Synthesis and Reactivity of Mg(II)–Fe(II)–Fe(III) Hydroxycarbonates

Green rust-like compounds (GRs) were discovered as natural minerals in various hydromorphic soils, where anoxic conditions allow their stability. They may control some redox processes in aquifers and participate to the transformation of various pollutants. Since Mg(II) cations are present in the fields where GRs were discovered, a partial substitution of Mg(II) to Fe(II) leading to intermediate compounds between GRs and usual Mg(II)–Fe(III) hydroxysalts is suspected. Mg(II)–Fe(II)–Fe(II) hydroxycarbonates can be obtained as intermediate oxidation products of (Mg, Fe)(OH)₂ in carbonate-containing aqueous media obeying to [Fe^II _4(1–x)Mg^II _4x Fe^III ₂(OH)₁₂]²⁺ [CO₃ ^2– nH₂O]^–2. TMS spectra at 12 K are similar to those of GRs, i.e., two quadrupole doublets, one due to Fe(II) with a large isomer shift =1.29 mms^–1 (with respect to -iron at room temperature) and quadrupole splitting E _Q=2.76 mms^–1, the other one due to Fe(III) with smaller hyperfine parameters =0.49 mms^–1 and E _Q=0.44 mms^–1. Fe(II) ions oxidise rapidly into Fe(III) with dissolved O₂. The reactivity is similar to that of Fe(II)–Fe(III) hydroxysalts GR, and thus the potential of Mg(II)–Fe(II)–Fe(III) compounds for reducing pollutants.     

Kinetics of Bi(I) → Bi(II) transition under very high pressurization rates

Abstract

The occurrence of Bi(I) → Bi(II) transition has been examined under constant pressurization rates in the range 0.03 to 0.1GPa/(μs) by monitoring the electrical resistance of the specimen as a function of time. Such high pressurization rates have been obtained by impacting a tungsten carbide opposed anvil setup with a low velocity projectile [Rev. Sci. Instum. 60, 253 (1989)]. The time taken for the completion of the transition decreases with the increasing pressurization rate.     

Spin-glass state and ferromagnetic order in Cu(II)－Fe(III) cyanides

The static and dynamic magnetic properties of a Prussian blue analogue, molecular magnet Cu^Ⅱ_{3}[Fe^Ⅲ(CN)_6]_2·3NH_3·6H_2O were investigated in detail. The H dependence of the linear AC susceptibility, the irreversibility in the field-cooled (FC)/zero-field-cooled (ZFC) magnetization (M_{FC}/M_{ZFC}) and the relaxation of M_{ZFC} suggest that the magnetic system can be visualized as containing a ferromagnetic cluster of spin below T_C, mixed with small spin-glass clusters formed below temperature T_g less than T_C. The observed magnetic properties are explained with a ferromagnetic-spin-glass phase model. The magnetic ordering of the sample occurs below 19.8K.     

~(56)Fe(n,p)~(56)Mn反应截面测量

在E_n=12—18MeV,用活化法测量了~(56)Fe(n,p)~(56)Mn反应截面,在E_n=14.61±0.20MeV处做了绝对测量,结果为108.0±2.7毫巴.中子通量用伴随粒子法测定,并与反冲质子望远镜相比较,两种方法在1—2%的误差范围内一致.~(56)Mn的γ放射性用φ10×7.6厘米的NaI(Tl)闪烁谱仪测量,谱仪探测效率用4πβ-γ符合法标定的~(56)Mn标准源刻度.测量结果与现有数据进行了比较.     

On the electronic structure of N,N′-ethylenebis(acetylacetonatiminato)Co(II), Co(II)acacen

Single crystal E.P.R. and cobalt ENDOR measurements on N,N′-ethylenebis(acetylacetonatiminato)Co(II), Coacacen, diluted in Niacacen·1/2 H₂O are reported. Forbidden Δm _Co = 1,2 transitions in the E.P.R. spectra have been observed. The g-tensor (E.P.R.) and the cobalt hyperfine and quadrupole tensors (ENDOR) have been determined. The g- and cobalt hyperfine tensors are discussed. They support the |² A ₂,yz? groundstate proposed for four coordinated low-spin Schiff base complexes of cobalt(II). The measured quadrupole coupling is also compatible with a |² A ₂,yz? groundstate, if anisotropic contraction of the cobalt 3d orbitals is taken into consideration.     

Synthesis and Spectral Studies of Novel Co(II), Ni(II), Cu(II), Cd(II), and Fe(II) Metal Complexes with N-[5′-Amino-2,2′-bis(1,3,4-thiadiazole)-5-yl]-2-hydroxybenzaldehyde Imine (HL)

Co(II), Ni(II), Cu(II), Cd(II), and Fe(II) complexes with Schiff base derived from 2-amino-5-(2-amino-1,3,4-thiadiazolyl)-1,3,4-thiadiazole (1) and salicylaldehyde have been prepared. The ligand and its complexes have been characterized by IR, ¹H NMR spectra, elemental analyses, magnetic susceptibility, UV-Vis. and thermogravimetry–differential thermal analysis (TGA-DTA). The analytical data show 1:2 metal-to-ligand ratio for Co(II), Ni(II), Cd(II), and Fe(II) and 2:2 metal-to-ligand ratio for Cu(II) complexes. The suggested structures for the N-[5′-Amino-2,2′-bis(1,3,4-thiadiazole)-5-yl]-2-hydroxybenzaldehyde Imine (HL) complexes of Fe(II), Co(II), and Cd(II) are octahedral, for the Ni(II) complex is tetrahedral, and for the Cu(II) complex is square-planar     

Template synthesis and characterisation of MCM-41 mesoporous molecular sieves containing various transition metal elements—TME (Cu,Fe, Nb,V, Mo)

A series of metallosilicates (transition metal elements—TME) MCM-41 (TME=Fe, Cu, Nb, V, Mo) mesoporous molecular sieves with variable Si/TME ratios have been synthesized and characterised by low temperature N₂ adsorption/desorption, XRD, XPS, H₂-TPR, FTIR combined with NO+NO₂ adsorption, diffuse reflectance UV–Vis spectroscopy, and ESR study. All the materials exhibit hexagonal arrangement of uniform mesopores (with exception of CuMCM-41). Defect holes amid the nanochanels besides well-ordered mesopores characterise mainly Fe-containing materials, in which the highest TME loading was reached. Similar but smaller defects take place in NbMCM-41. The amount of TME included into MCM-41 structure under the preparation conditions used in this work changes in the order: Fe>Nb>Cu≫V≫Mo. This sequence is not related to the oxidation state of metals which was estimated in calcined materials as Fe³⁺, Nb⁵⁺, Cu²⁺, V⁵⁺, Mo⁶⁺. It does not also correlate with cation sizes in a simple way. The possibility of forming tetrahedral coordination seems to limit the TME incorporation into the MCM-41 skeleton if free metal cations are used in the gel (Cu²⁺, Fe³⁺, Nb⁵⁺). Al in the gel makes the isomorphously substitution of silicon by copper easier, but part of Cu occupies extra framework cationic positions in the final material.     

Mössbauer studies of Fe(II) chelates of bromo substituted salicylhydroxamic acids

Mössbauer study of some hydroxamic acid chelates of Fe(II) viz. Fe(II)-benzohydroxamic (Fe(II)-BHA)-, Fe(II)-salicylhydroxamic (Fe(II)-SHA)-, Fe(II)-5-Bromo salicylhydroxamic (Fe(II)-5BSHA)-, and Fe(II)-3,5 dibromo salicylhydroxamic (Fe(II)-3,5DBSHA)- acids has been done. It is found that SHA, 5BSHA and 3,5DBSHA are acting as tridentate ligands. The strength of OH(phenolic) Fe bond is considerably affected by the substitution of Br in the aromatic nucleus.

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Mössbauer studies of Fe(II) chelates of bromo substituted salicylhydroxamic acids

     

Laboratory Intercomparison on the Determination of the Fe(II)/Fe(III) Ratio in Glass Using Mössbauer Spectroscopy

A Perturbed Angular Correlation (PAC) study was performed on the system that presents a rich variety of structural and magnetic phase transitions as a function of the oxygen content (δ) or as a function of temperature (T). The PAC signal at room temperature allowed the determination of the Electrical Field Gradient (EFG) parameters and to correlate them with the lattice average symmetry namely the orthorhombic (O′ or O*) Pbnm and rhombohedral (R) phases measured by X-ray diffraction.     

La(Fe,Si)_(13)化合物的居里温度机制

NaZn13型La(Fe,Si)13化合物随Si含量增加,相变性质由一级过渡为二级,化合物晶胞体积收缩,饱和磁化强度降低,居里温度升高.其居里温度与晶胞体积之间的关系不能用Bethe-Slater曲线给出合理的解释.本文利用添加间隙原子碳调节La(Fe,Si)13化合物晶胞体积和居里温度的方法,系统研究了该化合物居里温度与晶胞体积之间的关系.结果发现二者之间的变化规律遵循Jaccarino-Walker模型,即仅有5%甚至更少的3d电子被认为是真正的巡游电子,其余的3d电子仍是局域的.以极化的巡游电子为媒介,局域电子之间产生类似于Ruderman-Kittel-Kasuya-Yosida的长程相互作用,相互作用的符号和大小与距离呈周期性震荡.随Si含量的增加,La(Fe,Si)13化合物巡游电子数目增加,化合物的居里温度由晶胞体积和巡游电子的浓度共同决定.     

Mössbauer study of a novel binuclear Fe(II/III) delocalized-valence compound

In this paper, we briefly summarize the main conclusions of the Mössbauer analysis of [L₂Fe₂(-OH)₃] (ClO₄)₂·2CH₃OH·2H₂O with L=N,N',N"-trimethyl-1,4,7-triazacyclononane, a novel dimeric iron compound, which possesses a central exchange-coupled delocalized-valence Fe(II/III) unit. The complete delocalization of the excess electron in the dimeric iron center is concluded from the indistinguishability of the two iron sites in Mössbauer spectroscopy. The magnetic Mössbauer spectra imply a system spinS _t=9/2 for the dimer in its ground state. The values for hyperfine and spin-Hamiltonian parameters, obtained from simulations of the Mössbauer spectra, are =0.74 mms^–1, E _Q=–2.14 mms^–1,A =–10.6 T,A =–13.5 T andD=1.8 cm^–1. The system spinS _t=9/2 is interpreted to be a consequence of double-exchange coupling.     

~(59)Co(n,p)~(59)Fe,~(59)Co(n,α)~(56)Mn,~(59)Co(n,2n)~(58)Co反应截面的测量

本实验用活化法测量了中子能量在12.8MeV到17.8MeV的~(59)Co(n,p)~(59)Fe,~(59)Co(n,α)~(56)Mn,~(59)Co(n,2n)~(58)Co三个反应道的反应截面值,实验的测量误差在3.3％—6.9％范围内. 本文还计算了反应截面测量误差的协方差矩阵,并将实验测量值与理论计算值进行了比较.另外,还对上述三个反应道的截面进行编评,给出了推荐的激发曲线.     

Nd_2(Fe,Si)_(17)合金的结构与磁性

本文对Nd-Fe-Si三元系富铁区域相的结构和磁性进行了研究。结果表明,Nd-Fe-Si三元系富铁区域(Fe>40at％), 除出现NdFe_2Si_2三元金属间化合物外(Si>20at％),同时只出现Nd_2(Fe,Si)_(17)赝二元金属间化合物,其中Si取代9d位的Fe原子,而不能形成类似于Nd_2Fe_(14)B的三元金属间化合物,Si取代Nd_2Fe_(17)中的9d位Fe原子后,使晶胞体积缩小;使饱和磁化强度减小;同时使Fe次晶格的铁磁相互作用增强,导致居里温度增高;还使得Fe次晶格的易面各向异性减弱,造成室温下各向异性场减小。     

Spectra-Structure Correlations in 2,2′-Bipyridine Mercury(II) Saccharinate: Comparison With Mercury(II) Saccharinate And Chloromercury(II) Saccharinate∗

Abstract

The infrared spectrum of 1:1 complex of mercury(II) saccharinate with 2,2′-bipyridine, [Hg(C₇H₄NO₃S)₂(C₁₀H₈N₂)], was studied in the CO and SO₂stretching regions. The appearance of the spectrum in the region of the carbonyl stretching modes was correlated with the number of non-equivalent CO groups in the structure. The spectral and structural characteristics of the CO groups in the title compound were compared with the corresponding ones in the mercury(II) saccharinate and chloromercury(II) saccharinate. It was found that the frequency of the CO stretchings in the spectrum of Hg(bpy) (sac)₂ is significantly lower (1630 and 1615 cm^?1) than the frequency of the corresponding modes in the spectra of covalently bonded mercury(II) saccharinate (1705 and 1680 cm^?1) and chloromercury saccharinate (1694 cm^?1). An attempt was also made to assign the bands which are mainly due to the symmetric and the antisymmetric SO₂ stretching vibrations.

     

Study of phase transition on nanocrystalline (La, Sr)(Mn, Fe)O system using high-pressure Mössbauer spectroscopy and high-pressure X-ray diffraction

Pressure-induced structural changes on nano-crystalline La_0.8Sr_0.2Mn_0.8Fe_0.2O₃ were studied using high-pressure Mössbauer spectroscopy and high-pressure X-ray diffraction. Mössbauer measurements up to 10 GPa showed first order transition at 0.52 GPa indicating transformation of Fe^4?+? to high spin Fe^3?+?, followed by another subtle transition at 3.7 GPa due to the convergence of two different configurations of Fe into one. High-pressure X-ray diffraction measurements carried up to 4.3 GPa showed similar results at 0.6 GPa as well as 3.6 GPa. Attempts were made to explain the changes at 0.6 GPa by reorientation of grain/grain boundaries due to uniaxial stress generated on the application of pressure. Similarly variation at 3.6 GPa can be explained by orthorhombic to monoclinic transition.     

Y(Fe,M)12化合物的电子结构与磁性(M=Nb,Si)

采用新近发展的全势能线性缀加平面波((L)APW) 局域轨道(lo)和广义梯度近似(GGA)密度泛函方法计算了Y(Fe,M)12化合物(M=Nb,Si)的电子结构,得到了相应的总态密度和局域态密度,并分析了替代原子与替代晶位不同引起态密度的变化。根据计算结果预测的居里温度变化与实验结果基本一致。