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1.
Francesco Crea 《Talanta》2007,71(2):948-963
In this paper we investigated the interactions between dioxouranium(VI) and oxalate using (H+-glass electrode) potentiometry and titration calorimetry. Potentiometric measurements were carried out in NaCl aqueous solutions and at T = 25 °C in a wide range of experimental conditions (concentrations, ligand/metal molar ratio, pH, titrants) at low ionic strength values (I ≤ 0.090 mol L−1, without supporting electrolyte) and at I = 1.0 mol L−1; different procedures were employed for the acquisition of experimental data and careful analysis of these data performed. In all cases the speciation model that best fits experimental data takes into account the formation of the binary mononuclear species UO2(ox)0, UO2(ox)22−, UO2(ox)34− widely reported in literature, the ternary hydroxyl mononuclear species UO2(ox)OH, UO2(ox)(OH)22−, UO2(ox)2OH3−, UO2(ox)3OH5−, the protonated ternary mononuclear species UO2(ox)3H3− and the binuclear species (UO2)2(ox)56−.Calorimetric measurements were carried out following similar procedures and in the same experimental conditions as employed for the potentiometric measurements at I = 1.0 mol L−1 in NaCl. The stability of UO22+-oxalate2− complexes is fairly high and their main contribution to stability is entropic in nature. Some linear empirical relationships were found which make it possible to calculate (i) the contribution of a single bond: and ; (ii) chelate stabilisation per ring: and and (iii) the mean stability of negatively charged Na+-ion pair complexes: logTK = (0.46 ± 0.02)·|z| (z = charge of complex species), ΔG° = −(2.60 ± 0.1)·|z| kJ mol−1 and TΔS° = 2.5 ± 0.5 kJ mol−1. Both potentiometric and calorimetric results provide evidence of the penta-coordination of the species UO2(ox)34−. SIT parameters were calculated from the data at I = 0 and I = 1.02 mol kg−1. Comparisons are made with literature data. An insoluble dioxouranium(VI) ternary complex was synthesised (at I = 1.0 mol L−1 in NaCl) and characterised by thermoanalysis and elemental analysis.  相似文献   

2.
Clemente Bretti 《Talanta》2007,72(3):1059-1065
Protonation constants of succinic, 1,2,3-propanetricarboxylic and 1,2,3,4-butanetetracarboxylic anions were determined in NaClaq + KClaq mixtures, at three ionic strengths, I = 1.2, 3 and 4.5 mol L−1. Experimental evidences showed that the function log KH = f(y) (y = [Na+]/([Na+] + [K+])) is not linear, indicating mixing effects on the protonation constants. The Guggenheim zeroth approximation holds that the above function can be written as:
  相似文献   

3.
H2O + Ni(NO3)2 binary system were investigated in the temperature range from −25 °C to 55 °C. The solid-liquid equilibria of the ternary system H2O + Fe(NO3)3 + Ni(NO3)2 were studied using a synthetic method based on conductivity measurements. Tow isotherms were established at 0 °C and 30 °C, and the appearing stable solid phases are iron nitrate nonahydrate (Fe(NO3)3·9H2O), iron nitrate hexahydrate (Fe(NO3)3·6H2O), nickel nitrate hexahydrate (Ni(NO3)2·6H2O) and nickel nitrate tetrahydrate (Ni(NO3)2·4H2O).  相似文献   

4.
The activity coefficients of sodium chloride in the NaCl + NaBF4 + H2O ternary system were experimentally determined at 298.15 K, at ionic strengths of 0.3. 0.5, 1, 2 and 3 mol kg−1 from emf from the bi-ISE cell without liquid junction:
ISE-Na|NaCl(mA), NaBF4(mB)|ISE-Cl
  相似文献   

5.
The enthalpies of solution of NaRb[B4O5(OH)4]·4H2O in approximately 1 mol dm−3 aqueous hydrochloric acid and of RbCl in aqueous (hydrochloric acid + boric acid + sodium chloride) were determined. From these results and the enthalpy of solution of H3BO3 in approximately 1 mol dm−3 HCl(aq) and of sodium chloride in aqueous (hydrochloric acid + boric acid), the standard molar enthalpy of formation of −(5128.02 ± 1.94) kJ mol−1 for NaRb[B4O5(OH)4]·4H2O was obtained from the standard molar enthalpies of formation of NaCl(s), RbCl(s), H3BO3(s) and H2O(l). The standard molar entropy of formation of NaRb[B4O5(OH)4]·4H2O was calculated from the Gibbs free energy of formation of NaRb[B4O5(OH)4]·4H2O computed from a group contribution method.  相似文献   

6.
A pure calcium borate Ca2[B2O4(OH)2]·0.5H2O has been synthesized under hydrothermal condition and characterized by XRD, FT-IR and TG as well as by chemical analysis. The molar enthalpy of solution of Ca2[B2O4(OH)2]·0.5H2O in HC1·54.582H2O was determined. From a combination of this result with measured enthalpies of solution of H3BO3 in HC1·54.561H2O and of CaO in (HCl + H3BO3) solution, together with the standard molar enthalpies of formation of CaO(s), H3BO3(s) and H2O(l), the standard molar enthalpy of formation of −(3172.5 ± 2.5) kJ mol−1 of Ca2[B2O4(OH)2]·0.5H2O was obtained.  相似文献   

7.
By dynamic calorimetry the temperature dependence of heat capacity for two-dimensional (2D) polymerized tetragonal phase of C60 has been determined over the 300-650 K range at standard pressure mainly with an uncertainty ±1.5%. In the range 490-550 K, an irreversible endothermic transition of the phase, caused by the depolymerization of the polymer, has been found and characterized. Based on the experimental data obtained and literature information, the thermodynamic functions of 2D polymerized tetragonal phase of C60, namely, the heat capacity C°p(T), enthalpy H°(T)−H°(0), entropy S°(T), and Gibbs function G°(T)−H°(0), have been calculated over the range from T→0 to 490 K. From 150 to 330 K in an adiabatic vacuum calorimeter and between 330 and 650 K in a dynamic calorimeter the thermodynamic properties of the depolymerization products have been examined and compared with the corresponding data for the monomeric phase C60.  相似文献   

8.
A comprehensive thermodynamic model based on the electrolyte NRTL (eNRTL) activity coefficient equation is developed for the NaCl + H2O binary, the Na2SO4 + H2O binary and the NaCl + Na2SO4 + H2O ternary. The NRTL binary parameters for pairs H2O-(Na+, Cl) and H2O-(Na+, SO42−), and the aqueous phase infinite dilution heat capacity parameters for ions Cl and SO42− are regressed from fitting experimental data on mean ionic activity coefficient, heat capacity, liquid enthalpy and dissolution enthalpy for the NaCl + H2O binary and the Na2SO4 + H2O binary with electrolyte concentrations up to saturation and temperature up to 473.15 K. The Gibbs energy of formation, enthalpy of formation and heat capacity parameters for solids NaCl(s), NaCl·2H2O(s), Na2SO4(s) and Na2SO4·10H2O(s) are obtained by fitting experimental data on solubilities of NaCl and Na2SO4 in water. The NRTL binary parameters for the (Na+, Cl)-(Na+, SO42−) pair are regressed from fitting experimental data on dissolution enthalpies and solubilities for the NaCl + Na2SO4 + H2O ternary.  相似文献   

9.
In this research, thermodynamic properties of the ternary electrolyte system (MgCl2 + Mg(NO3)2 + H2O) were investigated using a potentiometric method. The galvanic cell used had no liquid junction of type: Mg-ISE|MgCl2 (mA), Mg(NO3)2 (mB), H2O|Ag/AgCl. The measurements were performed at T = 298.15 K and at total ionic strengths from 0.001 to 8.000 mol/kg for different series of salt ratios r=mMgCl2/mMg2(NO3) =1.00, 2.50, 5.00, 7.50, 10.00 and 15.00. The PVC based magnesium ion-selective electrode (Mg-ISE) and the Ag/AgCl electrode used in this work were prepared in our laboratory and showed a reasonably good Nernst response. The Pitzer ion interaction model and Harned rule were used to illustrate the ternary electrolyte system investigated. The experimental results showed that both Pitzer model and Harned rule were suitable to be used satisfactorily to describe this ternary system.  相似文献   

10.
The two new compounds, Sr4Cu3(AsO4)2(AsO3OH)4·3H2O (1) and Ba2Cu4(AsO4)2(AsO3OH)3(2), were synthesized under hydrothermal conditions. They represent previously unknown structure types and are the first compounds synthesized in the systems SrO/BaO-CuO-As2O5-H2O. Their crystal structures were determined by single-crystal X-ray diffraction [space group C2/c, a=18.536(4) Å, b=5.179(1) Å, c=24.898(5) Å, β=93.67(3)°, V=2344.0(8) Å3, Z=4 for 1; space group P42/n, a=7.775(1) Å, c=13.698(3) Å, V=828.1(2) Å3, Z=2 for 2]. The crystal structure of 1 is related to a group of compounds formed by Cu2+-(XO4)3− layers (X=P5+, As5+) linked by M cations (M=alkali, alkaline earth, Pb2+, or Ag+) and partly by hydrogen bonds. In 1, worth mentioning is the very short hydrogen bond length, D···A=2.477(3) Å. It is one of the examples of extremely short hydrogen bonds, where the donor and acceptor are crystallographically different. Compound 2 represents a layered structure consisting of Cu2O8 centrosymmetric dimers crosslinked by As1φ4 tetrahedra, where φ is O or OH, which are interconnected by Ba, As2 and hydrogen bonds to form a three-dimensional network. The layers are formed by Cu2O8 centrosymmetric dimers of CuO5 edge-sharing polyhedra, crosslinked by As1O4 tetrahedra. Vibrational spectra (FTIR and Raman) of both compounds are described. The spectroscopic manifestation of the very short hydrogen bond in 1, and ABC-like spectra in 2 were discussed.  相似文献   

11.
β-UP2O7 has been synthesized under hydrothermal conditions (θ=500°C, P=200 MPa), using UO2 and H3PO4. β-UP2O7 crystallizes in the orthorhombic space group Pn21a, with a=11.526 (2) Å, b=7.048 (2) Å, c=12.807 (2) Å and Z=4. Its structure has been determined through direct methods and difference Fourier synthesis and has been refined to R=0.0396. The structure is built on UO8 polyhedral chains along the b-axis. PO43− and P3O105− groups coexist in the structure and the latter groups form non-linear chains. Cohesion of the structure is made through the linkage of UO8 chains by PO4 and P3O10 groups leading to the formula U2(PO4)(P3O10) instead of β-UP2O7. Vibrational and optical spectra confirm the results obtained by X-ray diffraction. DTA-TGA measurements show that the transformation of U2(PO4)(P3O10) to the cubic α-UP2O7 occurs at θ=870°C.  相似文献   

12.
Hydroboration reactions of 1-octene and 1-hexyne with H2BBr·SMe2 in CH2Cl2 were studied as a function of concentration and temperature, using 11B NMR spectroscopy. The reactions exhibited saturation kinetics. The rate of dissociation of dimethyl sulfide from boron at 25 °C was found to be (7.36 ± 0.59 and 7.32 ± 0.90) × 10−3 s−1 for 1-octene and 1-hexyne, respectively. The second order rate constants, k2, for hydroboration worked out to be 7.00 ± 0.81 M s−1 and 7.03 ± 0.70 M s−1, while the overall composite second order rate constants, k K, were (3.30 ± 0.43 and 3.10 ± 0.37) × 10−2 M s−1, respectively at 25 °C. The entropy and enthalpy values were found to be large and positive for k1, whilst for k2 these were large and negative, with small values for enthalpies. This is indicative of a limiting dissociative (D) for the dissociation of Me2S and associative mechanism (A) for the hydroboration process. The overall activation parameters, ΔH and ΔS, were found to be 98 ± 2 kJ mol−1 and +56 ± 7 J K−1 mol−1 for 1-octene whilst, in the case of 1-hexyne these were found out to be 117 ± 7 kJ mol−1 and +119 ± 24 J K−1 mol−1, respectively. When comparing the kinetic data between H2BBr·SMe2 and HBBr2·SMe2, the results showed that the rate of dissociation of Me2S from H2BBr·SMe2 is on average 34 times faster than it is in the case of HBBr2·SMe2. Similarly, the rate of hydroboration with H2BBr·SMe2 was found to be on average 11 times faster than it is with HBBr2·SMe2. It is also clear that by replacing a hydrogen substituent with a bromine atom in the case of H2BBr·SMe2 the mechanism for the overall process changes from limiting dissociative (D) to interchange associative (Ia).  相似文献   

13.
Two solid-state coordination compounds of rare earth metals with glycin, [Gd4/3Y2/3(Gly)6(H2O)4](ClO4)6·5H2O and [ErY(Gly)6(H2O)4](ClO4)6·5H2O were synthesized. The low-temperature heat capacities of the two coordination compounds were measured with an adiabatic calorimeter over the temperature range from 78 to 376 K. [Gd4/3Y2/3(Gly)6(H2O)4](ClO4)6·5H2O melted at 342.90 K, while [ErY(Gly)6(H2O)4](ClO4)6·5H2O melted at 328.79 K. The molar enthalpy and entropy of fusion for the two coordination compounds were determined to be 18.48 kJ mol−1 and 53.9 J K−1 mol−1 for [Gd4/3Y2/3(Gly)6(H2O)4](ClO4)6·5H2O, 1.82 kJ mol−1 and 5.5 J K−1 mol−1 for [ErY(Gly)6(H2O)4](ClO4)6·5H2O, respectively. Thermal decompositions of the two coordination compounds were studied through the thermogravimetry (TG). Possible mechanisms of the decompositions are discussed.  相似文献   

14.
The anhydrous salt K2B12F12 crystallized from aqueous solution and its structure was determined by single crystal X-ray diffraction. The Ni2In-type structure it exhibits is rare for an A2X ionic compound at 25 °C and 1 atm., consisting of an expanded hexagonal close-packed array of B12F122− centroids (cent?cent distances: 7.204-8.236 Å) with half of the K+ ions filling all of the Oh holes and half of the K+ ions filling all of the D3h trigonal holes in the close-packed layers that are midway between two “empty” Td holes. The structure is also unusual in that the bond-valence sum for the K+ ions in Oh holes is less than or equal to 0.73 (the bond-valence sum for the other type of K+ ion is 1.16). A variation of the Ni2In structure is exhibited by the previously published monohydrate Cs2(H2O)B12F12, for which an improved structure is also reported here. For K2B12F12: monoclinic, C2/c, a = 8.2072(8), b = 14.2818(7), c = 11.3441(9) Å, β = 92.832(5)°, Z = 4, T = 120(2) K. For Cs2(H2O)B12F12: orthorhombic, P212121, a = 9.7475(4), b = 10.2579(4), c = 15.0549(5) Å, Z = 4, T = 110(1) K.  相似文献   

15.
The [Pt2(H2P2O5)4]4− ions in the ground and excited states and the excited-state complexes M-[Pt2(H2P2O5)4]3− and M2-[Pt2(H2P2O5)4]2− (M = Ag, Tl) were studied in solution with various density functional theory (DFT) functionals from Gaussian 09 and Amsterdam Density Functional (ADF) programs. Calculated results were compared with ultrafast X-ray solution scattering data. Time dependent DFT (TD-DFT) calculations with the B3PW91 functional and unrestricted open shell calculations with the mPBE functional produce good agreement with the experimental results. Compared to gas phase calculations, the surrounding solvent is found to play an important role to shorten the Pt-Pt and M-Pt (M = Ag, Tl) bond lengths, lowering the molecular orbital energies and influences the molecular orbital transitions upon excitation, which stabilizes the excited transient molecules in solution.  相似文献   

16.
A novel red light-emitting material, Ca3Al2O6:Eu3+, which is the first example found in the Ca3Al2O6 host, was prepared by calcination of a layered double hydroxide precursor at 1350 °C. The precursor, [Ca2.9−xAl2Eux(OH)9.8](NO3)2+x·2.5H2O, was prepared by coprecipitation of metal nitrates with sodium hydroxide. The material is a loose powder composed of irregular particles formed from aggregation of particles of a few nanometers, as shown in scanning electron microscope (SEM) images. It was found that the photoluminescence intensity reached the maximum when the calcination temperature was 1350 °C and the concentration of Eu3+ was 1.0%. The material emits bright red emission at 614 nm under a radiation of λ=250 nm.  相似文献   

17.
New compounds of the type M2(H2F3)(HF2)2(AF6) with M = Ca, A = As and M = Sr, A = As, P) were isolated. Ca2(H2F3)(HF2)2(AsF6) was prepared from Ca(AsF6)2 with repeated additions of neutral anhydrous hydrogen fluoride (aHF). It crystallizes in a space group P4322 with a = 714.67(10) pm, c = 1754.8(3) pm, V = 0.8963(2) nm3 and Z = 4. Sr2(H2F3)(HF2)2(AsF6) was prepared at room temperature by dissolving SrF2 in aHF acidified with AsF5 in mole ratio SrF2:AsF5 = 2:1. It crystallizes in a space group P4322 with a = 746.00(12) pm, c = 1805.1(5) pm, V = 1.0046(4) nm3 and Z = 4. Sr2(H2F3)(HF2)2(PF6) was prepared from Sr(XeF2)n(PF6)2 in neutral aHF. It crystallizes in a space group P4122 with a = 737.0(3) pm, c = 1793.7(14) pm, V = 0.9744(9) nm3 and Z = 4. The compounds M2(H2F3)(HF2)2(AF6) gradually lose HF at room temperature in a dynamic vacuum or during being powdered for recording IR spectra or X-ray powder ray diffraction patterns. All compounds are isotypical with coordination of nine fluorine atoms around a metal center forming a distorted Archimedian antiprism with one face capped. This is the first example of the compounds in which H2F3 and HF2 anions simultaneously bridge metal centers forming close packed three-dimensional network of polymeric compounds with low solubility in aHF. The HF2 anions are asymmetric with usual F?F distances of 227.3-228.5 pm. Vibrational frequency (ν1) of HF2 is close to that in NaHF2. The anion H2F3 exhibits unusually small F?F?F angle of 95.1°-97.6° most probably as a consequence of close packed structure.  相似文献   

18.
Crea F  Milea D  Sammartano S 《Talanta》2005,65(1):229-238
In order to analyze the formation of hetero-metal polynuclear hydrolytic species, in this paper, we reported some results of an investigation (at I = 0.16 mol L−1 in NaNO3, at t = 25 °C by potentiometry, ISE-H+, glass electrode) on the hydrolysis of several mixtures (in different ratios) of two couples of cations: dioxouranium(VI)/copper(II) and dioxouranium(VI)/diethyltin(IV). The elevated total concentrations of cations 0.005 ≤ ΣCM mol L−1 ≤ 0.05) adopted in these measurements induced us to study again the hydrolysis of uranyl, for which no suitable literature data are available in these particular experimental conditions. All measurements were performed by two different operators, using completely independent instruments and reagents. Many different speciation models were considered in the calculations, including the simultaneous refinement of homo- and hetero-metal species, and a statistical analysis of obtained results was proposed too. Main results can be summarized as follows: UO22+ and Cu2+ form three hetero-metal polynuclear hydrolytic species [(UO2)Cu(OH)3+, (UO2)Cu2(OH)2+ and (UO2)2Cu4(OH)2+, with log βpqr = −2.93 ± 0.01, −7.34 ± 0.03 and −13.78 ± 0.03, respectively], all those common to their simple speciation without the other cation; UO22+ and (C2H5)2Sn2+ form seven mixed hydrolytic species [(UO2)(DET)(OH)3+, (UO2)(DET)2(OH)2+, (UO2)2(DET)4(OH)2+, (UO2)(DET)24(OH)2+, (UO2)2(DET)+5(OH), (UO2)(DET)2+5(OH) and (UO2)2(DET)7(OH), with log βpqr = −2.5 ± 0.2, −4.74 ± 0.02, −10.70 ± 0.06, −10.34 ± 0.03, −15.70 ± 0.06, −15.58 ± 0.06 and −27.9 ± 0.1, respectively] that are of the same kind of those formed by uranyl; formation of mixed hydrolytic species causes a significant enhancement of the percentage of hydrolyzed metal cations, modifying the solubility and, therefore, the bioavailability of these cations. We also determined, for dioxouranium(VI)/copper(II) system, the corresponding complex formation enthalpies and entropies by direct calorimetric measurements. We obtained ΔH112 = 47.9 ± 0.6 and ΔH214 = 92.9 ± 0.5 kJ mol−1, TΔS112 = 6 ± 1 and TΔS214 = 14 ± 1 kJ mol−1 (±S.D.), respectively, for the formation of (UO2)(Cu)2(OH)2+ and (UO2)2(Cu)4(OH)2+ species (according to reaction 2). We also calculated the single enthalpic and entropic contributes to the extra-stability that these species show with respect to the corresponding homo polynuclear ones.  相似文献   

19.
In the system BaF2/BF3/PF5/anhydrous hydrogen fluoride (aHF) a compound Ba(BF4)(PF6) was isolated and characterized by Raman spectroscopy and X-ray diffraction on the single crystal. Ba(BF4)(PF6) crystallizes in a hexagonal space group with a=10.2251(4) Å, c=6.1535(4) Å, V=557.17(5) Å3 at 200 K, and Z=3. Both crystallographically independent Ba atoms possess coordination polyhedra in the shape of tri-capped trigonal prisms, which include F atoms from BF4 and PF6 anions. In the analogous system with AsF5 instead of PF5 the compound Ba(BF4)(AsF6) was isolated and characterized. It crystallizes in an orthorhombic Pnma space group with a=10.415(2) Å, b=6.325(3) Å, c=11.8297(17) Å, V=779.3(4) Å3 at 200 K, and Z=4. The coordination around Ba atom is in the shape of slightly distorted tri-capped trigonal prism which includes five F atoms from AsF6 and four F atoms from BF4 anions. When the system BaF2/BF3/AsF5/aHF is made basic with an extra addition of BaF2, the compound Ba2(BF4)2(AsF6)(H3F4) was obtained. It crystallizes in a hexagonal P63/mmc space group with a=6.8709(9) Å, c=17.327(8) Å, V=708.4(4) Å3 at 200 K, and Z=2. The barium environment in the shape of tetra-capped distorted trigonal prism involves 10 F atoms from four BF4, three AsF6 and three H3F4 anions. All F atoms, except the central atom in H3F4 moiety, act as μ2-bridges yielding a complex 3-D structural network.  相似文献   

20.
Garnet-structure related metal oxides with the nominal chemical composition of Li5La3Nb2O12, In-substituted Li5.5La3Nb1.75In0.25O12 and K-substituted Li5.5La2.75K0.25Nb2O12 were prepared by solid-state reactions at 900, 950, and 1000 °C using appropriate amounts of corresponding metal oxides, nitrates and carbonates. The powder XRD data reveal that the In- and K-doped compounds are isostructural with the parent compound Li5La3Nb2O12. The variation in the cubic lattice parameter was found to change with the size of the dopant ions, for example, substitution of larger In3+(rCN6: 0.79 Å) for smaller Nb5+ (rCN6: 0.64 Å) shows an increase in the lattice parameter from 12.8005(9) to 12.826(1) Å at 1000 °C. Samples prepared at higher temperatures (950, 1000 °C) show mainly bulk lithium ion conductivity in contrast to those synthesized at lower temperatures (900 °C). The activation energies for the ionic conductivities are comparable for all samples. Partial substitution of K+ for La3+ and In3+ for Nb5+ in Li5La3Nb2O12 exhibits slightly higher ionic conductivity than that of the parent compound over the investigated temperature regime 25-300 °C. Among the compounds investigated, the In-substituted Li5.5La3Nb1.75In0.25O12 exhibits the highest bulk lithium ion conductivity of 1.8×10−4 S/cm at 50 °C with an activation energy of 0.51 eV. The diffusivity (“component diffusion coefficient”) obtained from the AC conductivity and powder XRD data falls in the range 10−10-10−7 cm2/s over the temperature regime 50-200 °C, which is extraordinarily high and comparable with liquids. Substitution of Al, Co, and Ni for Nb in Li5La3Nb2O12 was found to be unsuccessful under the investigated conditions.  相似文献   

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