Solubilities of Benzene Derivatives in Supercritical Carbon Dioxide

The solubilities of benzene derivatives in supercritical carbon dioxide was determined by the saturation method over the pressure range (9.5 to 14.5) MPa. The solubilities were determined at (308 and 313) K for 1-chloro-2,4-dinitrobenzene and (308, 318, and 328) K for m-dinitrobenzene. At 308K, the solubility (in mole fraction) of 1-chloro-2,4-dinitrobenzene varied from (2.83 to 5.88).10(-3) while the solubility of m-dinitrobenzene increased from (2.05 to 5.54).10(-3) as the pressure increased from (9.5 to 14.5) MPa. However, the solubilities of both compounds decreased with increasing temperature. Models based on the solubility parameter and semiempirical models such as the Mendez-Santiago-Teja model, the Gordillo model, and the association model, were used to correlate the experimental solubility data for the benzene derivatives.

Theory of electron transfer processes via chemisorbed intermediates: Part II. Current-potential characteristics

Current-potential characteristics are obtained numerically for a lone-adsorbate-mediated anodic charge transfer at the electrode-solution interface. An increase in the overpotential leads to the appearance of maxima in the anodic current-potential plots instead of the extended activationless region (i.e. a saturation current at large positive overpotentials) predicted by the direct heterogeneous outer-sphere anodic charge transfer process. A detailed analysis of the dependence of current-potential profiles and other kinetic parameters on various system parameters is also presented.

Oxidation of Sulfur Dioxide in Aqueous Suspensions of Activated Carbon

Sulfur dioxide in aqueous solutions at low pH levels exists both in molecular SO2(aq) and in hydrolyzed ionic form HSO3-. Experiments indicate that only HSO3- is the reacting species in the oxidation catalyzed by activated carbon, while SO2(aq) deactivates by competing with HSO3 for the active sites of the catalyst particles. A mechanism is proposed and a rate model is developed that also accounts for the effect of sulfuric acid (product of the oxidation) on the solubility of sulfur dioxide. It predicts first order in HSO3-, half order in dissolved oxygen, and a linear deactivation effect of SO2(aq), which are confirmed by experimental data. The deactivation reaches a constant level corresponding to saturation of the active sites by SO2(aq). Activation energy for the oxidation is 93.55 kJ mol(-1) and for deactivation is 21.4 kJ mol(-1).

A Rotor Flux Estimation During Zero and Active Vector Periods Using Current Error Space Vector From a Hysteresis Controller for a Sensorless Vector Control of IM Drive

This paper proposes a sensorless vector control scheme for general-purpose induction motor drives using the current error space phasor-based hysteresis controller. In this paper, a new technique for sensorless operation is developed to estimate rotor voltage and hence rotor flux position using the stator current error during zero-voltage space vectors. It gives a comparable performance with the vector control drive using sensors especially at a very low speed of operation (less than 1 Hz). Since no voltage sensing is made, the dead-time effect and loss of accuracy in voltage sensing at low speed are avoided here, with the inherent advantages of the current error space phasor-based hysteresis controller. However, appropriate device on-state drops are compensated to achieve a steady-state operation up to less than 1 Hz. Moreover, using a parabolic boundary for current error, the switching frequency of the inverter can be maintained constant for the entire operating speed range. Simple sigma L-s estimation is proposed, and the parameter sensitivity of the control scheme to changes in stator resistance, R-s is also investigated in this paper. Extensive experimental results are shown at speeds less than 1 Hz to verify the proposed concept. The same control scheme is further extended from less than 1 Hz to rated 50 Hz six-step operation of the inverter. Here, the magnetic saturation is ignored in the control scheme.

Stability and throughput analysis of unslotted CDMA-ALOHA with finite number of users and code sharing

We consider a system comprising a finite number of nodes, with infinite packet buffers, that use unslotted ALOHA with Code Division Multiple Access (CDMA) to share a channel for transmitting packetised data. We propose a simple model for packet transmission and retransmission at each node, and show that saturation throughput in this model yields a sufficient condition for the stability of the packet buffers; we interpret this as the capacity of the access method. We calculate and compare the capacities of CDMA-ALOHA (with and without code sharing) and TDMA-ALOHA; we also consider carrier sensing and collision detection versions of these protocols. In each case, saturation throughput can be obtained via analysis pf a continuous time Markov chain. Our results show how saturation throughput degrades with code-sharing. Finally, we also present some simulation results for mean packet delay. Our work is motivated by optical CDMA in which "chips" can be optically generated, and hence the achievable chip rate can exceed the achievable TDMA bit rate which is limited by electronics. Code sharing may be useful in the optical CDMA context as it reduces the number of optical correlators at the receivers. Our throughput results help to quantify by how much the CDMA chip rate should exceed the TDMA bit rate so that CDMA-ALOHA yields better capacity than TDMA-ALOHA.

Magnetic properties of mechanically alloyed nanocrystalline Ni3Fe

Disordered nanocrystalline Ni3Fe alloy was prepared by mechanical alloying of elemental powders. X-ray diffractograms show the formation of Ni3Fe single phase. The chemical composition and morphology of the powder have been obtained by using EDAX and SEM analysis respectively. While the saturation magnetisation decreases with milling time, the coercivity increases. The width of the hyperfine field distributions obtained from Mossbauer studies shows that the alloy is highly disordered Atomic ordering is found to take place at a faster rate compared to that in the bulk alloy. (C) 1999 Acta Metallurgica Inc.

Magnetization properties of some quantum spin ladders

The experimental realization of various spin ladder systems has prompted their detailed theoretical investigations. Hen we study the evolution of ground-state magnetization with an external magnetic field for two different antiferromagnetic systems: a three-legged spin-1/2 ladder, and a two-legged spin-1/2 ladder with an additional diagonal interaction. The finite system density-matrix renormalization-group method is employed for numerical studies of the three-chain system, and an effective low-energy Hamiltonian is used in the limit of strong interchain coupling to study the two- and three-chain systems. The three-chain system has a magnetization plateau at one-third of the saturation magnetization. The two-chain system has a plateau at zero magnetization due to a gap above the singlet ground state. It also has a plateau at half of the saturation magnetization for a certain range of values of the couplings. We study the regions of transitions between plateaus numerically and analytically, and find that they are described, at first order in a strong-coupling expansion, by an XXZ spin-1/2 chain in a magnetic field; the second-order terms give corrections to the XXZ model, We also study numerically some low-temperature properties of the three-chain system, such as the magnetization, magnetic susceptibility and specific heat. [S0163-1829(99)303001-5].

Absolute Entropy and Energy of Carbon Dioxide Using the Two-Phase Thermodynamic Model

The two-phase thermodynamic (2PT) model is used to determine the absolute entropy and energy of carbon dioxide over a wide range of conditions from molecular dynamics trajectories. The 2PT method determines the thermodynamic properties by applying the proper statistical mechanical partition function to the normal modes of a fluid. The vibrational density of state (DoS), obtained from the Fourier transform of the velocity autocorrelation function, converges quickly, allowing the free energy, entropy, and other thermodynamic properties to be determined from short 20-ps MD trajectories. The anharmonic effects in the vibrations are accounted for by the broadening of the normal modes into bands from sampling the velocities over the trajectory. The low frequency diffusive modes, which lead to finite DoS at zero frequency, are accounted for by considering the DoS as a superposition of gas-phase and solid-phase components (two phases). The analytical decomposition of the DoS allows for an evaluation of properties contributed by different types of molecular motions. We show that this 2PT analysis leads to accurate predictions of entropy and energy of CO2 over a wide range of conditions (from the triple point to the critical point of both the vapor and the liquid phases along the saturation line). This allows the equation of state of CO2 to be determined, which is limited only by the accuracy of the force field. We also validated that the 2PT entropy agrees with that determined from thermodynamic integration, but 2PT requires only a fraction of the time. A complication for CO2 is that its equilibrium configuration is linear, which would have only two rotational modes, but during the dynamics it is never exactly linear, so that there is a third mode from rotational about the axis. In this work, we show how to treat such linear molecules in the 2PT framework.

Microstructural evolution and giant magnetoresistance in melt spun and annealed Cu-85(FeCo)(15) alloy

Granular alloys of Cu with FeCo were prepared by the melt-spinning technique. The alloy was characterized by x-ray, transmission electron microscopy, vibrating sample magnetometer, and magnetoresistance measurements. The alloys were heat treated for different temperatures to optimize the magnetoresistance properties. Structural characterization reveals that the FeCo phase initially precipitates out as fcc and later transforms to the bcc structure by martensitic transformation. It is seen that the trend in the magnetoresistance properties is different for the measurements carried out at room temperature and 4.2 K. This has been attributed to the transformation of fine fcc precipitates to the bcc structure during the low temperature measurements. It is seen that the presence of fine particles causes an increase in the field for saturation and is not suitable for applications where moderate field giant magnetoresistance is required. (C) 1999 American Institute of Physics. [S0021-8979(99)08317-6].

Relaxation behavior of twin nonlinear optical chromophores: Effect of the spacer length

A new series of twin nonlinear optical (NLO) molecules, having two 4-nitrophenol chromophores that are linked via a flexible polymethylene spacer of varying length [(CH2)(n), n = 1-12], were synthesized. Powder second harmonic generation measurements of these twin samples indicated a pronounced odd-even oscillation, with the odd twins exhibiting a high SHG value while the even ones gave no measurable SH signal. This behavior reflects the crystal packing preferences in such twin NLO systems that have odd and even numbers of atoms linking them - the even ones appear to prefer a centrosymmetric packing arrangement. The orientational/disordering dynamics of these twin NLO molecules, doped in a polymer (poly(methyl methacrylate)) matrix, has also been studied using SHG in electric field poled samples. Interestingly, the maximum attainable SH signal, chi((2)), in, the poled samples also showed an odd-even oscillation; the odd ones again having a higher value of chi((2)) This unprecedented odd-even oscillation in such molecularly doped systems is rationalized as being due to the intrinsically greater ease of a parallel alignment of the two chromophores in the twins with an odd spacer than in those with an even one. Further, the temporal stability of the SHG intensity at 70 degrees C, after the removal of the applied corona, was also studied. The relaxation of all the twin chromophores followed a biexponential decay; the characteristic relaxation time (tau(2)) for the slow decay component suggests that while the twin with a single methylene unit relaxes relatively slowly, the relaxation is significantly faster in cases where n = 2 and 3. In the twins with even longer spacer segments, the relaxation again becomes slower and reaches a saturation value. The observed minimum appears to reflect the interplay of two competing factors that affect the chromophore alignment in such twin systems, namely, the electrostatic repulsion between neighboring oriented dipoles and the intrinsic flexibility of the spacer.

An interesting feature of the vapour pressure curve

There exists a maximum in the products of the saturation properties such as T(p(c) - p) and p(T-c - T) in the vapour-liquid coexistence region for all liquids. The magnitudes of those maxima on the reduced coordinate system provide an insight to the molecular complexity of the liquid. It is shown that the gradients of the vapour pressure curve at temperatures where those maxima occur are directly given by simple relations involving the reduced pressures and temperatures at that point. A linear relation between the maximum values of those products of the form [p(r)(1 - T-r)](max) = 0.2095 - 0.2415 [T-r(1 - p(r))](max) has been found based on a study of 55 liquids ranging from non-polar monatomic cryogenic liquids to polar high boiling point liquids.

Investigation of reversible and irreversible polarizations in thin films of SrBi2(Ta-0.5,Nb-0.5)(2)O-9

The reversible and irreversible components of the total polarization in a thin film of SrBi2(Ta-0.5,Nb-0.5)(2)O-9 were calculated. The C-V loop was integrated to obtain the reversible part of the total polarization. The reversible polarization was only 20% of the total polarization and showed almost no hysteresis. However, the dielectric constant due to the total polarization was almost the same as that for the reversible polarization in the saturation region of the large signal P-E hysteresis loop. The reversible part was subtracted from the total polarization to calculate the irreversible counterpart of it. The irreversible polarization showed a near-square shaped hysteresis loop, while the reversible polarization was obeying the Rayleigh law. The small signal hysteresis was simulated from the parameters obtained from the Rayleigh-curve fit with the experimental curve and then it was compared with the result obtained from direct measurement with small amplitude. (C) 2002 Elsevier Science B.V. All rights reserved.

Microwave heating in multiphase systems: evaluation of series solutions

The 1D electric field and heat-conduction equations are solved for a slab where the dielectric properties vary spatially in the sample. Series solutions to the electric field are obtained for systems where the spatial variation in the dielectric properties can be expressed as polynomials. The series solution is used to obtain electric-field distributions for a binary oil-water system where the dielectric properties are assumed to vary linearly within the sample. Using the finite-element method temperature distributions are computed in a three-phase oil, water and rock system where the dielectric properties vary due to the changing oil saturation in the rock. Temperature distributions predicted using a linear variation in the dielectric properties are compared with those obtained using the exact nonlinear variation.

Synthesis of acicular hydrogoethite (alpha-FeOOH center dot xH(2)O; 0.1 < x < 0.22) particles using morphology controlling cationic additives and magnetic properties of maghemite derived from hydrogoethite

A method for the preparation of acicular hydrogoethite (alpha -FeOOH.xH(2)O, 0.1 < x < 0.22) particles of 0.3-1 mm length has been optimized by air oxidation of Fe( II) hydroxide gel precipitated from aqueous (NH4)(2)Fe(SO4)(2) solutions containing 0.005-0.02 atom% of cationic Pt, Pd or Rh additives as morphology controlling agents. Hydrogoethite particles are evolved from the amorphous ferrous hydroxide gel by heterogeneous nucleation and growth. Preferential adsorption of additives on certain crystallographic planes thereby retarding the growth in the perpendicular direction, allows the particles to acquire acicular shapes with high aspect ratios of 8-15. Synthetic hydrogoethite showed a mass loss of about 14% at similar to 280 degreesC, revealing the presence of strongly coordinated water of hydration in the interior of the goethite crystallites. As evident from IR spectra, excess H2O molecules (0.1- 0.22 per formula unit) are located in the strands of channels formed in between the double ribbons of FeO6 octahedra running parallel to the c- axis. Hydrogoethite particles constituted of multicrystallites are formed with Pt as additive, whereas single crystallite particles are obtained with Pd (or Rh). For both dehydroxylation as well as H-2 reduction, a lower reaction temperature (similar to 220 degreesC) was observed for the former (Pt treated) compared to the latter (Pd or Rh) (similar to 260 degreesC). Acicular magnetite (Fe3O4) was prepared either by reducing hydrogoethite (magnetite route) or dehydroxylating hydrogoethite to hematite and then reducing it to magnetite (hematite- magnetite route). According to TEM studies, preferential dehydroxylation of hydrogoethite along < 010 > leads to microporous hematite. Maghemite (gamma -Fe2O3 (-) (delta), 0 < < 0.25) was obtained by reoxidation of magnetite. The micropores are retained during the topotactic transformation to magnetite and finally to maghemite, whereas cylindrical mesopores are formed due to rearrangement of the oxygen sublattice from hexagonal to cubic close packing during the conversion of hydrogoethite to magnetite and then to maghemite. Accordingly, three different types of maghemite particles are realized: strongly oriented multicrystalline particles, single crystalline acicular particles with micropores or crystallites having mesopores. Higher values of saturation magnetization ((s) = 74 emu g(-1)) and coercivity (H-c = 320 Oe) are obtained for single crystalline mesoporous particles. In the other cases, the smaller size of particles and larger distribution of micropores decreases sigma (s) considerably ( < 60 emu g(-1)) due to relaxation effects of spins on the surface atoms as revealed by Mossbauer spectroscopy.

Effect of solvent on the ultrasonic degradation of poly(vinyl acetate)

The ultrasonic degradation of poly(vinyl acetate) was carried out in six different solvents and two mixtures of solvents. The evolution of molecular weight distribution (MWD) with time was determined with gel permeation chromatography. The observed MWDs were analyzed by continuous distribution kinetics. A stoichiometric kernel that accounts for preferential mid-point breakage of the polymer chains was used. The degradation rate coefficient of the polymer in each solvent was determined from the model. The variations of rate coefficients were correlated with vapor pressure of the solvent, the Flory–Huggins polymer–solvent interaction parameter and the kinematic viscosity of the solution. A lower saturation vapor pressure resulted in higher degradation rates of the polymer. The degradation rate increased with increasing kinematic viscosity.