Dual-stimuli responsive behaviors of diblock polyampholyte PDMAEMA-b-PAA in aqueous solution

The rheological behaviour of aqueous suspensions of boehmite (AlO(OH)) modified with different Ce-salts (Ce(NO(3))(3), CeCl(3), Ce(CH(3)COO)(3) and Ce(2)(SO(4))(3)) was investigated at a fixed Ce/Al molar ratio (0.05). Freshly prepared boehmite suspensions were near-Newtonian and time-independent. A shear-sensitive thixotropic network developed when Ce-salts with monovalent anions were introduced in the nanoparticle sols. The extent of particle aggregation dramatically increased with ageing for Ce(NO(3))(3) and CeCl(3) whereas an equilibrium value was reached with Ce(CH(3)COO)(3). The addition of Ce(2)(SO(4))(3) with divalent anions involved no thixotropy but rather a sudden phase separation. The combined data set of IRTF and DRIFT spectra indicated that free NO(3)(-) anions of peptized boehmite adsorb on the nanoparticle surface by H-bond. The introduction of Ce-salts in the boehmite sol led to the coordination between Ce(3+) ions and NO(3)(-) anions adsorbed on boehmite i.e. to [Ce(NO(3))(4)(H(2)O)(x)](-) complex. Such coordination led to a thixotropic behaviour which was lower with Ce(NO(3))(3) compared to CeCl(3) and Ce(CH(3)COO)(3). In contrast, Ce(2)(SO(4))(3) formed insoluble complexes with dissolved aluminium species. The formation of H-bonded surface nitrate complexes was found to play a decisive role on the particle-particle interactions and consequently on the rheological behaviour of the sols.     

Controlled growth and photocatalytic properties of CdS nanocrystals implanted in layered metal hydroxide matrixes

Layered double hydroxide Cd(1)(-)(x)()Al(x)()(OH)(2)(DS)(x)().3.0H(2)O (CdAlDS) and a related hydroxide salt compound Cd(2)(OH)(3)(DS).2.5H(2)O (CdDS), where DS stands for dodecyl sulfate sandwiched between two adjacent inorganic layers, have been synthesized and used as precursors for CdS nanoparticle growth. Through a gas/solid reaction, CdS nanocrystals implanted in the layer matrixes of the layered double hydroxides are grown, and the sizes of the nanocrystals vary in the range of 3-6 nm in diameter. The presence of trivalent Al cations in the layered double hydroxide can be taken advantage of to control the size of the CdS nanocrystals, and it also helps to prevent the formed nanocrystals from extraction from the solid matrixes. The nano-CdS implanted composite exhibits high photocatalytic activity for degradation of the nonbiodegradable rhodamine B under both UV and visible irradiations.     

The synthesis and spectroscopic characterisation of hydrotalcite formed from aluminate solutions

Raman spectroscopy has been used to characterise nine hydrotalcites prepared from aluminate and magnesium solutions (magnesium chloride and seawater). The aluminate hydrotalcites are proposed to have the following formula Mg(6)Al(2)(OH)(16)(CO(3)(2-))·xH(2)O, Mg(6)Al(2)(OH)(16)(CO(3)(2-),SO(4)(2-))·xH(2)O, and Mg(6)Al(2)(OH)(16)(SO(4)(2-))·xH(2)O. The synthesis of these hydrotalcites using seawater results in the intercalation of sulfate anions into the hydrotalcite interlayer. The spectra have been used to assess the molecular assembly of the cations and anions in the hydrotalcite structures. The spectra have been conveniently subdivided into spectral features based upon the carbonate anion, the hydroxyl units and water units. This investigation has shown the ideal conditions to form hydrotalcite from aluminate solutions is at pH 14 using a magnesium chloride solution at a volumetric ratio of 1:1. Changes in synthesis conditions resulted in the formation of impurity products aragonite, thenardite, and gypsum.     

Hydrothermal synthesis, structure, and luminescent properties of selected Zn(II)/Cd(II) coordination polymers constructed from 3,5-bis(x-pyridyl)-1,2,4-triazole (x = 3, 4)

Utilizing 3,5-bis(x-pyridyl)-1,2,4-triazole (x-Hpytz, x = 3; x = 4) as multidentate ligands, six novel coordination polymers with Zn(II) or Cd(II) metal ions were prepared: [Zn(3-pytz)(0.5)(OH)(0.5)Cl](n) (1, 1D ladder), {[Zn(3-Hpytz)(H(2)O)(4)] [Zn(3-Hpytz)(H(2)O)(3)·SO(4)]SO(4)·5H(2)O}(n) (2·5H(2)O, 1D chain), [Cd(3-Hpytz)(SO(4))](n) (3, 3D framework), {[Cd(3-Hyptz)SO(4)·3H(2)O]·2H(2)O}(n) (4·2H(2)O, 1D chain), [Zn(4-pytz)Cl](n) (5, 3D framework) and [Zn(2)(4-pytz)(SO(4))(OH)](n) (6, 3D framework). All compounds were obtained from hydrothermal reactions, with the exception of compound 4 which was obtained by solvent diffusion at room temperature. All compounds were characterized by FTIR, elemental analysis and TGA analysis and their structures were determined by X-ray diffraction. All compounds exhibited substantial thermal stability and showed photofluorescent properties that resulted from ligand π-π* transition.     

Pulse radiolysis study on free radical scavenger edaravone (3-methyl-1-phenyl-2-pyrazolin-5-one)

The reactions between edaravone and various one-electron oxidants such as (*)OH, N(3)(*), Br(2)(-), and SO(4)(-), have been studied by pulse radiolysis techniques. The transient species produced by the reaction of edaravone with (*)OH radical shows an absorption band with lambda(max)=320 nm, while the oxidation by N(3)(*), Br(2)(-), SO(4)(-) and CCl(3)OO(*) results in an absorption band with lambda(max)=345 nm. Different from the previous reports, the main transient species by the reaction of edaravone with (*)OH radical in the absence of O(2) is attributed to OH-adducts. At neutral condition (pH 7), the rate constants of edaravone reacting with (*)OH, N(3)(*), SO(4)(-), CCl(3)OO(*), and e(aq)(-) are estimated to be 8.5x10(9), 5.8x10(9), 6x10(8), 5.0x10(8) and 2.4x10(9)dm(3)mol(-1)s(-1), respectively. From the pH dependence on the formation of electron adducts and on the rate constant of edaravone with hydrated electron, the pK(a) of edaravone is estimated to be 6.9+/-0.1.     

Syntheses, structural characterization and properties of transition metal complexes of 5,5'-(1,4-phenylene)bis(1H-tetrazole) (H(2)bdt), 5',5'-(1,1'-biphenyl)-4,4'-diylbis(1H-tetrazole) (H(2)dbdt) and 5,5',5'-(1,3,5-phenylene)tris(1H-tetrazole) (H(3)btt)

The hydrothermal chemistry of a variety of M(II)SO(4) salts with the tetrazole (Ht) ligands 5,5'-(1,4-phenylene)bis(1H-tetrazole) (H(2)bdt), 5',5'-(1,1'-biphenyl)4,4'-diylbis(1H-tetrazole) (H(2)dbdt) and 5,5',5'-(1,3,5-phenylene)tris(1H-tetrazole) (H(3)btt) was investigated. In the case of Co(II), three phases were isolated, two of which incorporated sulfate: [Co(5)F(2)(dbdt)(4)(H(2)O)(6)]·2H(2)O (1·2H(2)O), [Co(4)(OH)(2)(SO(4))(bdt)(2)(H(2)O)(4)] (2) and [Co(3)(OH)(SO(4))(btt)(H(2)O)(4)]·3H(2)O (3·3H(2)O). The structures are three-dimensional and consist of cluster-based secondary building units: the pentanuclear {Co(5)F(2)(tetrazolate)(8)(H(2)O)(6)}, the tetranuclear {Co(4)(OH)(2)(SO(4))(2)(tetrazolate)(6)}(4-), and the trinuclear {Co(3)(μ(3)-OH)(SO(4))(2) (tetrazolate)(3)}(2-) for 1, 2, and 3, respectively. The Ni(II) analogue [Ni(2)(H(0.67)bdt)(3)]·10.5H(2)O (4·10.5H(2)O) is isomorphous with a fourth cobalt phase, the previously reported [Co(2)(H(0.67)bat)(3)]·20H(2)O and exhibits a {M(tetrazolate)(3/2)}(∞) chain as the fundamental building block. The dense three-dimensional structure of [Zn(bdt)] (5) consists of {ZnN(4)}tetrahedra linked through bdt ligands bonding through N1,N3 donors at either tetrazolate terminus. In contrast to the hydrothermal synthesis of 1-5, the Cd(II) material (Me(2)NH(2))(3)[Cd(12)Cl(3)(btt)(8)(DMF)(12)]·xDMF·yMeOH (DMF = dimethylformamide; x = ca. 12, y = ca. 5) was prepared in DMF/methanol. The structure is constructed from the linking of {Cd(4)Cl(tetrazolate)(8)(DMF)(4)}(1-) secondary building units to produce an open-framework material exhibiting 66.5% void volume. The magnetic properties of the Co(II) series are reflective of the structural building units.     

Characterization of aluminum species with nitrate, perchlorate and sulfate ions in the positive and negative ion mode by electrospray ionization mass spectrometry

The application of electrospray ionization mass spectrometry (ESI-MS) for aluminum speciation in the positive and negative ion modes was discussed. Aluminum nitrate, perchlorate and sulfate solutions were measured by ESI-MS. In the positive ion mode, aluminum species containing anions (Al-L; L=NO3, ClO4 and SO4) were identified, while [Al(OH)2(H2O)n]+ (n=2-4) were the main species. The affinity of the anions with Al3+ estimated by ESI-MS was consistent with the hardness of the anions (hard and soft acids and bases principle) and the results from 27Al nuclear magnetic resonance studies. This indicates that the results observed from the positive ion mode preserved the chemical state of aluminum in the solution. In the negative ion mode, [Al(OH)4-nLn]- (n=0-2, L=NO3, ClO4) were the main species, which were considered to be converted from positive aluminum species, [Al(OH)(H2O)n]+ (n=2-4), by the successive addition of anions. Anions did not only attach to one aluminum ion but also bridged two aluminum ions. In Al2(SO4)3 solution, the behavior of SO4(2-) in the negative ion mode differed from that of NO3- and ClO4-. This may reflect the affinity of SO4(2-) with Al3+ in the solution or in the mass spectrometer or in both. Finally, detection mechanisms for the aluminum species in the solution are proposed for both the positive and negative ion modes. It is shown that ESI-MS can be used to observe the interaction between Al3+ and anions. We show the importance of the interpretation of the results by ESI-MS for obtaining new information of the metal species in the solution.     

Model of uptake of OH radicals on nonreactive solids

A model of adsorption and recombination of OH radicals was developed for nonreactive solid surfaces of atmospheric interest. A parametrization of this heterogeneous mechanism was carried out to determine the role of the catalytic properties of these solid surfaces, taking into account the adsorption energy, defects, surface diffusion, and chemical reactions in the gas-solid interface. The uptake process was simulated for diffusion-controlled chemical reactions on the surface on the basis of Langmuir-Hinshelwood and Eley-Rideal mechanisms. Using an analytical approach and the Monte Carlo technique, we show the dependencies of the uptake probability of the heterogeneous reactions on the OH concentration and adsorption energy. The model is employed in the analysis of the empirically derived uptake coefficient for water ice, Al(2)O(3), NaCl, NH(4)NO(3), NH(4)HSO(4), and (NH(4))(2)SO(4). We found the following values for the free energy of adsorption of OH radicals: E(ice) = 7.3-7.6 kcal/mol, E(Al)(2)(O)(3) = 11-11.7 kcal/mol, E(NH)(4)(NO)(3) = 10.2 kcal/mol, E(NaCl) = 10.2 kcal/mol, E(NH)(4)(HSO)(4) = 9.8 kcal/mol, and E((NH)(4))(2)(SO)(4) = 9.8 kcal/mol. The atmospheric implications of the catalytic reactions of OH with adsorbed reactive molecules are discussed. The results of the modeling of the uptake process showed that the heterogeneous decay rate can exceed the corresponding gas-phase reaction rate under atmospheric conditions.     

助剂前体ZnSO_4浓度对苯选择加氢制环己烯Ru-Zn催化剂性能的影响

共沉淀法制备了Ru-Zn催化剂,在ZrO_2作分散剂下考察了助剂前体ZnSO_4浓度对苯选择加氢制环己烯Ru-Zn催化剂性能的影响.并用X-射线衍射(XRD)、X-射线荧光光谱(XRF)、N_2-物理吸附、透射电镜(TEM)和X-射线光电子能谱(XPS)等手段对催化剂进行了表征.结果表明,当ZnSO_4前体浓度低于0.10 mol/L时,Ru-Zn催化剂中Zn以ZnO形式存在,在加氢过程中ZnO可以与反应修饰剂ZnSO_4反应生成(Zn( OH)_2)_3(ZnSO_4)(H_2O)_3盐.继续增加ZnSO_4前体浓度,催化剂中Zn以ZnO和NaZn_4(SO_4)(Cl)(OH)_6·6H_2O盐存在,在加氢过程中ZnO和NaZn_4(SO_4)(Cl)(OH)_6·6H_2O盐可以与反应修饰剂ZnSO_4反应生成(Zn( OH)_2)_3(ZnSO_4)(H_2O)_5.(Zn( OH)_2)_3(ZnSO_4)(H_2O)_x(x=3或5)盐的Zn~(2+)可以转移金属Ru的部分电子.因此,随ZnSO_4前体浓度的增加,(Zn( OH)_2)_3(ZnSO_4)(H_2O)_x的量逐渐增加,金属Ru失电子越多,催化剂活性越低,环己烯选择性越高.0.08 mol/L ZnSO_4前体制备Ru-Zn催化剂给出了59.1%的环己烯收率,而且该催化剂具有良好的重复使用性能和稳定性.     

Photochemical investigation of Roussin's red salt esters: Fe2(mu-SR)2(NO)4

The photochemistry of various Roussin's red ester compounds of the general formula Fe(2)(SR)(2)(NO)(4), where R = CH(3), CH(2)CH(3), CH(2)C(6)H(5), CH(2)CH(2)OH, and CH(2)CH(2)SO(3)(-), were investigated. Continuous photolyses of these ester compounds in aerated solutions led to the release of NO with moderate quantum yields for the photodecomposition of the ester (Phi(RSE) = 0.02-0.13). Electrochemical studies using an NO electrode demonstrated that 4 mol of NO are generated for each mole of ester undergoing photodecomposition. Nanosecond flash photolysis studies of Fe(2)(SR)(2)(NO)(4) (where R = CH(2)CH(2)OH and CH(2)CH(2)SO(3)(-)) indicate that the initial photoreaction is the reversible dissociation of NO. In the absence of oxygen, the presumed intermediate, Fe(2)(SR)(2)(NO)(3), undergoes second-order reaction with NO to regenerate the parent cluster with a rate constant of k(NO) = 1.1 x 10(9) M(-1) s(-1) for R = CH(2)CH(2)OH. Under aerated conditions the intermediate reacts with oxygen to give permanent photochemistry.     

Synthesis and characterization of mesoporous silica from selectively acid-treated saponite as the precursors

Mesoporous silicas were synthesized by hydrothermal treatment of selectively acid-treated saponite (an ideal structural formula: Na(1/3)Mg(3)(Si(11/3)Al(1/3))O(10)(OH)(2)), having a 2:1 type layered structure as the silica source and its porous properties were examined and compared with that from kaolinite (an ideal structural formula: Al(2)Si(2)O(5)(OH)(4)), having a 1:1 type layered structure. Synthetic saponite was selectively leached in H(2)SO(4) solutions with various concentrations (0.05-1 M) at 70 degrees C for 0.5 h. The resulting products (precursors) were mixed with cetyltrimethylammonium bromide (CTABr), NaOH and H(2)O, hydrothermally treated at 110 degrees C and removed the CTABr by calcining at 560 degrees C. A hexagonal mesoporous phase was obtained with higher Si/(Al(+Mg)) ratios of the resulting precursors. The XRD patterns of these products show the peaks assigned by a hexagonal lattice with a(0)=4.0-4.6 nm and the crystallinity becomes higher with higher Si/(Al(+Mg)) ratios of the precursors. The specific surface area (S(BET)) values of the present mesoporous silicas range from 800 to 1100 m(2)/g at CTABr/precursor=0.1 and although they are not as high as those from precursors prepared from calcining and acid-treatment of kaolinite (1420 m(2)/g), they are increased to 1400-1500 m(2)/g by increasing the ratio CTABr/precursor 0.2. The reason for the difference in the optimum preparation conditions between saponite and kaolinite may be attributed to the difference in the linkage of the SiO(4) tetrahedra in these precursors (i.e. layered or framework structures), which result in great differences in the selective leaching rates and structures of the resulting silica-rich products.     

Stoichiometries and thermodynamic stabilities for aqueous sulfate complexes of U(VI)

The formation constants of UO2SO4 (aq), UO2(SO4)2(2-), and UO2(SO4)3(4-) were measured in aqueous solutions from 10 to 75 degrees C by time-resolved laser-induced fluorescence spectroscopy (TRLFS). A constant enthalpy of reaction approach was satisfactorily used to fit the thermodynamic parameters of stepwise complex formation reactions in a 0.1 M Na(+) ionic medium: log 10 K 1(25 degrees C) = 2.45 +/- 0.05, Delta r H1 = 29.1 +/- 4.0 kJ x mol(-1), log10 K2(25 degrees C) = 1.03 +/- 0.04, and Delta r H2 = 16.6 +/- 4.5 kJ x mol(-1). While the enthalpy of the UO2(SO4)2(2-) formation reaction is in good agreement with calorimetric data, that for UO2SO4 (aq) is higher than other values by a few kilojoules per mole. Incomplete knowledge of the speciation may have led to an underestimation of Delta r H1 in previous calorimetric studies. In fact, one of the published calorimetric determinations of Delta r H1 is here supported by the TRLFS results only when reinterpreted with a more correct equilibrium constant value, which shifts the fitted Delta r H1 value up by 9 kJ x mol(-1). UO2(SO 4) 3 (4-) was evidenced in a 3 M Na (+) ionic medium: log10 K3(25 degrees C) = 0.76 +/- 0.20 and Delta r H3 = 11 +/- 8 kJ x mol(-1) were obtained. The fluorescence features of the sulfate complexes were observed to depend on the ionic conditions. Changes in the coordination mode (mono- and bidentate) of the sulfate ligands may explain these observations, in line with recent structural data.     

High-resolution determination of H+ by ion chromatography. Application to the simultaneous determination of H+, Na+, NH4+ and K+ in acid rain.

An ion chromatographic (IC) method was developed for the high-resolution determination of a sample's free hydrogen ion concentration (H+). Highly purified lithium dodecyl sulfate was used as the stationary phase, a slightly acidified aqueous LiCl solution was used as the mobile phase and conductivity was used for analyte detection. An electrical double layer (EDL) containing H+ was established on the stationary phase by using a slightly acidified electrolyte solution as the eluent. H+ in the EDL protonated any weak acid groups (i.e., silanols) on the stationary phase so that H+ from the sample could be retained/separated purely by dodecyl sulfate. The optimum molar ratio of H+:Li+ in the EDL for this IC system was obtained by using an aqueous solution containing 40.0 mM LiCl and 0.07 mM H2SO4 as the eluent. After separation, H+ was detected by direct conductimetric measurement. An H+ detection limit of better than 8.2 x 10(-6) M was obtained from the analysis of standard aqueous H2SO4 solutions. Other monovalent cations could also be separated with this method, giving detection limits of 7.4 x 10(-5), 4.3 x 10(-5) and 4.2 x 10(-5) M for Na+, NH4+ and K+, respectively. The method was applied to the simultaneous determination of H+, Na+, NH4+ and K+ in acid rain. The results obtained showed a significant improvement in reproducibility when compared with those from a conventional pH-meter. Acid rain samples with a pH < 5 could be analyzed with this IC system.     

水热法合成α-MnO2纳米棒及其电化学性能

以KMnO4、氧化石墨(GO)和硫酸为原料,在120℃水热条件下3 h成功合成了直径为10~20 nm,长度为300~400 nm的α-MnO2纳米棒。研究发现GO的引入降低了纳米棒的制备温度,缩短了反应时间。电化学测试结果表明,在1 mol.L-1Na2SO4中性水系电解液中,该纳米棒表现出良好的电容性能,当扫描速率分别为2 mV.s-1和5 mV.s-1时,比电容分别为276 F.g-1和240F.g-1;该纳米材料是一种潜在的电化学电容器电极材料。     

Effective diffusion coefficients for methanol in sulfuric acid solutions measured by Raman spectroscopy

The diffusion of methanol into 0-96.5 wt % sulfuric acid solutions was followed using Raman spectroscopy. Because methanol reacts to form protonated methanol (CH 3OH 2 (+)) and methyl hydrogen sulfate in H 2SO 4 solutions, the reported diffusion coefficients, D, are effective diffusion coefficients that include all of the methyl species diffusing into H 2SO 4. The method was first verified by measuring D for methanol into water. The value obtained here, D = (1.4 +/- 0.6) x 10 (-5) cm (2)/s, agrees well with values found in the literature. The values of D in 39.2-96.5 wt % H 2SO 4 range from (0.11-0.3) x 10 (-5) cm (2)/s, with the maximum value of D occurring for 61.6 wt % H 2SO 4. The effective diffusion coefficients do not vary systematically with the viscosity of the solutions, suggesting that the speciation of both methanol and sulfuric acid may be important in determining these transport coefficients.     

Revealing the mechanisms behind SnO2 nanoparticle formation and growth during hydrothermal synthesis: an in situ total scattering study

The formation and growth mechanisms in the hydrothermal synthesis of SnO(2) nanoparticles from aqueous solutions of SnCl(4)·5H(2)O have been elucidated by means of in situ X-ray total scattering (PDF) measurements. The analysis of the data reveals that when the tin(IV) chloride precursor is dissolved, chloride ions and water coordinate octahedrally to tin(IV), forming aquachlorotin(IV) complexes of the form [SnCl(x)(H(2)O)(6-x)]((4-x)+) as well as hexaaquatin(IV) complexes [Sn(H(2)O)(6-y)(OH)(y)]((4-y)+). Upon heating, ellipsoidal SnO(2) nanoparticles are formed uniquely from hexaaquatin(IV). The nanoparticle size and morphology (aspect ratio) are dependent on both the reaction temperature and the precursor concentration, and particles as small as ~2 nm can be synthesized. Analysis of the growth curves shows that Ostwald ripening only takes place above 200 °C, and in general the growth is limited by diffusion of precursor species to the growing particle. The c-parameter in the tetragonal lattice is observed to expand up to 0.5% for particle sizes down to 2-3 nm as compared to the bulk value. SnO(2) nanoparticles below 3-4 nm do not form in the bulk rutile structure, but as an orthorhombic structural modification, which previously has only been reported at pressures above 5 GPa. Thus, adjustment of the synthesis temperature and precursor concentration not only allows control over nanoparticle size and morphology but also the structure.     

Hydroxo sulfate complexes of iron (III) in solution

The ternary Fe (III)-OH(-)-SO4(2-) complexes have been investigated at 25 degrees C in 3 M NaClO4 by potentiometric titration with glass electrode. The metal and sulfate concentrations ranged from 2.5 x 10(-3) to 0.03 M and from 5.10(-3) to 0.060 M, respectively. [H+] was decreased from 0.05 M to incipient precipitation of basic sulfate which occured at log[H+] between -2.3 and -2.5 depending on the concentration of the metal. For the interpretation of the data stability constants of HSO4(-), of binary hydroxo complexes (FeOH2+, Fe(OH)2+, Fe2(OH)2(4+), Fe3(OH)4(5+), Fe3(OH)5(4+)) and of sulfate complexes (FeSO4+, FeHSO4(2+), Fe(SO4)2-) were assumed from independent sources. The data are consistent with the presence of FeOHSO4, log beta 1-11 = -0.49 +/- 0.03. Equilibrium constants are defined as beta pqr for pFe3+ +qH+ +rSO4(2-) [symbol: see text] FepHq(SO4)r3p+q-2r. No substantial better fit could be found by adding a second mixed complex. Only a slightly smaller agreement factor resulted introducing as minor ternary complex Fe3(OH)6(SO4)3(3-) with log beta 3-63 = -5.8 +/- 0.5. Its evidence, however, cannot be considered conclusive.     

Nitrosyl induces phosphorous-acid dissociation in ruthenium(II)

The trans-[Ru(NO)(NH(3))(4)(P(OH)(3))]Cl(3) complex was synthesized by reacting [Ru(H(2)O)(NH(3))(5)](2+) with H(3)PO(3) and characterized by spectroscopic ((31)P-NMR, δ = 68 ppm) and spectrophotometric techniques (λ = 525 nm, ε = 20 L mol(-1) cm(-1); λ = 319 nm, ε = 773 L mol(-1) cm(-1); λ = 241 nm, ε = 1385 L mol(-1) cm(-1); ν(NO(+)) = 1879 cm(-1)). A pK(a) of 0.74 was determined from infrared measurements as a function of pH for the reaction: trans-[Ru(NO)(NH(3))(4)(P(OH)(3))](3+) + H(2)O ? trans-[Ru(NO)(NH(3))(4)(P(O(-))(OH)(2))](2+) + H(3)O(+). According to (31)P-NMR, IR, UV-vis, cyclic voltammetry and ab initio calculation data, upon deprotonation, trans-[Ru(NO)(NH(3))(4)(P(OH)(3))](3+) yields the O-bonded linkage isomer trans- [Ru(NO)(NH(3))(4)(OP(OH)(2))](2+), then the trans-[Ru(NO)(NH(3))(4)(OP(H)(OH)(2))](3+) decays to give the final products H(3)PO(3) and trans-[Ru(NO)(NH(3))(4)(H(2)O)](3+). The dissociation of phosphorous acid from the [Ru(NO)(NH(3))(4)](3+) moiety is pH dependent (k(obs) = 2.1 × 10(-4) s(-1) at pH 3.0, 25 °C).     

Electrical conductances of aqueous Na2SO4, H2SO4, and their mixtures: limiting equivalent ion conductances, dissociation constants, and speciation to 673 K and 28 MPa

The electrical conductivities of aqueous solutions of Na(2)SO(4), H(2)SO(4), and their mixtures have been measured at 373-673 K at 12-28 MPa in dilute solutions for molalities up to 10(-2) mol kg(-1). These conductivities have been fit to the conductance equation of Turq et al.(1) with a consensus mixing rule and mean spherical approximation activity coefficients. Provided the concentration is not too high, all of the data can be fitted by a solution model that includes ion association to form NaSO(4)(-), Na(2)SO(4)(0), HSO(4)(-), H(2)SO(4)(0), and NaHSO(4)(0). The adjustable parameters of this model are the dissociation constants of the SO(4)(-) species and the H(+), SO(4)(-2), and HSO(4)(-) conductances (ion mobilities) at infinite dilution. For the 673 K and 230 kg m(-3) state point with the lowest dielectric constant, epsilon = 3.5, where the Coulomb interactions are the strongest, this model does not fit the experimental data above a solution molality of 0.016. Including the species H(9)(SO(4))(5)(-) gave satisfactory fits to the conductance data at the higher concentrations.     

水热法制备核—壳结构勃姆石超细粉体

以硫酸铝水溶液和尿素为原料,两亲嵌段共聚物聚苯乙烯-嵌段-聚丙烯酸-2-羟基乙酯(P(St)-b-P(HEA))为结构引导剂,通过水热法合成了核壳状勃姆石超细粉体。使用X-射线衍射技术(XRD),透射电子显微镜(TEM)和扫描电子显微镜(SEM)对产物进行了表征。并在试验的基础上,对可能的形成机理进行了讨论。