THE STATE OF CHROMIUM (Ⅲ) ION IN AQUEOUS SOLUTION

So far few systematic studies on the hydrolytic polymerization of Cr(Ⅲ) were reported because of inertness of the ion and complication of the process. We studied it in equilibrium by pH method systematically in a wide concentration range (0.0002—0.32 M). The results show that, in the low concentration range, the composition of the polynuclear hydrolysis products may be represented as [Cr_3(OH)_4] (OH)_n (n=1,2,3); in the medium range, the composition of products as Cr[Cr(OH)_2]_n~((3+n))~+ (n=1,2,3); in the high range, the composition of products as Cr[Gr(OH)]_n~((3+2n))~+ (n=1, 2), and in the intermediate range between medium and high range where the hydrolysis system is in a transition state, the composition of products as [Cr_3(OH)_3]~(6+) and [Cr_3(OH)_4]~(5+). The values of hydrolysis constants of the identical species measured in different Cr concentration ranges and calculated by different methods were found in good agreement with each other. A predominance-arca diagram was made by using the hy     

THE REFINEMENT OF CRYSTAL STRUCTURE OF BALIPHOLITE

Balipholite is a new mineral discovered in China. Its space group is C cca with the lattice parameters a=13.587(6), b=20.164(10), c=5.144(1). The structure was refined to an R value of 0.047 for 949 independent reflections with (|F_0|>3σ|F_0|). Balipholite has the simailar structure as that of the carpholite group but with large cations Ba occupying the caves of the structure. It is very interesting to point out that the additional anions F and OH occupy different crystallographic positions. Formula of balipolite can he written a BaMg_2LiAl_3(Si_2O_6)_2(OH)_4F_4.     

Calorimetric Study of Thermal Denaturation of Superoxide Dismutase

The thermal denaturation of superoxide dismutase (SOD) from bovine erythrocytes was studied at various pH values of different buffers and at various concentrations of solutions of two neutral salts by differential scanning calorimetry. The experiments performed indicate that the PIPES is a buffer non-coordinating with the SOD, and that the binding of the anions studied influences more or less the thermal denaturation of SOD, but the effect on the oxidation form of SOD is more apparent. A new conformer of SOD with lower thermostability was discovered by the experiments performed in different buffers at certain pH values higher than the isoelectric point of SOD, or at higher concentrations of neutral salt solutions. The new conformer may be converted irreversibly into the usual conformer with high thermostability during heating. Based on the thermodynamic parameters obtained in distilled water and by thermodynamic analysis using the Ooi's model, it is revealed that the large enthalpy △Hdc contributed by     

The hydrogen sulfate recognition properties of azo-salicylaldehyde schiff base receptors

Azo-salicylaldehyde Schiff base-typed receptors containing an acidic H-bond donor moiety were syn-thesized and characterized. The UV-Vis data indicate that these receptors could act as selective col-orimetric sensors for basic anions and acidic species hydrogen sulfate by different color changes in a water-containing medium. The experiment of Brφnsted acid-base reaction by adding the sodium hy-droxide or perchloric acid revealed that the mechanism of recognition of anions might be deprotona-tion/protonation of the OH fragments by interacting with different anions and that the deprotona-tion/protonation process is fully reversible. The deprotonation/protonation of the receptors is respon-sible for the dramatic color change.     

Novel Lanthanide Cluster Polymers Based on Cubane-like [Ln_4(OH)_4]~(8+) Clusters and Sulfate Anions

Two lanthanide-oxo-cluster polymers were synthesized by hydrothermal reaction using Ln_2O_3 as initial lanthanide materials:[Ln_4(SO_4)_4(OH)_4(H_2O)_7]·_4H_2O(Ln = Er 1,Ho 2),and characterized by PXRD,IR spectra,X-ray single-crystal diffraction,2D IR correlation spectra and UV-visible absorption spectra.Single-crystal X-ray analyses reveal that compounds 1 and 2 are isostructural,and they are both crystallized in the orthorhombic system Pccn space group.Compound 1 is a 3D lanthanide cluster polymer based on tetranuclear cubane-like [Er_4(μ_3-OH)_4]~(8+) cations and SO_4~(2-) anions.The overall structure of 1 can be assigned to 6-connected pcu-type topology with the point symbol of(4~(12).6~3).     

DETERMINATION OF SOLUBILITY OF Fe_2O_3 IN DILUTE AQUEOUS SOLUTIONS AT 300℃ AND 10 MPa——APPENDING A DISCUSSION ABOUT THE TRANSPORTING FORM OF IRON IN HYDROTHERMAL SOLUTIONS

The solubility of Fe_2O_3 in dilute KOH and HClO_4 aqueous solutions was determined at 300℃ and 10 MPa. The analysis of the solubility data indicated that in neutral and alkaline hydrothermal solutions iron mostly existed as Fe(OH)_3~0 and Fe(OH)_4~-, and it was calculated that △G_(Fe(OH)_3~0)~0=-561.9±3.3kJ/mol, and △G_(Fe(OH)_4~0)~0=-662.7±5.0 kJ/mol at 300℃. According to the analysis on the previous experimental studies about the transporting form of iron, the existing form of iron in hydrothermal solutions is discussed in this paper.     

Structure effect of nucleotides in terbium(Ⅲ)-nucleotide fluorescent reaction—-New evidence for the binding sites of terbium(Ⅲ) on nucleotides

Upon addition of Tb~(3+) to 16 nucleotides and homopolynucleotides, all of them showeda characteristic green emission from Tb~(3+), but with much different intensity, upon excitation inthe aromatic region of bases. The result suggested that nucleotides with at least one carbonylgroup in nucleotide bases are better enhancers to the fluorescence of Tb3+. The complexes of ATP,GDP and GTP with T5~(3+) are synthesized as two types of models. Guanine tpye nucleotides withone carbonyl group in the bases are the best enhancers, while adenine type nucleotides with nocarbonyl group in the bases are poorest enhancers to the fluorescence of Tb~(3+). Comparing theIR spectra of ATP, GTP, GDP and their Tb~(3+) complexes suggested that C-6 carbonyl group inGTP and GDP may be involved in complex formation, which may be responsible for the effectiveenergy transfer. This is further supported by comparing the UV spectra of ATP, Poly(A), GTP,and Poly(G) with their Tb~(3+) complexes in water solution.     

Domain Structures in Minerals

Domain structures in mineral crystals could be categorized into three groups and several subgroups within each group, based on characteristics of domain structures and mechanisms causing domain structures: (ⅰ) domain structures constituted by domains with the same (or identical) crystal structure and chemical composition, including anti-phase domain structures, twinning domain structures, inversion domain structures, and translationtwinning domain structures; (ⅱ) domain structures constituted by two or more than two kinds of domains with the same chemical composition but different crystal structures; and (ⅲ) domain structures constituted by two kinds of compositional and structural different domains, including exsolution-induced and polysomatic reaction-induced domain structures. Different types of domain structures may display different phenomena in their TEM images and SAED patterns, due to different crystallographic characteristics of different domain structures. The domain structures in minerals     

Raman Spectroscopic Studies on the Complexation and Adsorbed Behaviour of Thiourea

Raman spectroscopic studies on thiourea (TU) in highly acidic media (e. g. >3 mol/L HC1O4) show that TU as a solution species is protonated through its sulphur atom and forms complex with anions. However, as an adsorbed species, TU is protonated via the nitrogen atom and adsorbed at the silver electrode surface through the sulphur atom. The distinct effects of pH and anions of the solution on the surface enhanced Raman (SER) spectra of TU were investigated. In acidic and neutral solutions, TU is coadsorbed with anions through its NH3 and - NH2 groups respectively.     

Langmuir-Blodgett Films from Schiff Base Aluminium (Ⅲ) Complex

The characteristics of the LB films of Schiff base aluminium(Ⅲ), tris(2-hydroxy-5-nitro-N-dodecyl-benzylideneaminato) aluminium(Ⅲ)[Al(TA12)_3], were studied. The surface pressure-area(π-A) isotherm of Al(TA12)_3 in the pure water subphase was investigated. The molecular area, 0.48 nm~2, is one-third of the expected value that indicates the formation of an aggregate. The Langmuir-Blodgett(LB) films of Al(TA12)_3 were transferred and characterized. The UV-Vis spectra and the AFM image both confirmed that the J-aggregates formed. The polarized UV-Vis spectra indicated that the complex plane had to be oriented with an angle of about 30° to the substrate surface. The IR spectra suggested that the complexation took place between aluminium ions and the oxygen atoms of the ligand rather than the nitrogen atom.     

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.     

铝酸钠溶液的紫外吸收峰

分别用量子化学MNDO和DV-X_α方法计算了二聚铝酸离子[Al_2O(OH)_6]~(2-)和Al(OH)_4~-。结果表明前者旋转势垒很低, 只有10.08 kJ·mol~(-1), 最稳定平衡构型为C_s。用X_α过渡态理论计算获得这两个离子紫外吸收峰的理论值分别为266.6 nm和234.4 nm, 与实验值270.0 nm和230.0 nm相当接近。因此可以认为, 紫外吸收峰270.0 nm和230.0 nm分别为[Al_2O(OH)_6]~(2-)和Al(OH)_4~-离子的最高占有轨道电子向最低空轨道跃迁时产生的吸收峰。计算结果支持铝酸钠溶液中存在二聚铝酸离子的观点。     

The Influence of Alkali Metal Ions on Homogeneous Nucleation of Al(OH)(3) Crystals from Supersaturated Caustic Aluminate Solutions

Homogeneous nucleation of Al(OH)(3) crystals from synthetic, optically clear, caustic aluminate solutions and the influence of alkali metal ion (Na(+) versus K(+)) have been investigated under isothermal, batch crystallization conditions. The nucleation kinetics showed a seventh-order dependence upon Al(III) relative supersaturation and a strong temperature effect. Activation energy of 160 kJ mol(-1) and interfacial energy of 33 mJ m(-2) were estimated and found to be independent of alkali ion, as was the Al(OH)(3) equilibrium solubility. The nucleation rate, however, was faster in aging sodium than in potassium aluminate solutions. It appears that Na(+) ions provide greater stability for the formation and densification of Al(III)-containing, supramolecular clusters which grow more rapidly into Al(OH)(3) crystallites than do K(+) ions. The development of the Al-OH octahedral structure of Al(OH)(3) nuclei is an alkali metal ion-mediated, chemical reaction-controlled condensation process, displaying specific gibbsite (gamma-Al(OH)(3))-bayerite (alpha-Al(OH)(3)) dimorphism. Furthermore, significant differences in the level of alkali ion incorporation, reflecting in the purity and morphology of the crystalline product, were observed. Copyright 2000 Academic Press.     

溶胶-凝胶法制备纳米氢氧化铝溶胶

研究了利用铝酸钠溶液碳酸化产生的沉淀, 经胶溶作用制备出纳米氢氧化铝溶胶的过程. 分析了铝酸钠溶液滴加到大量碳酸氢钠溶液中时发生的反应. X射线衍射研究结果表明, 在纳米氢氧化铝溶胶制备过程中, 从无定形氢氧化铝沉淀到拟薄水铝石的晶型转变过程是氢氧化铝沉淀胶溶时溶解再析出的过程. 将碳酸氢钠加入到苛性比为1.7的铝酸钠溶液中, 中和至苛性比为1.3后, 溶液诱导期中的紫外光谱显示270 nm处的Al(OH)3-6吸收增强. 经与含铝原子六配位的晶体紫外光谱对比后表明, 在铝酸钠分解生成氢氧化铝的过程中, 其铝的配位结构从四配位转化为六配位. 拟薄水铝石溶胶粒子的形貌与胶溶所用的酸和分散剂有关.     

Aluminum-27 NMR studies of alcoholic (2-hydroxyethyl)trimethylammonium aluminate solutions

²⁷Al NMR spectroscopy is a power tool for investigation of the aluminate species existing in both aqueous and non-aqueous solutions. Aluminum-27 nuclear magnetic resonance (NMR) spectroscopy also can be used to determine thermodynamic properties of complexes in the solution. In this report, ²⁷Al NMR spectroscopy was used to characterize species present in alkaline alcoholic aluminate solutions. (2-Hydroxyethyl)trimethylammonium (2-EHTMA) hydroxide was used as base. In solution of CH₃OH and H₂O in a mole ratio of 64:1 it was possible to detect five signals by aluminum-27 NMR, indicating formation of [Al(OH)_4−n(CH₃OH)_n]⁽ⁿ⁻¹⁾⁺ (n = 0,1, 2, 3 and 4) species. Aluminum-27 NMR spectroscopy has also used for investigation of the species present in the ethanolic 2-HETMA aluminate solutions. The equilibrium constants for the formation of aluminate complexes were also determined for both methanolic and ethanolic aluminate solutions. Aluminum-27 NMR spectra of propanolic and butanolic 2-HETMA aluminate solutions were also studied.     

Aluminium complexes in methanol-water mixture as studied by 27Al NMR nuclear magnetic resonance

(27)Al NMR spectroscopy can be used for study of coordination and solvation in both aqueous and non-aqueous solutions. Various octahedral and tetrahedral aluminium complexes have been proved to exist in solution by (1)H and (27)Al NMR spectroscopy. (27)Al nuclear magnetic resonance (NMR) spectroscopy also can be used to determine thermodynamic properties of complexes in the solution. The formation of [Al(OH)(4-n)(CH(3)OH)(n)]((n-1)+) (n=1, 2, 3 and 4) species through the reaction of aluminate anion with methanol has been investigated by (27)Al NMR spectroscopy. (27)Al NMR spectra reveal evidence for Al bound to one, two, three and four CH(3)OH, the production of aluminate species is affected by the MeOH/H(2)O. Results obtained from 2D EXSY experiments clearly confirm there are exchanges among the species.     

Kinetics of silicate exchange in alkaline aluminosilicate solutions

In strongly alkaline aqueous KOH solutions containing SiIV in large excess over AlIII, the kinetics of exchange of monomeric silicate with small acyclic aluminosilicate solute species is much more rapid than with either cyclic aluminosilicates or any all-silicate anions. Selective inversion recovery 29Si NMR studies of homogeneous solutions of stoichiometric composition 3.0 mol kg-1 of SiO2, 0.1 mol kg-1 of Al2O3, and 8.0 mol kg-1 of K2O in 60-75% D2O gave rate constants of 2.0 +/- 0.2 kg mol-1 s-1 and 17 +/- 4 s-1 for the forward and reverse reactions of monomeric silicate with (HO)3AlOSiOn(OH)(3-n)(n+1)- (n = 2 or 3) at 0 degree C. These rate constants are more than 10(4)-fold faster than those extrapolated from 60 to 90 degrees C for comparable reactions of silicate anions. The greater lability of acyclic aluminate centers relative to silicate is ascribed partly to the availability of HO- groups for condensation reactions on Al and mainly to the ease of expansion of the coordination number of AlIII beyond 4. The latter attribute is diminished when AlIII is constrained to be tetrahedral in cyclic structures. With respect to the mechanism of formation of zeolites from alkaline aqueous media, it is suggested that small, labile AlOSi units add rapidly to growing zeolitic structures "on demand", whereas the more kinetically inert cage or ring structures cannot. This would explain why a silicate or aluminosilicate structure that is dominant among solute species at equilibrium in the presence of a particular cation may bear little or no geometric relation to the zeolitic framework promoted kinetically by that same cation.     

Complexation of aluminate anion by bis-tris in aqueous media at 25–50°C

Gibbsite, Al(OH)₃, solubility studies in aqueous NaCl solutions at pH 9 demonstrate that the aluminate anion forms a strong complex with the neutral Bis-tris molecule 2,2-Bis(hydroxymethyl)-2,2,2-nitrilotriethanol, at low temperatures. The logarithm of the molal concentration quotient for the reaction

浓碱高苛性比铝酸钠溶液中水合铝硅酸钠形成的动力学研究

研究了沈碱高苛性比铝酸钠溶液中水合铝硅酸钠形成的动力学行为,反应对Ａｌ（ＯＨ）４＾－,ＳｉＯ２（ＯＨ）２＾２－均为一级反应。结合溶液的结构和沸石形成机理,提出了五配位中间体形成机理。提高反应温度,降低碱浓度,加强搅拌或加入晶种（或杂质）均有利于水合铝硅酸钠的形成。