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1.
The solubility of SnO2(cassiterite) was studied at 23±2?°C as a function of time (7 to 49 days) and pH (0 to 14.5). Steady state concentrations were reached in <7 days. The data were interpreted using the SIT model. The data show that SnO2(cassiterite) is the stable phase at pH values of 10 K 0 value of ?64.39±0.30 for the reaction (SnO2(cassiterite) +2H2O?Sn4++4OH?) and values of 1.86±0.30, ≤?0.62, ?9.20±0.34, and ?20.28±0.34 for the reaction ( $\mathrm{Sn}^{4+} + n\mathrm{H}_{2}\mathrm{O} \rightleftarrows \mathrm{Sn}(\mathrm{OH})_{n}^{4 - n} + n\mathrm{H}^{+}$ ) with values of “n” equal to 1, 4, 5, and 6 respectively. These thermodynamic hydrolysis constants were used to reinterpret the extensive literature data for SnO2(am) solubility, which provided a log?10 K 0 value of ?61.80±0.29 for the reaction (SnO2(am)+2H2O?Sn4++4OH?). SnO2(cassiterite) is unstable under highly alkaline conditions (NaOH concentrations >0.003 mol?dm?3) and transforms to a double salt of SnO2 and NaOH. Although additional well-focused studies will be required for confirmation, the experimental data in the highly alkaline region (0.003 to 3.5 mol?dm?3 NaOH) can be well described with log?10 K 0 of ?5.29±0.35 for the reaction Na2Sn(OH)6(s)?Na2Sn(OH)6(aq).  相似文献   

2.
The acid?Cbase behavior of $\mathrm{Fe}(\mathrm{CN})_{6}^{4-}$ was investigated by measuring the formal potentials of the $\mathrm{Fe}(\mathrm{CN})_{6}^{3-}$ / $\mathrm{Fe}(\mathrm{CN})_{6}^{4-}$ couple over a wide range of acidic and neutral solution compositions. The experimental data were fitted to a model taking into account the protonated forms of $\mathrm{Fe}(\mathrm{CN})_{6}^{4-}$ and using values of the activities of species in solution, calculated with a simple solution model and a series of binary data available in the literature. The fitting needed to take account of the protonated species $\mathrm{HFe}(\mathrm{CN})_{6}^{3-}$ and $\mathrm{H}_{2}\mathrm{Fe}(\mathrm{CN})_{6}^{2-}$ , already described in the literature, but also the species $\mathrm{H}_{3}\mathrm{Fe}(\mathrm{CN})_{6}^{-}$ (associated with the acid?Cbase equilibrium $\mathrm{H}_{3}\mathrm{Fe}(\mathrm{CN})_{6}^{-}\rightleftharpoons \mathrm{H}_{2}\mathrm{Fe}(\mathrm{CN})_{6}^{2-} + \mathrm{H}^{+}$ ). The acidic dissociation constants of $\mathrm{HFe}(\mathrm{CN})_{6}^{3-}$ , $\mathrm{H}_{2}\mathrm{Fe}(\mathrm{CN})_{6}^{2-}$ and $\mathrm{H}_{3}\mathrm{Fe}(\mathrm{CN})_{6}^{-}$ were found to be $\mathrm{p}K^{\mathrm{II}}_{1}= 3.9\pm0.1$ , $\mathrm{p}K^{\mathrm{II}}_{2} = 2.0\pm0.1$ , and $\mathrm{p}K^{\mathrm{II}}_{3} = 0.0\pm0.1$ , respectively. These constants were determined by taking into account that the activities of the species are independent of the ionic strength.  相似文献   

3.
In order to obtain a clue to the antitumor mechanism of $\left[ {{\text{Me}}_{ 3} {\text{NH}}} \right]_{ 6} \left[ {{\text{H}}_{ 2} {\text{Mo}}_{ 1 2}^{\text{V}} {\text{O}}_{ 2 8} \left( {\text{OH}} \right)_{ 1 2} \left( {{\text{Mo}}^{\text{VI}} {\text{O}}_{ 3} } \right)_{ 4} } \right]$ ·2H2O (PM-17), the interaction of PM-17 with flavin mononucleotide (FMN) as a prosthetic group of the flavoprotein has been investigated by both polarographic analysis and isothermal titration calorimetry (ITC) technique at the physiological solution pH (7.5). The half-wave potential (?0.50 V vs. Ag/AgCl) of the d.c. polarogram for the quasi-reversible one-electron reduction of FMN was shifted by PM-17 toward a more positive potential with a resultant deviation from one-electron reduction to formally more than one-electron reduction waves. The PM-17 effect on the d.c. polarogram could be explained by a variety of FMN···(PM-17)n (n > 0) aggregates with multiple conformations which was supported by the thermodynamic parameters (ΔH = ?29.7 kJ mol?1, ΔS = ?28.2 J mol?1 K?1, ΔG = ?21.5 kJ mol?1, and number of FMN in the binding with PM-17 (N) = 0.053 at 20 °C) estimated by the ITC technique. A large conformational change of the FMN domain by the FMN···(PM-17)n aggregates is suggested to prevent the movement of the FMN centers into close proximity with nicotinamide adenine dinucleotide (NADH) with a resultant depression of the electron transport in NADH dehydrogenase.  相似文献   

4.
The β-distonic ion $ ^ \cdot {\rm CH}_2 {\rm CH}_2 \mathop {\rm O}\limits^ + {\rm HCH}_2 {\rm CH}_2 {\rm CH}_3 $ has been shown previously to be an intermediate in the fragmentation of ionized ethyl propyl ether. The reactions of this ion (generated by fragmentation in the ion source of alkyl propyl ethers of glycol) were studied in this work. Labelling showed that this ion undergoes competing hydrogen transfers leading to a series of isomeric distonic ions. Each of them was submitted to an isotope effect.  相似文献   

5.
The major objective of this study, based on critical review and experimental studies, was to develop a reliable thermodynamic model for the Nd–F system at 25 °C. The SIT model was used to convert concentration constants reported in the literature to constants at zero ionic strengths for cross comparison and selection of reliable values. The critically evaluated thermodynamic constants for the formation of NdF2+ and NdF 2 + were then used to interpret the extensive NdF3(cr) solubility data in NaF and NH4F solutions, ranging in concentrations from extremely low values to as high as 1.0 mol·kg?1, equilibrated for different periods ranging up to as long as 72 days. These efforts have resulted in $ \log_{10} \beta_{n}^{0} $ log 10 β n 0 for the reaction [Nd3+ + nF? ? NdF n 3?n ] of (3.81 ± 0.10), (5.89 ± 0.77), and <12.48 for n values of 1–3, respectively. The $ \log_{10} K_{\text{sp}}^{0} $ log 10 K sp 0 for the solubility of NdF3(cr) (NdF3(cr) ? Nd3+ + 3F?) was determined to be (?20.49 ± 0.37). Because (1) Nd is an excellent analog for trivalent actinides—An(III) (i.e., Pu(III), Am(III), and Cm(III)), and (2) the available data for the An(III)–F system, especially the solubility products of AnF3(cr), are of extremely poor quality, the critical literature review in combination with the experimental Nd–F system data have been used to assign thermodynamic constants for the An(III)–F reactions until good quality specific data for them becomes available.  相似文献   

6.
The solubility of NdPO4(c) was studied at 23±2 °C from both the over and undersaturation directions, with pH ranging from 0 to 9, P concentrations ranging from 0.0003 to 1.00M, and equilibration periods ranging from 6 to 57 days. Equilibrium was reached in <6 days. From the H+, Nd, and P concentrations in equilibrated solutions, the logarithm of the thermodynamic equilibrium constant for the reaction (NdPO4(c) Nd3++PO4 3-) was calculated to be -24.65±0.23 and the value of the Pitzer ion-interaction parameter (2)for Nd3+-H2PO4 - was determined to be -92.9. Predictions based on these thermodynamic quantities were in excellent agreement with the experimental data.  相似文献   

7.
Only a limited number of experimental investigations have been conducted to determine hydrolysis constants of Pd(II) or the solubility product of Pd(II) hydroxide, and the reported values differ considerably from each other. No comprehensive reliable thermodynamic model is available for the Pd?COH and Pd?CCl systems. To obtain such a model, thermodynamic data for palladium compounds and complexes with chloride and hydroxide were critically evaluated using the SIT model. These evaluations, in most cases, involved reinterpretation of the original data reported in various publications to produce values of equilibrium constants for various reactions that are consistent with all of available reliable literature data. Final recommended values for solubility products and complexes of Pd(II) with hydroxide and chloride, along with the values for SIT ion interaction parameters, are tabulated.  相似文献   

8.
杂多化合物在催化、医药、材料及光化学等方面具有广泛的应用前景 [1~ 4 ] ,其中钼磷多金属氧酸盐具有优异的氧化催化性能 [5,6 ] .近年来合成的新奇结构的钼磷多金属氧酸盐中已测定结构的有含帽[7,8] 和非帽[9~ 12 ] 系列 .本文利用水热法合成了未见文献报道的结构新颖的夹心型磷钼多金属氧酸盐[( CH3CH2 ) 4N]4 H3O{Na[( HMo2 O5) 3( HPO4 ) ( H2 PO4 ) 3]2 }· ( H2 PO4 ) 2 · 1 0 H2 O,并测定了其晶体结构 .1 实验与晶体结构分析1 .1 仪器与试剂 元素 Na用美国原子吸收分光光度计测定 ;C,H和 N用 Perkin- Elmer 2 4 0…  相似文献   

9.
The complexation reactions of dibenzo-18-crown-6 (DB18C6) with Ce3+, Y3+, UO22 +\mathrm{UO}_{2}^{2 +} and Sr2+ cations were studied in acetonitrile–dioxane (AN–dioxane) binary solvent solutions at different temperatures by the conductometric method. The stability constants of the resulting 1:1 complexes were determined from computer fitting of the conductance–mole ratio data. The results show that dibenzo-18-crown-6 does not exhibit selectivity for the cation whose ionic size is closest to the cavity size of this macrocyclic ligand in AN–dioxane binary solvent solutions. A nonlinear relationship was observed between the stability constants (log 10 K f) of these complexes with the composition of the AN–dioxane binary solvent. Values of thermodynamic parameters (DHc°, DSc°\Delta H_{\mathrm{c}}^{\circ}, \Delta S_{\mathrm{c}}^{\circ}) for complexation reactions were obtained from the temperature dependence of the stability constants. The results show that the values along with the sign of these parameters are influenced by the nature and composition of the mixed solvent.  相似文献   

10.
Complexes \(\rm[{Ph_{3}PR]_2^+[RuCl_6]^{2-}}\), where R = C2H5 (I), CH=CHCH3 (II), CH2CH=CHCH3 (III), and CH2OCH3 (IV), have been prepared by the reaction between ruthenium(III) chloride hydrate and triphenylorganylphosphonium chlorides in dimethylsulfoxide in the presence of hydrochloric acid. A hydrochloric acid solution of ruthenium(III) chloride hydrate when mixed with an aqueous solution of 2-butylene-1,4- bis(triphenylphosphonium dichloride) followed by recrystallization from dimethylsulfoxide results in complex \(\rm[{Ph_{3}PCH_2CH=CHCH_2{PPh_3}]_2^{2+}[Ru_2Cl_{10}O]^{4-}}\)· 4H2O (V). According to X-ray diffraction data, phosphorus atoms in mono- and binuclear cations have slightly distorted tetrahedral coordination (CPC 105.54(13)°?113.00(8)°, P?C 1.758(9)?1.839(7) Å). In slightly distorted octahedral anions [RuCl6]2? of complexes I–IV, the Ru?Cl bond lengths vary in the range 2.3222(6)?2.340(2) Å; the cis-ClRuCl and trans-ClRuCl angles are 89.133(18)°–90.867(18)° and 179.53(13)°–180°, respectively. In the binuclear [(RuCl5)2O]4? anion of complex V, RuCl5 fragments are bonded by a bridging oxygen atom. The Ru–Cl bond lengths fall in the range 2.3375(8)?2.3957(8) Å; the Ru–O bond length is 1.7832(2) Å. The cis-ClRuCl, trans-ClRuCl, cis-ORuCl, and trans-ORuCl angles are 86.67(3)°?91.28(3)°, 174.60(3)°?174.83(3)°, 91.49(2)°?93.65(2)°, and 178.39(2)°, respectively. In crystals I–V, interionic hydrogen bonds Cl···Hcation (2.63?2.95 Å), Cl··· \({\rm{H}_{{H_2}O}}\) (2.35?2.79 Å), and Hcation···\({\rm{O}_{{H_2}O}}\) (1.72?1.93 Å) (for V) are found.  相似文献   

11.
In this work, an alkoxide solution route to synthesize Ca phosphates was developed. For the precursors, a CaO2C2H4 solution was prepared by dissolving Ca metal powder into ethylene glycol, and a PO(OH)x(OBut)3–x solution was prepared by dissolving P2O5 inton -butanol under reflux conditions. In order to obtain a mixed solution of the two precursors, acetic acid was used as an additive. The experimental results show that (1) -2CaO · P2O5, -3CaO · P2O5, and hydroxyapatite can be easily synthesized by converting the corresponding mixed solutions to powder products in a hot plate, and calcining the as prepared products at 1100°C; (2) acetic acid behaves as a good agent for controlling the reactions between the two precursors by modifying the CaO2C2H4 species in solution and decreasing the reactivity of the PO(OH)x(OBut)3–x species.  相似文献   

12.
A new reduced molybdenum(Ⅴ) phosphate (H3dien)2(H2dien)2[NaMo12O24 (OH)6 (H2PO4)(HPO4)5(PO4)2]·nH2O(n= 10.92,dien = diethylenetriamine) has been synthesized under hydrothermal conditions and characterized by elemental analyses, IR and X-ray diffraction. C16H96.84MO12N12NaO72.92P8 (Mr = 3046.73) crystallizes in the monoclinic system, space group P21/c with a = 13.3575(18), b = 21.907(3), c = 15.654(2) A, β= 110.22(2)°, V= 4298.4(10) (A)3, Dc = 2.354 g/cm3, Z = 2, μ(MoKα) = 1.966 mm-1, F(000) = 2990.4, the final R = 0.0357 and wR = 0.1086 for 8739 observed reflections with Ⅰ> 2σ(Ⅰ). It consists of sandwich-shaped cluster anions [Na{Mo6P4}2]10- held together into a three-dimensional supramolecular framework through intermolecular hydrogen-bonding contacts. A probe reaction of the oxidation of acetaldehyde with H2O2 showed that this compound has high catalytic activity in the reaction.  相似文献   

13.
The reaction of UI3 in THF with KTpMe2 and the subsequent addition of [K2(C8H6{SiiPr3-1,4}2)] or [K2(C8H4{SiiPr3-1,4}2)] yields dark red [U(κ3-TpMe2)(C8H6{SiiPr3-1,4}2)] 1 and purple [U(κ3-TpMe2)(C8H4{SiiPr3-1,4}2)] 2, respectively. The 1H NMR of 1 at room temperature suggests a rigid structure, whereas 2 is fluxional in solution on the NMR timescale. 1 is unreactive towards CO, CO2 and MeNC under mild conditions; density functional calculations were used to compare the electronic and steric effects of the TpMe2 vs. Cp* ligands in mixed sandwich complexes of the type [U(L)(C8H6{SiH3-1,4}2)] (L = Cp* or (κ3-TpMe2)). On heating at 80 °C, 1 reacts with excess MeNC to yield [U(C8H6{SiiPr3-1,4}2)(κ2-dmpz)21-CNMe)] 3. The structures of 13 have been determined by single crystal X-ray diffraction.  相似文献   

14.
We report the electrochemical and chemical synthesis of the first isolable iron carbonyls obtained directly from an {Fe4S4}-cluster and carbon monoxide: the structure of one product of chemical reduction, [Fe3S(CO)9]2−, had been determined by X-ray crystallography.  相似文献   

15.
Using H3PO3 as a phosphorus source and oxalic acid as a reducing agent, the first three-dimensional open-framework gallium phosphate–phosphite formula as (C6N2H18)2(C6N2H17)Ga15(OH)8(PO4)2(HPO4)12(HPO3)6·2H2O (1), has been hydrothermally synthesized in the presence of N,N,N′,N′-tetramethylenediamine (TMEDA) as a structure-directing agent. Compound 1 crystallizes in trigonal system with space group P ? 3, a = b = 19.046(3) Å, c = 8.3306(17) Å, γ = 120°, V = 2617.1(7) Å3, and Z = 1. Its 3-D network is based on alternated Ga-centered (GaO4 tetrahedra, GaO5 trigonal bipyramids, and GaO6 octahedra) and P-centered (PO43?, HPO42?, and HPO32?) units. Protonated organic amines and water molecules are located in the 12-membered ring channels.  相似文献   

16.
<正> Mr=2548.12, Triclinic, P1, a=15.941(5), b=15.957(2),c=20.240(6)A, α=76.41(2),β=83.87(2),γ=74.41(2)°,V=4814.6A3, Z=4, Dc=1.757g.cm-3, Final R=0.053 for 11867 reflections. There are two crystallographically independent M1 type trinuclear Mo cluster molecules with 'loose coordination site', A and B, in an asymmetric unit of the title crystal. They are formulated as {Mo3S4(u-dtp)(dtp)3.PhCH2CN}(dtp=[S2P(OEt)2]-) and have essentially identical cluster molecular configuration, but differ from each other in the conformations for the phenyl rings of the ligands PhCH2CN. The lengths of the Mo-Mo bonds are 2.750(1), 2.753(1),and 2.768(1)A for molecule A and 2.742(1), 2.756(1), and 2.764(1)A for molecule B, while the dihedral angles betweem the phenyl ring and the {Mo3} triangle are 25.0° and 94.9° for A and B respectively.  相似文献   

17.
1 INTRODUCTION Polyoxomolybdates have been of great interest due to their unique structural varieties, associated multitude of properties and applications as catalysis, medicine and material[1, 2]. One of the most impor- tant aspects is the synthesis and investigation of the materials on polyoxomolybdates containing organo- metallic groups[3~5]. Such materials can provide molecular models for heterogeneous catalysis and display cooperative effects or bifunctional catalytic activity[6]. O…  相似文献   

18.
Journal of Structural Chemistry - Reduction of 4,4′-bis-(phenyl azo)-diphenyl thiodiimide S(=N–C6H4–N=N–C6H5)2 (1) in tetrahydrofuran (ТHF) with potassium-intercalated...  相似文献   

19.
Introduction The chemistry of organotin(IV) dithiocarbamate complexes was extensively studied due to their biological activities.1-5 To date, a large number of transition-metal complexes with dithiocarbamate have been synthesized and structurally characterized,6-9 including Ni(S2CNC4H8O)2, Cu(S2CNC4H8)2, Zn(S2CNC4H8O)2 and Fe(S2CNC4H8O)2(DMF). However, the chemistry of main-group metal complexes with dithiocarbamate has been scarcely studied, and few reports have appeared on the s…  相似文献   

20.
Dark red transparent crystals of [Co{1,4-C(6)H(4)(CN)(2)}(2){NTf(2)}(2)][SnI{Co(CO)(4)}(3)](2) are obtained by reacting SnI(4), Co(2)(CO)(8) and 1,4-C(6)H(4)(CN)(2) in the ionic liquid [EMIm][NTf(2)] (EMIm: 1-ethyl-3-methylimidazolium; NTf(2): bis(trifluoromethylsulfonyl)imide). According to X-ray structure analysis based on single crystals, the title compound crystallizes in a triclinic manner and contains the novel (2)(∞)[Co{1,4-C(6)H(4)(CN)(2)}(2){NTf(2)}(2)] coordination network. This infinite 2D network is composed of Co(2+) ions that are planarily interlinked by four 1,4-dicyanobenzene ligands. As a non-charged 2D network, Co(2+) is furthermore coordinated by two [NTf(2)](-) anions. The (2)(∞)[Co{1,4-C(6)H(4)(CN)(2)}(2){NTf(2)}(2)] layers are stacked on top of each other with SnI[Co(CO)(4)](3) molecules intercalated in distorted cubic gaps between the layers. The title compound is furthermore characterized by energy dispersive X-ray (EDX) analysis, thermogravimetry (TG), infrared spectroscopy (FT-IR) and optical spectroscopy (UV-Vis).  相似文献   

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