Treatment of electroplating effluent through emulsion-free liquid embrane

Separation of dissolved heavy metals such-as Cr(VI) and Cu(II) from electroplating effluents using a new technique of emulsion-free liquid membrane (EFLM) has been studied. Experimental results show that nearly 95% extraction is obtained resulting in stripping phase enrichment up to 50 times relative to feed. It is also found that emulsion-free liquid membranes are highly efficient and superior to other types of liquid membranes.

Flow of liquid/liquid dispersions in a Hele-Shaw cell

Flow of liquid/liquid dispersions have been investigated in a Hele-Shaw cell which contained a thin disk held between two parallel plates. This device offers a well defined flow field and also permits visual observation of the dispersed drop movement. The dispersed drops coalesce with the disk for the systems where the dispersed phase wets the disk surface. The dispersed phase accumulate at the downstream end of the disk and they detach from there as blobs. Through an accurate measurement of accumulated dispersed phase volume, the coalescence rate was determined. The coalescence efficiency in the Hele Shaw cell is determined by dividing the coalescence hate by the undisturbed flow rate of the dispersed phase through an area equal to the projected area of the disk on a plane normal to the flow direction. The coalescence efficiency first increases and then decreases with the flow rate of dispersion. The coalescence rate/disk dimensions increases with the decrease in the disk dimensions. The rate of coalescence increases with the increase in the dispersed drop diameter and it decreases with the increase in the continuous phase viscosity. The presence of surfactants reduces the coalescence rate. All these results are quantitatively explained through a model, which takes into account several important features like various mechanism of drainage, the roles of dispersion and continuous phase viscosities, and the drop deformation.

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.

Subquadratic quantum number dependence and other anomalies of vibrational dephasing in liquid nitrogen: Molecular dynamics simulation study from the triple point to the critical point and beyond

Vibrational phase relaxation near gas-liquid and liquid-solid phase coexistence has been studied by molecular dynamics simulations of N-N stretch in N-2. Experimentally observed pronounced insensitivity of phase relaxation from the triple point to beyond the boiling point is found to originate from a competition between density relaxation and resonant-energy transfer terms. The sharp rise in relaxation rate near the critical point (CP) can be attributed at least partly to the sharp, rise in vibration-rotation coupling contribution. Substantial subquadratic quantum number dependence of overtone dephasing rate is found near the CP and in supercritical fluids. [S0031-9007 (99)09318-7].

A fixed-grid finite element based enthalpy formulation for generalized phase change problems: role of superficial mushy region

The enthalpy method is primarily developed for studying phase change in a multicomponent material, characterized by a continuous liquid volume fraction (phi(1)) vs temperature (T) relationship. Using the Galerkin finite element method we obtain solutions to the enthalpy formulation for phase change in 1D slabs of pure material, by assuming a superficial phase change region (linear (phi(1) vs T) around the discontinuity at the melting point. Errors between the computed and analytical solutions are evaluated for the fluxes at, and positions of, the freezing front, for different widths of the superficial phase change region and spatial discretizations with linear and quadratic basis functions. For Stefan number (St) varying between 0.1 and 10 the method is relatively insensitive to spatial discretization and widths of the superficial phase change region. Greater sensitivity is observed at St = 0.01, where the variation in the enthalpy is large. In general the width of the superficial phase change region should span at least 2-3 Gauss quadrature points for the enthalpy to be computed accurately. The method is applied to study conventional melting of slabs of frozen brine and ice. Regardless of the forms for the phi(1) vs T relationships, the thawing times were found to scale as the square of the slab thickness. The ability of the method to efficiently capture multiple thawing fronts which may originate at any spatial location within the sample, is illustrated with the microwave thawing of slabs and 2D cylinders. (C) 2002 Elsevier Science Ltd. All rights reserved.

High temperature phase chemistry of system Eu-Pd-O

An isothermal section of the phase diagram for the system Eu - Pd - O at 1223 K has been established by equilibration of samples representing 20 different compositions, and phase identification after quenching by optical and scanning electron microscopy, X-ray powder diffraction, and energy dispersive spectroscopy. Three ternary oxides, Eu4PdO7, Eu2PdO4, and Eu2Pd2O5, were identified. Liquid alloys and the intermetallic compounds EuPd2 and EuPd3 were found to be in equilibrium with EuO. The compound EuPd3 was also found to coexist separately with Eu3O4 and Eu2O3. The oxide phase in equilibrium with EuPd5 and Pd rich solid solution was Eu2O3. Based on the phase relations, four solid state cells were designed to measure the Gibbs energies of formation of the three ternary oxides in the temperature range from 925 to 1350 K. Although three cells are sufficient to obtain the properties of the three compounds, the fourth cell was deployed to crosscheck the data. An advanced version of the solid state cell incorporating a buffer electrode with yttria stabilised zirconia solid electrolyte and pure oxygen gas at a pressure of 0.1 MPa as the reference electrode was used for high temperature thermodynamic measurements. Equations for the standard Gibbs energy of formation of the interoxide compounds from their component binary oxides Eu2O3 with C type structure and PdO have been established. Based on the thermodynamic information, isothermal chemical potential diagrams and isobaric phase diagrams for the system Eu - Pd - O have been developed.

Stress induced phase transition in a monomolecular perfluroalkylsilane film self assembled on aluminium surface

We control the stiffnesses of two dual double cantelevers placed in series to control penetration into a perflurooctyltrichlorosilane monolayer self assembled on aluminium and silicon substrates. The top cantilever which carries the probe is displaced with respect to the bottom cantilever which carries the substrate, the difference in displacement recorded using capacitors gives penetration. We further modulate the input displacement sinusoidally to deconvolute the viscoelastic properties of the monolayer. When the intervention is limited to the terminal end of the molecule there is a strong viscous response in consonance with the ability of the molecule to dissipate energy by the generation of gauche defects freely. When the intervention reaches the backbone, at a contact mean pressure of 0.2GPa the damping disappears abruptly and the molecule registers a steep rise in elastic modulus and relaxation time constant, with increasing contact pressure. We offer a physical explanation of the process and describe this change as due to a phase transition from a liquid like to a solid like state.

Phase Characterization and Study of Molecular Order of a Three-Ring Mesogen by (13)C NMR in Smectic C and Nematic Phases

Molecules exhibiting a thermotropic liquid-crystalline property have acquired significant importance due to their sensitivity to external stimuli such as temperature, mechanical forces, and electric and magnetic fields. As a result, several novel mesogens have been synthesized by the introduction of various functional groups in the vicinity of the aromatic core as well as in the side chains and their properties have been studied. In the present study, we report three-ring mesogens with hydroxyl groups at one terminal. These mesogens were synthesized by a multistep route, and structural characterization was accomplished by spectral techniques. The mesophase properties were studied by hot-stage optical polarizing microscopy, differential scanning calorimetry, and small-angle X-ray scattering. An enantiotropic nematic phase was noticed for lower homologues, while an additional smectic C phase was found for higher homologues. Solid-state high-resolution natural abundance (13)C NMR studies of a typical mesogen in the solid phase and in the mesophases have been carried out. The (13)C NMR spectrum of the mesogen in the smectic C and nematic phases indicated spontaneous alignment of the molecule in the magnetic field. By utilizing the two-dimensional separated local field (SLF) NMR experiment known as SAMPI4, (13)C-(1)H dipolar couplings have been obtained, which were utilized to determine the orientational order parameters of the mesogen.

Solubility and activity of oxygen in liquid indium and copper indium alloys

The solubility of oxygen in liquid indium in the temperature range 650–820 °C and in liquid copper-indium alloys at 1100 °C in equilibrium with indium sesquioxide has been measured by a phase equilibration technique. The solubility of oxygen in pure indium is given by the relation log(at.% O) = −4726/T + 3.73 (±0.08) Using the recently measured values for the standard free energy of formation of In2O3 and assuming that oxygen obeys Sievert's law up to saturation, the standard free energy of solution of molecular oxygen in liquid indium is calculated as View the MathML sourceΔG°= −51 440 + 8.07 T (±500) cal where the standard state for dissolved oxygen is an infinitely dilute solution in which activity is equal to atomic per cent. The effect of indium additions on the activity coefficient of oxygen dissolved in liquid copper was measured by a solid oxide galvanic cell. The interaction parameter ϵ0In is given by View the MathML source The experimentally determined variation of the activity coefficient of oxygen in dilute solution in Cu-In alloys is in fair agreement with that predicted by a quasichemical model in which each oxygen atom is assumed to be interstitially coordinated to four metal atoms and the nearest neighbour metal atoms are assumed to lose approximately half their metallic cohesive energies.

Solubility and activity of oxygen in liquid germanium and germanium copper alloys

The solubility of oxygen in liquid germanium in the temperature range 1233 to 1397 K, and in liquid germanium-copper alloys at 1373 K, in equilibrium with GeO2 has been measured by the phase equilibration technique. The solubility of oxygen in pure germanium is given by the relation R470 log(at. pct 0)=-6470/T+4.24 (±0.07). The standard free energy of solution of oxygen in liquid germanium is calculated from the saturation solubility, and recently measured values for the free energy of formation of GeO2, assuming that oxygen obeys Sievert’s law up to the saturation limit. For the reaction, 1/2 O2(g)→ OGe ΔG° =-39,000 + 3.21T (±500) cal = -163,200 + 13.43T (±2100) J. where the standard state for dissolved oxygen is that which makes the value of activity equal to the concentration (in at. pct), in the limit, as concentration approaches zero. The effect of copper on the activity of oxygen dissolved in liquid germanium is found to be in good agreement with that predicted by a quasichemical model in which each oxygen was assumed to be bonded to four metal atoms and the nearest neighbor metal atoms to an oxygen atom are assumed to lose approximately half of their metallic bonds.

Three phase equilibria for activity determinations: system Co Mn

A solid state e.m.f. cell with yttria-doped thoria as the electrolyte and a mixture of Cr + Cr sub 2 O sub 3 as the reference electrode, was employed for the measurement of the activity of manganese in the Co--Mn system at 1760 deg K, for 0.3 > X sub Mn > 0.05. The liquid alloy was contained in an alumina crucible and saturated with MnAl sub 2+2x O sub 4+3x . The cell can be represented by Pt, W, (Co--Mn) + MnAl sub 2+2x O sub 4+3x + Al sub 2 O sub 3 /ThO sub 2 --Y sub 2 O sub 3 /Cr + Cr sub 2 O sub 3 , Pt. The activity of manganese shows negative deviations from Raoult's law. The activities in the Co--Mn system are intermediate between those in the Fe--Mn and Ni--Mn systems. The Gibbs' energies of mixing in these systems follow the trends given by Miedema's model. 14 ref.--AA.

Thermodynamic properties and phase boundaries of Co O solutions

The thermodynamic properties of liquid unsaturated Co--O solutions have been determined by electrochemical measurements using (Y sub 2 O sub 3 )ThO sub 2 as solid electrolyte. The cell can be represented as, Pt. MoO sub 2 + Mo | (Y sub 2 O sub 3 )ThO sub 2 | O sub Co , tungsten, Pt, Emf of the cell was measured as a function of oxygen concentration in liquid Co at 1798, 1873 and 1973K. Least-mean squares regression analysis of the experimental data gives for the free energy of solution of diatomic oxygen in liquid Co Delta G exp 0 sub O(Co) = --84935--7.61 T ( plus/minus 400) J/g-atom and self interaction parameter for oxygen epsilon exp O sub O = --97240/T + 40.52 ( plus/minus 1) where the standard state for O is an infinitely dilute solution in which the activity is equal to atomic percent. The present data are discussed in comparison with those reported in the literature and the phase diagram for the Co--O system. 18 ref.--AA.

Oxygen content of liquid cobalt in equilibrium with CoO.(1+x)Al2O3 and -Al2O3

The oxygen concentration of liquid cobalt in equilibrium with cobalt aluminate and a-alumina has been measured by suction sampling and crucible quenching techniques at temperatures between 1770 and 1975 K. Experiments were made with cobalt of high and low initial oxygen contents, and with and without the addition of cobalt aluminate. The effect of temperature on the equilibrium oxygen content is represented by the equation, log (at.% 0) = -10,4001T(K) + 4.64 (±0.008). The composition of the spinel phase, CoO.(1+x)AI20 3, saturated with alumina, has been determined by electron probe microanalysis. The values of x are 0.22 at 1770 Kand 0.28 at 1975 K. The oxygen potential corresponding to the three-phase equilibrium between cobalt, aluminate and alumina, and the standard Gibbs' energy of formation of nonstoichiometric cobalt aluminate are evaluated by combining the results of this study with recently published data on the activity of oxygen in liquid cobalt. Implications of the present results to aluminium deoxidation of liquid cobalt are discussed.

Phase equilibria and thermodynamics of the system Dy-Mg-Cl at 1073 K

The phase relations in the system Dy–Mg–Cl at 1073 K have been established by isothermal equilibration and chemical analysis of quenched samples. Liquid Mg-rich alloy was found to be in equilibrium with molten DyCl2. Therefore, DyCl2 can be synthesized by reduction of MgCl2 with excess of metallic Dy at 1073 K. The Gibbs energy of formation of DyCl2 at 1073 K was evaluated by two different methods. From voltammetric determination of decomposition voltage, the upper limit for the standard Gibbs energy of formation of DyCl2 was estimated to be −505(±20) kJ mol−1. A value of −543(±10) kJ mol−1 was deduced from phase relations using Gibbs–Duhem integration. The value for the standard Gibbs energy of DyCl2 indicates that the Dy2+ ion has a potential capability for reducing TiCl4 to metal titanium. At the same time, Mg is a reductant for Dy3+ produced during the reduction of TiCl4. Thus, it is thermodynamically confirmed that reduction of TiCl4 by magnesium using a reaction mediator in the salt phase is feasible.

System Nd-Pd-O: Phase diagram and thermodynamic properties of oxides using a solid-state cell with advanced features

An isothermal section of the phase diagram for the system Nd-Pd-O at 1350 K has been established by equilibration of samples representing 13 different compositions and phase identification after quenching by optical and scanning electron microscopy, x-ray diffraction, and energy dispersive analysis of x-rays. The binary oxides PdO and NdO were not stable at 1350 K. Two ternary oxides Nd4PdO7 and Nd2Pd2O5 were identified. Solid and liquid alloys, as well as the intermetallics NdPd3 and NdPd5, were found to be in equilibrium with Nd2O3. Based on the phase relations, three solidstate cells were designed to measure the Gibbs energies of formation of PdO and the two ternary oxides. An advanced version of the solid-state cell incorporating a buffer electrode was used for high-temperature thermodynamic measurements. The function of the buffer electrode, placed between reference and working electrodes, was to absorb the electrochemical flux of the mobile species through the solid electrolyte caused by trace electronic conductivity. The buffer electrode prevented polarization of the measuring electrode and ensured accurate data. Yttria-stabilized zirconia was used as the solid electrolyte and pure oxygen gas at a pressure of 0.1 MP a as the reference electrode. Electromotive force measurements, conducted from 950 to 1425 K, indicated the presence of a third ternary oxide Nd2PdO4, stable below 1135 (±10) K. Additional cells were designed to study this compound. The standard Gibbs energy of formation of PdO (†f G 0) was measured from 775 to 1125 Kusing two separate cell designs against the primary reference standard for oxygen chemical potential. Based on the thermodynamic information, chemical potential diagrams for the system Nd-Pd-O were also developed.