2 {\text{Tp}}^{{{\text{Me}}_{2} }} ]2Ga}+. Likewise, [
\textTp\textMe2 {\text{Tp}}^{{{\text{Me}}_{2} }} ]M (M = K, Tl) reacts with (HGaCl2)
2
and Ga[GaCl4] to give [
\textTp\textMe2 {\text{Tp}}^{{{\text{Me}}_{2} }} ]Ga→GaCl3, {[
\textTp\textMe2 {\text{Tp}}^{{{\text{Me}}_{2} }} ]2Ga}[GaCl4], and {[
\textTp\textMe2 {\text{Tp}}^{{{\text{Me}}_{2} }} ]GaGa[
\textTp\textMe2 {\text{Tp}}^{{{\text{Me}}_{2} }} ]}[GaCl4]2. The adduct [
\textTp\textMe2 {\text{Tp}}^{{{\text{Me}}_{2} }} ]Ga→B(C6F5)3 may be obtained via treatment of [
\textTp\textMe2 {\text{Tp}}^{{{\text{Me}}_{2} }} ]K with “GaI” followed by addition of B(C6F5)3. Comparison of the deviation from planarity of the GaY3 ligands in [
\textTp\textMe2 {\text{Tp}}^{{{\text{Me}}_{2} }} ]Ga→GaY3 (Y = Cl, I) and [
\textTm\textBu\textt {\text{Tm}}^{{{\text{Bu}}^{\text{t}} }} ]Ga→GaY3, as evaluated by the sum of the Y–Ga–Y bond angles, Σ(Y–Ga–Y), indicates that the [
\textTm\textBu\textt {\text{Tm}}^{{{\text{Bu}}^{\text{t}} }} ]Ga moiety is a marginally better donor than [
\textTp\textMe2 {\text{Tp}}^{{{\text{Me}}_{2} }} ]Ga. In contrast, the displacement from planarity for the B(C6F5)3 ligand of [
\textTp\textMe2 {\text{Tp}}^{{{\text{Me}}_{2} }} ]Ga→B(C6F5)3 is greater than that of [
\textTm\textBu\textt {\text{Tm}}^{{{\text{Bu}}^{\text{t}} }} ]Ga→B(C6F5)3, an observation that is interpreted in terms of interligand steric interactions in the former complex compressing the C–B–C
bond angles. 相似文献
3.
Olga Impert Anna Katafias Przemysław Kita Grzegorz Wrzeszcz Joanna Fenska Gábor Lente István Fábián 《Transition Metal Chemistry》2011,36(7):761-766
The mer-[Ru(pic)3] isomer, where pic is 2-pyridinecarboxylic acid, undergoes base hydrolysis at pH > 12. The reaction was monitored spectrophotometrically
within the UV–Vis spectral range. The product of the reaction, the [Ru(pic)2(OH)2]− ion, is formed via a consecutive two-stage process. The chelate ring opening is proceeded by the nucleophilic attack of OH− ion at the carbon atom of the carboxylic group and the deprotonation of the attached hydroxo group. In the second stage,
the fast deprotonation of the coordinated OH− ligand leads to liberation of the monodentato bonded picolinate. The dependence of the observed pseudo-first-order rate constant
on [OH−] is given by
k\textobs1 = \frack + k1 [\textOH - ] + k + k2 K1 [\textOH - ]2 k - + k1 + ( k + + k2 K1 )[\textOH - ] + k + K1 [\textOH - ]2 k_{{{\text{obs}}1}} = \frac{{k_{ + } k_{1} [{\text{OH}}^{ - } ] + k_{ + } k_{2} K_{1} [{\text{OH}}^{ - } ]^{2} }}{{k_{ - } + k_{1} + \left( {k_{ + } + k_{2} K_{1} } \right)[{\text{OH}}^{ - } ] + k{}_{ + }K_{1} [{\text{OH}}^{ - } ]^{2} }} and
( k\textobs2 = \frackca + kcb K2 [\textOH - ]1 + K2 [\textOH - ] ) \left( {k_{{{\text{obs}}2}} = \frac{{k_{ca} + k_{cb} K_{2} [{\text{OH}}^{ - } ]}}{{1 + K_{2} [{\text{OH}}^{ - } ]}}} \right) for the first and the second stage, respectively, where k
1, k
2, k
-, k
ca
, k
cb
are the first-order rate constants and k
+ is the second-order one, K
1 and K
2 are the protolytic equilibria constants. 相似文献
4.
Ponnusamy Sami Kandasamy Venkateshwari Natarajan Mariselvi Arunachalam Sarathi Kasi Rajasekaran 《Transition Metal Chemistry》2010,35(2):137-142
l-cysteine undergoes facile electron transfer with heteropoly 10-tungstodivanadophosphate,
[ \textPV\textV \textV\textV \textW 1 0 \textO 4 0 ]5 - , \left[ {{\text{PV}}^{\text{V}} {\text{V}}^{\text{V}} {\text{W}}_{ 1 0} {\text{O}}_{ 4 0} } \right]^{5 - } , at ambient temperature in aqueous acid medium. The stoichiometric ratio of [cysteine]/[oxidant] is 2.0. The products of the
reaction are cystine and two electron-reduced heteropoly blue, [PVIVVIVW10O40]7−. The rates of the electron transfer reaction were measured spectrophotometrically in acetate–acetic acid buffers at 25 °C.
The orders of the reaction with respect to both [cysteine] and [oxidant] are unity, and the reaction exhibits simple second-order
kinetics at constant pH. The pH-rate profile indicates the participation of deprotonated cysteine in the reaction. The reaction
proceeds through an outer-sphere mechanism. For the dianion −SCH2CH(NH3
+)COO−, the rate constant for the cross electron transfer reaction is 96 M−1s−1 at 25 °C. The self-exchange rate constant for the
- \textSCH2 \textCH( \textNH3 + )\textCOO - \mathord | / |
\vphantom - \textSCH2 \textCH( \textNH3 + )\textCOO - ·\textSCH2 \textCH( \textNH3 + )\textCOO - ·\textSCH2 \textCH( \textNH3 + )\textCOO - {{{}^{ - }{\text{SCH}}_{2} {\text{CH}}\left( {{{\text{NH}}_{3}}^{ + } } \right){\text{COO}}^{ - } } \mathord{\left/ {\vphantom {{{}^{ - }{\text{SCH}}_{2} {\text{CH}}\left( {{{\text{NH}}_{3}}^{ + } } \right){\text{COO}}^{ - } } {{}^{ \bullet }{\text{SCH}}_{2} {\text{CH}}\left( {{{\text{NH}}_{3}}^{ + } } \right){\text{COO}}^{ - } }}} \right. \kern-\nulldelimiterspace} {{}^{ \bullet }{\text{SCH}}_{2} {\text{CH}}\left( {{{\text{NH}}_{3}}^{ + } } \right){\text{COO}}^{ - } }} couple was evaluated using the Rehm–Weller relationship. 相似文献
5.
Oxidation of 3-(4-methoxyphenoxy)-1,2-propanediol (MPPD) by bis(hydrogenperiodato) argentate(III) complex anion, [Ag(HIO6)2]5− has been studied in aqueous alkaline medium by use of conventional spectrophotometry. The major oxidation product of MPPD
has been identified as 3-(4-methoxyphenoxy)-2-ketone-1-propanol by mass spectrometry. The reaction shows overall second-order
kinetics, being first-order in both [Ag(III)] and [MPPD]. The effects of [OH−] and periodate concentration on the observed second-order rate constants k′ have been analyzed, and accordingly an empirical expression has been deduced:
6.
Balesh A. Deganatti Nagaraj P. Shetti Sharanappa T. Nandibewoor 《Transition Metal Chemistry》2009,34(2):143-152
The oxidation of l-valine (l-val) by diperiodatocuprate(III) (DPC) in aqueous alkaline medium at a constant ionic strength of 3.0 × 10−3 mol dm−3 was studied spectrophotometrically at 298 K and follows the rate law;
7.
E. Makrlík P. Vaňura P. Selucky 《Journal of Radioanalytical and Nuclear Chemistry》2009,281(3):547-551
Extraction of microamounts of cesium by a nitrobenzene solution of ammonium dicarbollylcobaltate
( \textNH 4 + \textB - ) ( {{\text{NH}}_{ 4}^{ + } {\text{B}}^{ - } }) and thallium dicarbollylcobaltate
( \textTl + \textB - ) ( {{\text{Tl}}^{ + } {\text{B}}^{ - } }) in the presence of 2,3-naphtho-15-crown-5 (N15C5, L) has been investigated. The equilibrium data have been explained assuming
that the complexes
\textML + {\text{ML}}^{ + } and
\textML 2 + {\text{ML}}_{ 2}^{ + }
( \textM + = \textNH4 + ,\textTl + ,\textCs + ) ( {{\text{M}}^{ + } = {\text{NH}}_{4}^{ + } ,{\text{Tl}}^{ + } ,{\text{Cs}}^{ + } } ) are present in the organic phase. The stability constants of the
\textML + {\text{ML}}^{ + } and
\textML2 + {\text{ML}}_{2}^{ + } species
( \textM + = \textNH4 + ,\textTl + ) ( {{\text{M}}^{ + } = {\text{NH}}_{4}^{ + } ,{\text{Tl}}^{ + } }) in nitrobenzene saturated with water have been determined. It was found that the stability of the complex cations
\textML + {\text{ML}}^{ + } and
\textML2 + {\text{ML}}_{2}^{ + }
(\textM + = \textNH4 + ,\textTl + ,\textCs + ; \textL = \textN15\textC5) ({{\text{M}}^{ + } = {\text{NH}}_{4}^{ + } ,{\text{Tl}}^{ + } ,{\text{Cs}}^{ + } ;\;{\text{L}} = {\text{N}}15{\text{C}}5}) in the mentioned medium increases in the
\textCs + < \textNH4 + < \textTl + {\text{Cs}}^{ + }\,<\, {\text{NH}}_{4}^{ + }\,<\,{\text{Tl}}^{ + } order. 相似文献
8.
The standard molar Gibbs free energy of formation of YRhO3(s) has been determined using a solid-state electrochemical cell wherein calcia-stabilized zirconia was used as an electrolyte.
The cell can be represented by:
( - )\textPt - Rh/{ \textY2\textO\text3( \texts ) + \textYRh\textO3( \texts ) + \textRh( \texts ) }//\textCSZ//\textO2( p( \textO2 ) = 21.21 \textkPa )/\textPt - Rh( + ) \left( - \right){\text{Pt - Rh/}}\left\{ {{{\text{Y}}_2}{{\text{O}}_{\text{3}}}\left( {\text{s}} \right) + {\text{YRh}}{{\text{O}}_3}\left( {\text{s}} \right) + {\text{Rh}}\left( {\text{s}} \right)} \right\}//{\text{CSZ//}}{{\text{O}}_2}\left( {p\left( {{{\text{O}}_2}} \right) = 21.21\;{\text{kPa}}} \right)/{\text{Pt - Rh}}\left( + \right) . The electromotive force was measured in the temperature range from 920.0 to 1,197.3 K. The standard molar Gibbs energy of
the formation of YRhO3(s) from elements in their standard state using this electrochemical cell has been calculated and can be represented by:
D\textfG\texto{ \textYRh\textO3( \texts ) }/\textkJ \textmo\textl - 1( ±1.61 ) = - 1,147.4 + 0.2815 T ( \textK ) {\Delta_{\text{f}}}{G^{\text{o}}}\left\{ {{\text{YRh}}{{\text{O}}_3}\left( {\text{s}} \right)} \right\}/{\text{kJ}}\;{\text{mo}}{{\text{l}}^{ - 1}}\left( {\pm 1.61} \right) = - 1,147.4 + 0.2815\;T\;\left( {\text{K}} \right) . Standard molar heat capacity Cop,m C^{o}_{{p,m}} (T) of YRhO3(s) was measured using a heat flux-type differential scanning calorimeter in two different temperature ranges from 127 to
299 K and 305 to 646 K. The heat capacity in the higher temperature range was fitted into a polynomial expression and can
be represented by: $ {*{20}{c}} {\mathop C\nolimits_{p,m}^{\text{o}} \left( {{\text{YRh}}{{\text{O}}_3},{\text{s,}}T} \right)\left( {{\text{J}}\;{{\text{K}}^{ - 1}}{\text{mo}}{{\text{l}}^{ - 1}}} \right)} & { = 109.838 + 23.318 \times {{10}^{ - 3}}T\left( {\text{K}} \right)} & { - 12.5964 \times {{10}^5}/{T^2}\left( {\text{K}} \right).} \\ {} & {\left( {305 \leqslant T\left( {\text{K}} \right) \leqslant 646} \right)} & {} \\ $ \begin{array}{*{20}{c}} {\mathop C\nolimits_{p,m}^{\text{o}} \left( {{\text{YRh}}{{\text{O}}_3},{\text{s,}}T} \right)\left( {{\text{J}}\;{{\text{K}}^{ - 1}}{\text{mo}}{{\text{l}}^{ - 1}}} \right)} & { = 109.838 + 23.318 \times {{10}^{ - 3}}T\left( {\text{K}} \right)} & { - 12.5964 \times {{10}^5}/{T^2}\left( {\text{K}} \right).} \\ {} & {\left( {305 \leqslant T\left( {\text{K}} \right) \leqslant 646} \right)} & {} \\ \end{array} The heat capacity of YRhO3(s) was used along with the data obtained from the electrochemical cell to calculate the standard enthalpy and entropy of
formation of the compound at 298.15 K. 相似文献
9.
Theoretical study of several para-substituted O-nitrosyl carboxylate compounds has been performed using density functional B3LYP method with 6-31G(d,p) basis set. Geometries obtained from DFT calculation were used to perform natural bond orbital analysis. It is noted that weakness in the O3–N2 sigma bond is due to $ n_{{{\text{O}}_{1} }} \to \sigma_{{{\text{O}}_{3} - {\text{N}}_{2} }}^{*}
10.
Ricardo Picciochi Hermínio P. Diogo Manuel E. Minas da Piedade 《Journal of Thermal Analysis and Calorimetry》2010,100(2):391-401
Combustion calorimetry, Calvet-drop sublimation calorimetry, and the Knudsen effusion method were used to determine the standard
(p
o = 0.1 MPa) molar enthalpies of formation of monoclinic (form I) and gaseous paracetamol, at T = 298.15 K:
\Updelta\textf H\textm\texto ( \textC 8 \textH 9 \textO 2 \textN,\text cr I ) = - ( 4 10.4 ±1. 3)\text kJ \textmol - 1 \Updelta_{\text{f}} H_{\text{m}}^{\text{o}} \left( {{\text{C}}_{ 8} {\text{H}}_{ 9} {\text{O}}_{ 2} {\text{N}},{\text{ cr I}}} \right) = - ( 4 10.4 \pm 1. 3){\text{ kJ}}\;{\text{mol}}^{ - 1} and
\Updelta\textf H\textm\texto ( \textC 8 \textH 9 \textO 2 \textN,\text g ) = - ( 2 80.5 ±1. 9)\text kJ \textmol - 1 . \Updelta_{\text{f}} H_{\text{m}}^{\text{o}} \left( {{\text{C}}_{ 8} {\text{H}}_{ 9} {\text{O}}_{ 2} {\text{N}},{\text{ g}}} \right) = - ( 2 80.5 \pm 1. 9){\text{ kJ}}\;{\text{mol}}^{ - 1} . From the obtained
\Updelta\textf H\textm\texto ( \textC 8 \textH 9 \textO 2 \textN,\text cr I ) \Updelta_{\text{f}} H_{\text{m}}^{\text{o}} \left( {{\text{C}}_{ 8} {\text{H}}_{ 9} {\text{O}}_{ 2} {\text{N}},{\text{ cr I}}} \right) value and published data, it was also possible to derive the standard molar enthalpies of formation of the two other known
polymorphs of paracetamol (forms II and III), at 298.15 K:
\Updelta\textf H\textm\texto ( \textC 8 \textH 9 \textO 2 \textN,\text crII ) = - ( 40 8.4 ±1. 3)\text kJ \textmol - 1 \Updelta_{\text{f}} H_{\text{m}}^{\text{o}} \left( {{\text{C}}_{ 8} {\text{H}}_{ 9} {\text{O}}_{ 2} {\text{N}},{\text{ crII}}} \right) = - ( 40 8.4 \pm 1. 3){\text{ kJ}}\;{\text{mol}}^{ - 1} and
\Updelta\textf H\textm\texto ( \textC 8 \textH 9 \textO 2 \textN,\text crIII ) = - ( 40 7.4 ±1. 3)\text kJ \textmol - 1 . \Updelta_{\text{f}} H_{\text{m}}^{\text{o}} \left( {{\text{C}}_{ 8} {\text{H}}_{ 9} {\text{O}}_{ 2} {\text{N}},{\text{ crIII}}} \right) = - ( 40 7.4 \pm 1. 3){\text{ kJ}}\;{\text{mol}}^{ - 1} . The proposed
\Updelta\textf H\textm\texto ( \textC 8 \textH 9 \textO 2 \textN,\text g ) \Updelta_{\text{f}} H_{\text{m}}^{\text{o}} \left( {{\text{C}}_{ 8} {\text{H}}_{ 9} {\text{O}}_{ 2} {\text{N}},{\text{ g}}} \right) value, together with the experimental enthalpies of formation of acetophenone and 4′-hydroxyacetophenone, taken from the
literature, and a re-evaluated enthalpy of formation of acetanilide,
\Updelta\textf H\textm\texto ( \textC 8 \textH 9 \textON,\text g ) = - ( 10 9. 2 ± 2. 2)\text kJ \textmol - 1 , \Updelta_{\text{f}} H_{\text{m}}^{\text{o}} \left( {{\text{C}}_{ 8} {\text{H}}_{ 9} {\text{ON}},{\text{ g}}} \right) = - ( 10 9. 2\,\pm\,2. 2){\text{ kJ}}\;{\text{mol}}^{ - 1} , were used to assess the predictions of the B3LYP/cc-pVTZ and CBS-QB3 methods for the enthalpy of a isodesmic and isogyric
reaction involving those species. This test supported the reliability of the theoretical methods, and indicated a good thermodynamic
consistency between the
\Updelta\textf H\textm\texto \Updelta_{\text{f}} H_{\text{m}}^{\text{o}} (C8H9O2N, g) value obtained in this study and the remaining experimental data used in the
\Updelta\textr H\textm\texto \Updelta_{\text{r}} H_{\text{m}}^{\text{o}} calculation. It also led to the conclusion that the presently recommended enthalpy of formation of gaseous acetanilide in
Cox and Pilcher and Pedley’s compilations should be corrected by ~20 kJ mol−1. 相似文献
11.
The stoichiometries of limiting carbonate complexes of lanthanide(III) ions were investigated by solubility measurements of
hydrated NaLn(CO3)2 solid compounds (Ln = La, Nd, Eu and Dy) at room temperature in aqueous solutions of high ionic strength (3.5 mol⋅kg−1 NaClO4) and high CO32-\mathrm{CO_{3}^{2-}} concentrations (0.1 to 1.5 mol⋅kg−1). The results were interpreted by considering the stability of carbonate complexes, with limiting species found to be La(CO3)45-\mathrm{La(CO_{3})_{4}^{5-}}, Nd(CO3)45-\mathrm{Nd(CO_{3})_{4}^{5-}}, Eu(CO3)33-\mathrm{Eu(CO_{3})_{3}^{3-}} and Dy(CO3)33-\mathrm{Dy(CO_{3})_{3}^{3-}}. TRLFS measurements on the Eu and Dy solutions confirmed the predominance of a single aqueous complex in all the samples.
Equilibrium constants were determined for the reaction Ln(CO3)33-+CO32-\mathrm{Ln(CO_{3})_{3}^{3-}}+\mathrm{CO_{3}^{2-}} ⇌ Ln(CO3)45-\mathrm{Ln(CO_{3})_{4}^{5-}}: log10K3.5m NaClO44,La=0.7±0.3\log_{10}K\mathrm{^{3.5m\:NaClO_{4}}_{4,La}=0.7\pm0.3}, log10K3.5m NaClO44,Nd=1.3±0.3\log_{10}K\mathrm{^{3.5m\:NaClO_{4}}_{4,Nd}=1.3\pm0.3}, and for Ln = Eu and Dy, log10K3.5m NaClO44,Ln £ -0.4\log_{10}K\mathrm{^{3.5m\:NaClO_{4}}_{4,Ln}\leq-0.4}. These results suggest that tetracarbonato complexes are stable only for the light lanthanide ions in up to 1.5 molal CO32-\mathrm{CO_{3}^{2-}} aqueous solutions, in agreement with our recent capillary electrophoresis study. Comparison with literature results indicates
that analogies between actinide(III) and lanthanide(III) ions of similar ionic radii do not hold in concentrated carbonate
solutions. Am(CO3)33-\mathrm{Am(CO_{3})_{3}^{3-}} was previously evidenced by solubility measurements, whereas we have observed that Nd(CO3)45-\mathrm{Nd(CO_{3})_{4}^{5-}} predominates in similar conditions. We may speculate that small chemical differences between Ln(III) and An(III) could result
in macroscopic differences when their coordination sphere is complete. 相似文献
12.
E. Makrlík P. Vaňura P. Selucký 《Journal of Radioanalytical and Nuclear Chemistry》2011,287(1):217-222
Extraction of microamounts of calcium and strontium by a nitrobenzene solution of hydrogen dicarbollylcobaltate (H+B−) in the presence of tetraisopropyl methylene diphosphonate [T(iPr)MDP, L] has been investigated. The equilibrium data have
been explained assuming that the species HL+,
\textHL2 + {\text{HL}}_{2}^{ + } ,
\textML22 + {\text{ML}}_{2}^{2 + } and
\textML32 + {\text{ML}}_{3}^{2 + } (M2+ = Ca2+, Sr2+) are extracted into the organic phase. The values of extraction and stability constants of the cationic complexes in nitrobenzene
saturated with water have been determined. In the considered nitrobenzene medium, it was found that the stability constants
of the
\textCaLn2 + {\text{CaL}}_{n}^{2 + } complexes, where n = 2, 3 and L is T(iPr)MDP, are somewhat higher than those of the corresponding complex species
\textSrLn2 + {\text{SrL}}_{n}^{2 + } . 相似文献
13.
E. Makrlík P. Vaňura P. Selucky V. A. Babain I. V. Smirnov 《Journal of Radioanalytical and Nuclear Chemistry》2010,283(3):839-844
Extraction of microamounts of europium and americium by a phenyltrifluoromethyl sulfone (FS 13) solution of hydrogen dicarbollylcobaltate
(H+B−) in the presence of N,N,N′,N′-tetraethyl-2,6-dipicolinamide (TEtDPA, L) has been investigated. The equilibrium data have been explained assuming that the
species HL+,
\textHL 2 + , {\text{HL}}_{ 2}^{ + } ,
\textML23 + {\text{ML}_{2}^{3 +}} and
\textML 3 3+ {\text{ML}_{ 3}^{ 3+}} (M3+ = Eu3+, Am3+) are extracted into the organic phase. The values of extraction and stability constants of the cationic complex species in
FS 13 saturated with water have been determined. It was found that the stability constants of the corresponding complexes
\textEuLn 3+ {\text{EuL}}_{n}^{ 3+ } and
\textAmLn 3+ {\text{AmL}}_{n}^{ 3+ }, where n = 2, 3 and L is TEtDPA, in the mentioned FS 13 medium are comparable. 相似文献
14.
E. Makrlík P. Vaňura P. Selucký I. V. Smirnov V. A. Babain 《Journal of Radioanalytical and Nuclear Chemistry》2011,287(1):335-340
Extraction of microamounts of calcium and strontium by a nitrobenzene solution of hydrogen dicarbollylcobaltate (H+B−) in the presence of diphenyl-N,N-dibutylcarbamoylmethyl phosphine oxide (DPDBCMPO, L) has been investigated. The equilibrium data have been explained assuming
that the species HL+,
\textHL2 + {\text{HL}}_{2}^{ + } , CaL2+,
\textCaL 2 2 + {\text{CaL}}_{ 2}^{{ 2 { + }}} ,
\textCaL 3 2 + {\text{CaL}}_{ 3}^{{ 2 { + }}} , SrL2+,
\textSrL 2 2 + {\text{SrL}}_{ 2}^{{ 2 { + }}} ,
\textSrL 3 2 + {\text{SrL}}_{ 3}^{{ 2 { + }}} and
\textSrL 4 2 + {\text{SrL}}_{ 4}^{{ 2 { + }}} are extracted into the organic phase. The values of extraction and stability constants of the cationic complexes in nitrobenzene
saturated with water have been determined. In the considered nitrobenzene medium, it was found that the stability constants
of the complexes CaL2+,
\textCaL 2 2 + {\text{CaL}}_{ 2}^{{ 2 { + }}} and
\textCaL 3 2 + {\text{CaL}}_{ 3}^{{ 2 { + }}} , where L is DPDBCMPO, are somewhat higher than those of the corresponding complex species SrL2+,
\textSrL 2 2 + {\text{SrL}}_{ 2}^{{ 2 { + }}} and
\textSrL 3 2 + {\text{SrL}}_{ 3}^{{ 2 { + }}} . 相似文献
15.
Extraction of microamounts of strontium and barium by a nitrobenzene solution of hydrogen dicarbollylcobaltate (H+B−) in the presence of polyethylene glycol PEG 1000 (L) has been investigated. The equilibrium data have been explained assuming
that the complexes
\textH 2 \textL2 + {\text{H}}_{ 2} {\text{L}}^{2 + } ,
\textML 2+ {\text{ML}}^{ 2+ } and
\textMHL 3+ {\text{MHL}}^{ 3+ }
( \textM 2+ = \textSr 2+ , \textBa 2+ ) \left( {{\text{M}}^{ 2+ } = {\text{Sr}}^{ 2+ } ,\,\,{\text{Ba}}^{ 2+ } } \right) 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 in water-saturated nitrobenzene the stability constant of the
\textBaL 2+ {\text{BaL}}^{ 2+ } cationic complex species is somewhat higher than that of the complex
\textSrL 2+ {\text{SrL}}^{ 2+ } . 相似文献
16.
The oxidation of aquaethylenediaminetetraacetatocobaltate(II) [Co(EDTA)(H2O)]−2 by N-bromosuccinimide (NBS) in aqueous solution has been studied spectrophotometrically over the pH 6.10–7.02 range at 25 °C.
The reaction is first-order with respect to complex and the oxidant, and it obeys the following rate law:
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