Gas phase reactions of Cl2O with X−(D2O)n=0–4 (X = O,OD, O2, DO2, and O3)

The reactions of Cl₂O with the cluster ions X⁻(D₂O)_n=0–4 (X = O, OD, O₂, DO₂, and O₃) were studied in a He buffer gas at temperatures within the range 171–298 K and pressures of 0.27–0.51 Torr, using a flow-tube apparatus. All ions were found to react with Cl₂O at rates slower than predicted by the collision rate and the charge center was transferred from X⁻ to Cl⁻ or ClO⁻. The primary product ions Cl⁻(DOCl) and ClO⁻(DOCl) were observed to react further to produce the ions Cl₃O⁻ and Cl₃O₂⁻. The rate constants for the observed reactions are reported and the role that thermodynamics plays in determining possible reaction channels is discussed.     

Recovery of Mn0.8Zn0.2Fe2O4 from Zn–C battery: auto-combustion synthesizes,characterization, and electromagnetic properties

Journal of Sol-Gel Science and Technology - Mn0.8Zn0.2Fe2O4 ferrites were successfully prepared via a recycling process of spent Zn–C batteries (SZCBs) using sol–gel auto-combustion...     

Investigation of the Crystallization Kinetics of Zn(Leu)SO _4·0.5H_2O in Mixing Solvent by

IntroductionZincisanessentialtraceelementtoorganism .α Aminoacidisthebasicunitofproteinrelatedwithlife .L α Leu(leucine)isoneofeightsortsofaminoacidsindispensabletolifewhichareabsorbedfromfoodbecauseitcannotbesyn thesizedinhumanbody .Thecomplexesofzincsaltswithα aminoacidasadditivehaveawideapplicationinmedicine ,foodstuffandcosmetics.1 3Thesyntheticmethodsofthecom plexesofzincsaltswithα aminoacidhavebeenreviewed .4 ,5ThesolubilityofZnSO4 Leu H2 Osystemat 2 98 15Khasbeeninvestigatedbys…     

Thermal Behavior and Decomposition Kinetics of the Complexes of CuX_2 (X=NO_3, Br, Cl and ClO_4) with 3,3''''-Dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanone

Introduction N-1-Alkyl-substituted 1,2,4-triazole compounds, like some other heterocyclic derivatives containing nitrogen, have recently been the subjects of numerous studies due to their fungicidal action1 and plant growth regulation.2 Among them, the complexes with a sort of triazole as ligand are of considerable interest because of their broad-spectrum bioactivity, coordination and photo-chemical properties, as well as many potential applica-tions in various fields.3,4 In our previous paper…     

Kinetics and modeling of the H2?O2?NOx system

The addition of NO (0 to 400ppm) to mixtures of H₂ (ca. 1%) and O₂ (0.7 to 22%) has been studied over the temperature range 700 to 825 K, in a flow reactor at atmospheric pressure. The overall effect of NO is to promote the oxidation of H₂ but high concentrations of O₂ actually inhibit the NO-promoted oxidation of H₂. A detailed kinetic mechanism has been constructed and found to describe the experimental observations. The promotion of the oxidation of H₂ arises through the catalytic cycle The ability of R.34 to reactivate chains normally terminated by the formation of HO₂ is a key feature of this system. The predictions are highly sensitive to the rate of the reaction R.5 and the rate constants for this reaction is the only adjustable parameter required in the model. The value of k_5,N2 found to describe all the results has an absolute uncertainty <35%. The uncertainty relative to other important rate constants in the H₂? O₂ system is less than 10%. © 1995 John Wiley & Sons, Inc.     

Comparison of the crystal structures of Co2(X 2O7)·2H2O,X=P and As

Summary Crystals of Co₂(X ₂O₇)·2H₂O,X=P/As were synthesized under hydrothermal conditions. Their crystal structures were determined by single crystal X-ray diffraction:a=6.334(1)/6.531(2),b=13.997(2)/14.206(4),c=7.637(1)/7.615(2)Å, =94.77(2)/94.74(2)°, space group P2₁/n,R=0.032/0.046,R _w=0.028/0.034 for 2423/2042 reflections and 131/119 variables. Within the twoXO₄ tetrahedra connected via a common corner to anX ₂O₇ group the average P-O bond lengths are approximately equal (1.540 and 1.543 Å), but As-O differs significantly (1.685 and 1.696 Å). A comparison with the isotypic Mn and Mg pyrophosphates shows a correlation between the ratio Me-O/X-O and the angle O-X-O.

---

Vergleich der Kristallstrukturen von Co₂(X ₂O₇)·2H₂O,X=P und As

Zusammenfassung Kristalle von Co₂(X ₂O₇)·2H₂O,X=P/As wurden unter Hydrothermalbedingungen synthetisiert. Ihre Kristallstrukturen wurden mittels Röntgenbeugung an Einkristallen bestimmt:a=6.334(1)/6.531(2),b=13.997(2)/14.206(4),c=7.637(1)/7.615(2) Å, =94.77(2)/97.74(2)°, Raumgruppe P2₁/n,R=0.032/0.046,R _w=0.028/0.034 für 2423/2042 Reflexe und 131/119 Variable. In den beiden über eine gemeinsame Ecke zuX ₂O₇-Gruppen verknüpftenXO₄-Tetraedern sind die mittleren P-O-Abstände ungefähr gleich (1.540 und 1.543 Å), hingegen differiert As-O signifikant (1.685 und 1.696 Å). Ein Vergleich mit den isotypen Mn- und Mg-Pyrophosphaten zeigt eine Korrelation zwischen dem Quotienten Me-O/X-O und dem WinkelX-O-X.

     

Preparation of graphene/BaFe12O19–Ni0.8Zn0.2Fe2O4 nanocomposite and its microwave absorbing properties

BaFe₁₂O₁₉–Ni_0.8Zn_0.2Fe₂O₄/graphene nanocomposites were prepared by a deoxidation technique. The structure, morphology and electromagnetic properties of the samples were detected by means of X-ray diffraction, scanning electron microscope, transmission electron microscopy, Raman, thermogravimetric analysis. Results show that the BaFe₁₂O₁₉–Ni_0.8Zn_0.2Fe₂O₄ nanoparticles dispersed on the graphene sheets. The magnetic properties of the composites decreased with the increasing of graphene contents, However, the electrical conductivity is in the contrary. Measurement of electromagnetic parameters shows that when the mass ratio of BaFe₁₂O₁₉–Ni_0.8Zn_0.2Fe₂O₄ to graphene is 5:1, it can be matched well. The microwave absorption property of it is below ?10 dB at 6.8–8.2 GHz and the minimum loss value is ?19.63 dB at 7.2 GHz. The introduction of graphene can increase the dielectric loss and has an important effect on the microwave absorption properties.     

AFM investigations on the influence of CO2 exposure on Ba0.5Sr0.5Co0.8Fe0.2O3–δ

In this work, fresh and CO₂-exposed specimens of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3–δ (BSCF) are examined by atomic force microscopy (AFM) using amplitude-modulated Kelvin probe force microscopy (KPFM) and also electrostatic force microscopy (EFM) to characterize the early stages of the formation of reaction products due to reaction with gaseous CO₂. A comparison is made with results from electron microscopy on the same samples. BSCF specimens exposed for 24 and 240 h to an atmosphere of 99.9 % CO₂ at 900 °C, respectively, were analyzed and compared with non-exposed specimens. The observation of interconnected carbonate islands on BSCF forming a continuous carbonate layer after some exposure to CO₂ indicates a Stranski–Krastanov or Volmer–Weber growth mechanism of the carbonate layer. Our results demonstrate that the measurement of surface potential variations by means of KPFM and EFM constitutes a very sensitive technique to detect the formation of reaction layers on gas permeation membranes such as BSCF. In contrast to electron microscopy techniques, scanning probe techniques permit the investigation of the topography and of electrochemical characteristics of the sample surface as received and without further preparation.     

Synthesis and characterization of LiMn0.8Fe0.2PO4/rGO/C for lithium-ion batteries via in-situ coating of Mn0.8Fe0.2C2O4·2H2O precursor with graphene oxide

Journal of Solid State Electrochemistry - LiMn0.8Fe0.2PO4 is a potential candidate cathode material to balance the energy density, safety, and cost of power lithium ion batteries. However, the low...     

Redox chemistry and magnetism of LaSrM(0.5)Ru(0.5)O(4±δ) (M = Co, Ni and Zn) Ruddlesden-Popper phases

The n = 1 Ruddlesden-Popper (RP) phases LaSrM(0.5)Ru(0.5)O(4±δ) (M = Co, Ni and Zn) have been prepared by solid state reactions and structurally characterized by powder X-ray and electron diffraction. All the samples adopt the tetragonal I4/mmm space group with random M and Ru cation occupation on the B-sites. The potential causes of no cation ordering are discussed. A combined analysis of the tolerance factors, the distortion of the octahedral coordination of M and Ru cations and the magnetic interactions between M and Ru cations provide a better understanding for forming a phase with 3D cation ordering on the B-sites in the n = 1 RP phases. The investigation of XPS spectra suggests that the transition element species exist as mixed ion pairs, Ru((4-δ)+)-Ru(4+)? Co(2+)-Co(3+) in LaSrCo(0.5)Ru(0.5)O(4), and Ru(4+)-Ru((4+δ)+)? Ni(+)-Ni(2+) in LaSrNi(0.5)Ru(0.5)O(4), which is consistent with cation disorder over the B sites. LaSrCo(0.5)Ru(0.5)O(4) shows a weakly ferromagnetic behaviour below 50 K; LaSrNi(0.5)Ru(0.5)O(4) is evidenced by the presence of long-range magnetic ordering at a Néel temperature of 125 K, and LaSrZn(0.5)Ru(0.5)O(4) exhibits a paramagnetic behaviour down to 5 K. Due to atomic disorder, Ru4d, O2p covalent coupling is weakened, strengthening the intraatomic spin-spin coupling among the π* electrons. Charge transfer between Ru and Co or Ru and Ni, as well as the increasing overlap of both nearest-neighbour and next-nearest-neighbour Ru 4d electrons due to atomic disorder, favour the formation of ferromagnetic interactions. Although antiferromagnetism is dominant, particularly in LaSrNi(0.5)Ru(0.5)O(4), ferromagnetic interactions are stronger in the title compounds than in the related La(2)MRuO(6) (M = Co, Ni) double perovskites where the B-site cations are ordered.     

Crystallization of Mg(Fe0.8Ga0.2)2O4-δ films on silicon with SiO2 and TiO2 buffer layers

The results of analysis of conceivable interactions between film and substrate materials during crystallization of Mg(Fe_0.8Ga_0.2)₂O_4-δ films with SiO₂ and TiO₂ buffer layers on silicon are reported. The calculated data are compared with the physicochemical parameters of Mg(Fe_0.8Ga_0.2)₂O_4-δ/Si, Mg(Fe_0.8Ga_0.2)₂O_4-δ/TiO₂/Si, and Mg(Fe_0.8Ga_0.2)₂O_4-δ/SiO₂/Si film heterostructures.     

Study of the process of the formation of Mg(Fe0.8Ga0.2)2O4 − δ films on Si

Conditions of the synthesis of magnetic semiconductor films of composition Mg(Fe_0.8Ga_0.2)₂O_4?δ on silicon have been optimized. As the barrier layer, which prevents the interaction between the film and the substrate during high-temperature crystallization of the films, a film of nanosized silicon dioxide was used. This, together with a high homogeneity of the composition of the target, allowed us to obtain Mg(Fe_0.8Ga_0.2)₂O_4?δ films on silicon characterized by the saturation magnetization (37 A m²/kg) that noticeably exceeds that for the volumetric analog (28 A m²/kg).     

Kinetics of CH(X2Π) radical reactions with propane,isobutane and neopentane

Rate constants over the temperature range 298–689 K are reported for the reaction of CH(X²Π) radicals with C₃H₈, i-C₄H₁₀ and neo-C₅H₁₂. The CH radical was generated by multiphoton laser photolysis of CHBr₃ and its disappearance monitored by laser-induced fluorescence (LIF) at 429.8 nm. Absolute rate constants were determined as a function of temperature and total pressure. The following Arrhenius parameters were derived: k = (1.85 ± 0.13) × 10⁻¹⁰ exp[(240±30)/T] cm³/s for CH+propane; k = (2.03±0.19)×10⁻¹⁰ exp[(240±40)/T] cm³/s for CH+isobutane; k = (1.61±0.10)×10⁻¹⁰ exp[(340±30)/T] cm³/s for CH+neopentane, all independent of total pressure. The negative temperature dependences along with the energetics and lack of pressure effects lead to the conclusion that the reactions proceed by CH insertion into the alkane. The activated adduct thus formed rapidly decomposes via many energetically accessible channels. An analysis of CH reactions with C₁ to C₅ alkanes shows an increase in the room temperature rate constants in going from C₁ to C₄ irrespective of the nature of CH bonds. The rate constant then begins to level off near ≈ 5 × 10⁻¹⁰ cm/s for C₄ and C₅ alkanes.     

Kinetics and mechanism of the dehydration of α-NiSO4·6H2O

A study of the thermal dehydration of α-NiSO₄·6H₂O has been performed by power compensation differential scanning calorimetry in flowing nitrogen. No significant differences in behaviour were observed using either uncrushed crystalline powders or single crystal slabs cleaved parallel to {001}. In good agreement with previous findings, the kinetic analysis of the thermal curves confirms the validity of an=2 Avrami-Erofeev equation (AE2) in isothermal experiments at low (338–343 K) temperatures or in the initial portions of variable temperature runs. The kinetic obedience is however of an ‘order of reaction’ type for the main portion of the variable temperature runs and, for isothermal experiments, in the upper part of the temperature range investigated. Values of activation energies and frequency factors are reported. Parallel studies by optical microscopy showed relevant changes of surface texture when partially (thermally or vacuum) dehydrated {001} cleaved surface were submitted to rehydration. This phenomenon (named orange peel formation) indicates that a dehydrated layer forms on the crystal surfaces preceding the appearance of product crystals (germination or nucleation). Microscopy also revealed that reaction goes on inside the crystal and that product formation takes place in the bulk phase, following lattice collapse in experiments at high heating rates. Combined with previous results, these new experimental findings allow us to formulate a mechanism for the present transformation, comprising three main rate processes:

1. the reaction (detachment of water molecules from their lattice positions in the reactant);
2. the migration of the water molecules freed by the reaction through the initially formed, water-depleted layer enveloping the reactant crystal;
3. the crystallization of such a layer to form the product.

     

Microwave-induced combustion synthesis and characterization of NixCo1−xFe2O4 nanocrystals (x = 0.0, 0.4, 0.6, 0.8, 1.0)

A series of Ni-doped cobalt ferrites Ni_xCo1_−xFe₂O₄ (x = 0.0, 0.4, 0.6, 0.8, and 1.0) were prepared using microwave-induced combustion. Nickel, cobalt, and ferric nitrates were used as starting materials and glycine as fuel. The influence of Ni content on the lattice parameter, stretching vibrations, and magnetization was studied. XRD, FTIR, and SEM were used for structure, composition, and morphology investigation. A porous network structure was observed with average particle size 60–67 nm. All samples had a cubic spinel structure. The unit cell parameter “a” decreases linearly with nickel concentration due to the smaller ionic radius of nickel. Magnetization measurements showed that coercivity decreased as Ni content increased; it increased with decreasing temperature.      

Vibrational Properties of LaNb0.8M0.2O4-δ (M=As,Sb, V,and Ta)

LaNb_0.8M_0.2O_4-δ (where M=As, Sb, V, and Ta) oxides with pentavalent elements of different ionic sizes were synthesized by a solid-state reaction method. The vibrational properties of these oxides have been investigated. These studies revealed that the substituent element influences both Debye temperature value as well as the Raman active vibrational modes. Additionally, the low-temperature vibrational properties of LaNb_0.8Sb_0.2O_4-δ have been determined to show the phase transition occurrence at 260 K which is lower than previously reported.     

Magnetic and high rate adsorption properties of porous Mn(1-x)Zn(x)Fe2O4 (0 ≤ x ≤ 0.8) adsorbents

Porous spinel ferrites Mn(1-x)Zn(x)Fe(2)O(4) (0 ≤ x ≤ 0.8) are synthesized by a simple sol-gel method with egg white. All samples exhibit porous morphologies and large BET surface area (S(BET)). The substitution of Zn(2+) affects the magnetic properties of ferrites and the adsorption properties of methylene blue (MB) on ferrites, obviously. The saturation magnetization (Ms) of Mn(1-x)Zn(x)Fe(2)O(4) increases before x=0.4, and decreases with further increase of Zn(2+) substitution. This can be ascribed to the changes of the cationic distribution and the variation of spin arrangement in A-site and B-site of spinel structure. All samples show high adsorption capacity and the removal efficiencies of MB reach up to >90% within 3 h. The Zn(2+) substitution accelerates the adsorption rate and capacity of MB on Mn(1-x)Zn(x)Fe(2)O(4). The quickest adsorption occurred at x=0.2 and the largest adsorption capacity occurred at x=0.8.     

Synthesis,Crystal Structures,and Properties of (4,4'-Hbipy)2[Sn2(C2O4)3] and (4,4'-Hmbipy)[SnX2] (X = C2O42–, m = 2; X = Cl,m = 0; bipy = bipyridine)

Three new tin coordination compounds (4,4'-Hbipy)₂[Sn₂(C₂O₄)₃] ( 1 ), (4,4'-H₂bipy)[Sn(C₂O₄)₂] ( 2 ), and SnCl₂(4,4'-bipy) ( 3 ) were synthesized under hydro-(solvo-)thermal conditions and their crystal structures were determined by single-crystal X-ray diffraction. Compound 1 exhibits a ionic structure based on discrete [4,4'-Hbipy]⁺ cations and [Sn₂(C₂O₄)₃]^2– anions. These two units are linked via N–H ··· O hydrogen bonds to form a pseudo-one-dimensional zigzag hydrogen-bonded chain. In compound 2 , four-coordinate Sn atoms form monomeric tin dioxalato complexes, which are connected to the doubly protonated [4,4'-H₂bipy]²⁺ cations through N–H ··· O hydrogen bonded to give a one-dimensional zigzag hydrogen-bonded chain. Compound 3 forms a three-dimensional hydrogen-bonded network, in which ¹_∞[SnCl₂(4,4'-bipy)] linear chains are interconnected to each other by C–H ··· Cl hydrogen bonding. The solid-state UV/Vis/NIR diffuse reflectance spectroscopy shows that three compounds are broadband semiconductors. The thermogravimetric analysis evidences the thermal stability of the three compounds up to 175, 201, and 246 °C, respectively.     

Bending modes of the water molecules and the MO stretching modes in the series MF2 · 4H2O (M = Fe,Co, Ni,Zn)

The infrared spectra of the series MF₂·4X₂O (M = Fe, Co, Ni, Zn; X = H, D) are reported in the frequency ranges of the bending vibrations of the water molecules (ν₂) at 296 and ∼100 K and the MO lattice vibrations (ν_MO) at 296 K. Four ν_MO vibrations consisting of two doublets are identified using deuterium substitution. The various ν_ZnO vibrations correlate well with the metal-oxygen distances R(ZnO), and this correlation is further used to calculate R(MO)'s of the remainder of the series and to refine R(ZnO). Four ν₂(H₂O, HDO, D₂O) vibrations, consisting of two sharp overlapping bands flanked by two broad shoulders, are identified. The number of ν₂(H₂O) components, the sequence of ν₂ in the series and the correlation with R(MO) suggest that the ν₂ frequencies are mainly determined by R(MO). Using this assignment the two types of ν₂ bands are assigned to the two types of crystallographically distinct water molecules found in the MF₂·4H₂O structure.