Impact of Sulphate counter ion in the migration of sodium ion through soils

Laboratory advection-diffusion tests are performed on two regional soils-Brown Earth and Red Earth-in order to assess their capacity to control contaminant migration with synthetic contaminant solution of sodium sulphate with sodium concentration of 1000 mg/L. The test was designed to study the transport/attenuation behaviour of sodium in the presence of sulphate. Effective diffusion coefficient (De) that takes into consideration of attenuation processes is used. Cation exchange capacity is an important factor for the attenuation of cationic species. Monovalent sodium ion cannot usually replace other cations and the retention of sodium ion is very less. This is particularly true when chloride is anion is solution. However, sulphate is likely to play a role in the attenuation of sodium. Cation exchange capacity and type of exchangeable ions of soils are likely to play an important role. The effect of sulphate ions on the effective diffusion coefficient of sodium, in two different types of soils, of different cation exchange capacity has been studied. The effective diffusion coefficients of sodium ion for both the soils were calculated using Ogata Bank’s equation. It was shown that effective diffusion coefficient of sodium in the presence of sulphate is lower for Brown Earth than for Red Earth due to exchange of sodium with calcium ions from the exchangeable complex of clay. The soil with the higher cation exchange retained more sodium. Consequently, the breakthrough times and the number of pore volumes of sodium ion increase with the cation exchange capacity of soil.

Ion exchange equilibria between (Mn,Co)O solid solution and (Mn,Co)Cr2O4 and (Mn,Co)Al2O4 spinel solid solutions at 1100oC

The compositions of the (Mn,Co)O solid solution with rock salt structure in equilibrium with (Mn,Co)Cr2O4 and (Mn,Co)Al2O4 spinel solid solutions have been determined by X-ray diffraction measurements at 1100° C and an oxygen partial pressure of 10–10 atm. The ion exchange equilibria are quantitatively analysed, using values for activities in the (Mn,Co)O solid solution available in the literature, in order to obtain activities in the spinel solid solutions. The MnAl2O4-CoAl2O4 solid solution exhibits negative deviations from Raoult's law, consistent with the estimated cation disorder in the solid solution, while the MnCr2O4-CoCr2O4 solid solution shows slightly positive deviations. The difference in the Gibbs free energy of formation of the two pure chromites and aluminates derived from the results of this study are in good agreement with recent results obtained from solid oxide galvanic cells and gas-equilibrium techniques.

Inter and intra crystalline ion exchange equilibria in the system Fe Cr Al O

The tie lines delineating ion-exchange equilibria between FeCr2O4FeAl2O4 spinel solid solution and Cr2O3Al2O3 solid solution with corundum structure have been determined at 1373 K by electron microprobe and EDAX point count analysis of oxide phases equilibrated with metallic iron. Activities in the spinel solid solution are derived from the tie lines and the thermodynamic data on Cr2O3Al2O3 solid solution available in the literature. The oxygen potentials corresponding to the tie-line composition of oxide phases in equilibrium with metallic iron were measured using solid oxide galvanic cells with CaOZrO2 and Y2O3ThO2 electrolytes. These electrochemical measurements also yield activities in the spinel solid solution, in good agreement with those obtained from tie lines. The activity-composition relationship in the spinel solid solution is analysed in terms of the intra-crystalline ion exchange between the tetrahedral and octahedral sites of the spinel structures. The ion exchange is governed by site-preference energies of the cations and the entropy of cations mixing on each site.

On the magnetization reversal of the oxide-based exchange spring magnet

The role of the soft phase (Ni0.8Zn0.2Fe2O4) on the magnetization reversal and coercivity mechanism of the Ni0.8Zn0.2Fe2O4/BaFe12O19 nanocomposite has been investigated. The presence of the interacting field and the disorder in the nanocomposite has been confirmed by the variation of Jr/Jr(∞) vs Jd/Jr(∞) and the irreversible magnetization. To understand the relative strength of the pinning and the nucleation, the magnetic viscosity measurement has been done and the thermal activation volume has been estimated. From the Barbier plot and the activation volume measurement, the dominant mechanism governing the magnetization reversal process has been proposed.

Gold(I)-selenolate complexes: Synthesis, characterization and ligand exchange reactions

In this paper, the synthesis and characterization of some imidazole-based gold-selenolates are described. This study indicates that the nature of selenolate plays an important role in ligand exchange reactions in gold(I) selenolates. Furthermore, the reactivity of imidazole-based gold(I) selenolates toward nucleophiles such as selenols and phosphines is strikingly different from that of the N,N-dimethylaminobenzylamine-based gold(I) complexes. The presence of Se ... N non-bonded interactions in N,N-dimethylaminobenzylamine-based gold(I) complexes modulates the reactivity of Au(I) centre towards incoming nucleophiles.

Low temperature synthesis of layered NaxCoO2 and KxCoO2 from NaOH/KOH fluxes and their ion exchange properties

We report a low temperature synthesis of layered Na0×20CoO2 and K0×44CoO2 phases from NaOH and KOH fluxes at 400°C. These layered oxides are employed to prepare hexagonal HCoO2, LixCoO2 and Delafossite AgCoO2 phases by ion exchange method. The resulting oxides were characterised by powder X-ray diffraction, X-ray photoelectron spectroscopy, SEM and EDX analysis. Final compositions of all these oxides are obtained from chemical analysis of elements present. Na0×20CoO2 oxide exhibits insulating to metal like behaviour, whereas AgCoO2 is semiconducting.

Density matrix renormalization group algorithm for Bethe lattices of spin-1/2 or spin-1 sites with Heisenberg antiferromagnetic exchange

A density matrix renormalization group (DMRG) algorithm is presented for the Bethe lattice with connectivity Z = 3 and antiferromagnetic exchange between nearest-neighbor spins s = 1/2 or 1 sites in successive generations g. The algorithm is accurate for s = 1 sites. The ground states are magnetic with spin S(g) = 2(g)s, staggered magnetization that persists for large g > 20, and short-range spin correlation functions that decrease exponentially. A finite energy gap to S > S(g) leads to a magnetization plateau in the extended lattice. Closely similar DMRG results for s = 1/2 and 1 are interpreted in terms of an analytical three-site model.

Oscillatory exchange bias and training effects in nanocrystalline Pr0.5Ca0.5MnO3

We report on exchange bias effects in 10 nm particles of Pr0.5Ca0.5MnO3 which appear as a result of competing interactions between the ferromagnetic (FM)/anti-ferromagnetic (AFM) phases. The fascinating new observation is the demonstration of the temperature dependence of oscillatory exchange bias (OEB) and is tunable as a function of cooling field strength below the SG phase, may be attributable to the presence of charge/spin density wave (CDW/SDW) in the AFM core of PCMO10. The pronounced training effect is noticed at 5 K from the variation of the EB field as a function of number of field cycles (n) upon the field cooling (FC) process. For n > 1, power-law behavior describes the experimental data well; however, the breakdown of spin configuration model is noticed at n >= 1. Copyright 2012 Author(s). This article is distributed under a Creative Commons Attribution 3.0 Unported License. http://dx.doi.org/10.1063/1.3696033]

Variation of diffusivity with the cation radii in molten salts of superionic conductors containing iodine anion: A molecular dynamics study

A molecular dynamics study of the dependence of diffusivity of the cation on ionic radii in molten AgI is reported. We have employed modified Parinello-Rahman-Vashistha interionic pair potential proposed by Shimojo and Kobayashi.(1) Our results suggest that the diffusivity of the cation exhibits an increase followed by a decrease as the ionic radius is increased. Several structural and dynamical properties are reported.

Influence of anion on the quadratic nonlinearity and depolarization ratios of scattered second harmonic light from cation-pi complexes

We have investigated quadratic nonlinearity (beta(HRS)) and linear and circular depolarization ratios (D and D', respectively) of a series of 1:1 complexes of tropyliumtetrafluoroborate as a cation and methyl-substituted benzenes as pi-donors by making polarization resolved hyper-Rayleigh scattering measurements in solution. The measured D and D' values are much lower than the values expected from a typical sandwich or a T-shaped geometry of a complex. In the cation-pi complexes studied here, the D value varies from 1.36 to 1.46 and D' from 1.62 to 1.72 depending on the number of methyl substitutions on the benzene ring. In order to probe it further, beta, D and D' were computed using the Zerner intermediate neglect of differential overlap-correction vector self-consistent reaction field technique including single and double configuration interactions in the absence and presence of BF4- anion. In the absence of the anion, the calculated value of D varies from 4.20 to 4.60 and that of D' from 2.45 to 2.72 which disagree with experimental values. However, by arranging three cation-pi BF4- complexes in a trigonal symmetry, the computed values are brought to agreement with experiments. When such an arrangement was not considered, the calculated beta values were lower than the experimental values by more than a factor of two. This unprecedented influence of the otherwise ``unimportant'' anion in solution on the beta value and depolarization ratios of these cation-pi complexes is highlighted and emphasized in this paper. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4716020]

Charge order suppression, emergence of ferromagnetism and absence of exchange bias effect in Bi0.25Ca0.75MnO3 nanoparticles: Electron paramagnetic resonance and magnetization studies

We report the results of magnetization and electron paramagnetic resonance (EPR) studies on nanoparticles (average diameter similar to 30 nm) of Bi0.25Ca0.75MnO3 (BCMO) and compare them with the results on bulk BCMO. The nanoparticles were prepared using the nonaqueous sol-gel technique and characterized by XRD and TEM analysis. Magnetization measurements were carried out with a commercial physical property measurement system (PPMS). While the bulk BCMO exhibits a charge ordering transition at similar to 230 K and an antiferromagnetic (AFM) transition at similar to 130 K, in the nanoparticles, the CO phase is seen to have disappeared and a transition to a ferromagnetic (FM) state is observed at T-c similar to 120 K. However, interestingly, the exchange bias effect observed in other nanomanganite ferromagnets is absent in BCMO nanoparticles. EPR measurements were carried out in the X-band between 8 and 300 K. Lineshape fitting to a Lorentzian with two terms (accounting for both the clockwise and anticlockwise rotations of the microwave field) was employed to obtain the relevant EPR parameters as functions of temperature. The results confirm the occurrence of ferromagnetism in the nanoparticles of BCMO. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4730612]

A Rare Phenoxido/Acetato/Azido Bridged Trinuclear and an Unprecedented Phenoxido/Azido Bridged One-Dimensional Polynuclear Nickel(II) Complexes: Synthesis, Crystal Structure, and Magnetic Properties with Theoretical Investigations on the Exchange Mechanism

The reaction of a tridentate Schiff base ligand HL (2-(3-dimethylaminopropylimino)-methyl]-phenol) with Ni(II) acetate or perchlorate salts in the presence of azide as coligand has led to two new Ni(II) complexes of formulas Ni3L2(OAc)(2)(mu(1,1)-N-3)(2)(H2O)(2)]center dot 2H(2)O (1) and Ni2L2(mu(1,1)-N-3) (mu(1,3)-N-3)](n)(2). Single crystal X-ray structures show that complex 1 is a linear trinuclear Ni(II) compound containing a mu(2)-phenwddo, an end-on (EO) azido and a syn-syn acetato bridge between the terminal and the central Ni(II) ions. Complex 2 can be viewed as a one-dimensional (1D) chain in which the triply bridged (di-mu(2)-phenoxido and EO azido) dimeric Ni-2 units are linked to each other in a zigzag pattern by a single end-to-end (EE) azido bridge. Variable-temperature magnetic susceptibility studies indicate the presence of moderate ferromagnetic exchange coupling in complex 1 with J value of 16.51(6) cm(-1). The magnetic behavior of 2 can be fitted in an alternating ferro- and antiferromagnetic model J(FM) = +34.2(2.8) cm(-1) and J(AF) = -21.6(1.1) cm(-1)] corresponding to the triple bridged dinuclear core and EE azido bridge respectively. Density functional theory (DFT) calculations were performed to corroborate the magnetic results of 1 and 2. The contributions of the different bridges toward magnetic interactions in both compounds have also been calculated.

Urea-based constructs readily amplify and attenuate nonlinear optical activity in response to H-bonding and anion recognition

Urea-based molecular constructs are shown for the first time to be nonlinear optically (NLO) active in solution. We demonstrate self-assembly triggered large amplification and specific anion recognition driven attenuation of the NLO activity. This orthogonal modulation along with an excellent nonlinearity-transparency trade-off makes them attractive NLO probes for studies related to weak self-assembly and anion transportation by second harmonic microscopy.

Structural and magnetic properties of SmCo5/Co exchange coupled nanocomposite thin films

We investigated the structural and magnetic properties of SmCo5/Co exchange coupled nanocomposite thin films grown by magnetron sputtering from Sm and Co multitargets successively. The growth of the films was carried out at elevated substrate temperature followed by in situ annealing. On Si (100) substrate, X-ray diffraction confirms the formation of textured (110) SmCo5 hard phase, whereas on MgO (110) substrate, the diffraction pattern shows the epitaxial growth of SmCo5 phase with crystalline orientation along 100] direction. Secondary Ion Mass Spectroscopy reveals the structural transformation from multilayered (Sm/Co) to SmCo5/Co nano-composite films due to high reactivity of Sm at elevated temperature. Transmission electron microscopy indicates the existence of nanocrystalline phase of SmCo5 along with unreacted Co. Observed single phase behavior in magnetic hysteresis measurements indicates well exchange coupling between the soft and the hard phases in these nano-composite films. For samples with samarium layer thickness, t(sm)=3.2 nm and cobalt layer thickness, t(Co)= 11.4 nm, the values of (BH)(max) were obtained as 20.1 MGOe and 12.38 MGOe with H-c value similar to 3.0 kOe grown on MgO and Si substrates, respectively.