Reactivity in the spinel formation reaction in CuO/Al2O3, Fe2O3, Cr2O3 systems

Abstract is not available.

Drop formation studies in liquid—liquid systems

Benzene drops were formed in continuous media of water and glycerine of varying physical properties. The effect on drop volumes of variables like volumetric flow-rate, interfacial tension, continuous phase viscosity and capillary diameter was studied. An equation has been developed, based on a two stage drop formation mechanism, which predicts drop volumes within an average error of 7 per cent for the range of physical properties employed in this investigation.

Polarographic and redox potential studies on copper(I) and copper(II) and their complexes. Part III. Copper (I and II)-ethylene diamine and edta complexes and theory of formation of step reduction waves in cupric copper systems

Polarographic and redox potential measurements on the cupric and cuprous complexes of ethylenediamine and EDTA have been carried out. From the ratio of the stability constants of the cupric and cuprous complexes, and the stability constant of the cupric complex, the stability constant of the cuprous-ethylenediamine complex is obtained. In the case of the EDTA complex it has been possible to obtain only βic/β2ous from the equilibrium concentrations of the cuprous and cupric complexes and the disproportionation constant. The inequalities for the appearance of step reduction waves have been given. The values of the stability constants of the cupric and cuprous complexes determined by the polarographic-redox potential method have been used to explain the appearance of step reduction waves in some systems and the non-appearance in other systems.

Phase relations in the systems Cu–O–R2O3(R = Tm, Lu) and Gibbs energies of formation of Cu2R2O5 compounds

The phase relations in the systems Cu–O–R2O3(R = Tm, Lu) have been determined at 1273 K by X-ray diffraction, optical microscopy and electron probe microanalysis of samples equilibrated in evacuated quartz ampules and in pure oxygen. Only ternary compounds of the type Cu2R2O5 were found to be stable. The standard Gibbs energies of formation of the compounds have been measured using solid-state galvanic cells of the type, Pt|Cu2O + Cu2R2O5+ R2O3‖(Y2O3)ZrO2‖CuO + Cu2O‖Pt in the temperature range 950–1325 K. The standard Gibbs energy changes associated with the formation of Cu2R2O5 compounds from their binary component oxides are: 2CuO(s)+ Tm2O3(s)→Cu2Tm2O5(s), ΔG°=(10400 – 14.0 T/K)± 100 J mol–1, 2CuO(s)+ Lu2O3(s)→Cu2Lu2O5(s), ΔG°=(10210 – 14.4 T/K)± 100 J mol–1 Since the formation is endothermic, the compounds become thermodynamically unstable with respect to component oxides at low temperatures, Cu2Tm2O5 below 743 K and Cu2Lu2O5 below 709 K. When the chemical potential of oxygen over the Cu2R2O5 compounds is lowered, they decompose according to the reaction, 2Cu2R2O5(s)→2R2O3(s)+ 2Cu2O(s)+ O2(g) The equilibrium oxygen potential corresponding to this reaction is obtained from the emf. Oxygen potential diagrams for the Cu–O–R2O3 systems at 1273 K are presented.

Monte Carlo simulation of network formation based on structural fragments in epoxy-anhydride systems

A method combining the Monte Carlo technique and the simple fragment approach has been developed for simulating network formation in amine-catalysed epoxy-anhydride systems. The method affords a detailed insight into the nature and composition of the network, showing the distribution of various fragments. It has been used to characterize the network formation in the reaction of the diglycidyl ester of isophthalic acid with hexahydrophthalic anhydride, catalysed by benzyldimethylamine. Pre-gel properties like number and weight distributions and average molecular weights have been calculated as a function of epoxy conversion, leading to a prediction of the gel-point conversion. Analysis of the simulated network further yields other characteristic properties such as concentration of crosslink points, distribution and concentration of elastically active chains, average molecular weight between crosslinks, sol content and mass fraction of pendent chains. A comparison has been made of the properties obtained through simulation with those predicted by the fragment approach alone, which, however, gives only average properties. The Monte Carlo simulation results clearly show that loops and other cyclic structures occur in the gel. This may account for the differences observed between the results of the simulation and the fragment model in the post-gel phase. Copyright (C) 1996 Elsevier Science Ltd.

Gibbs energies of formation of intermetallic phases in the systems Pt Mg, Pt Ca and Pt Ba and some applications

The standard Gibbs energies of formation of platinum-rich intermetallic compounds in the systems Pt-Mg, Pt-Ca, and Pt-Ba have been measured in the temperature range of 950 to 1200 K using solid-state galvanic cells based on MgF2, CaF2, and BaF2 as solid electrolytes. The results are summarized by the following equations: ΔG° (MgPt7) = −256,100 + 16.5T (±2000) J/mol ΔG° (MgPt3) = −217,400 + 10.7T (±2000) J/mol ΔG° (CaPt5) = −297,500 + 13.0T (±5000) J/mol ΔG° (Ca2Pt7) = −551,800 + 22.3T (±5000) J/mol ΔG° (CaPt2) = −245,400 + 9.3T (±5000) J/mol ΔG° (BaPt5) = −238,700 + 8.1T (±4000) J/mol ΔG° (BaPt2) = −197,300 + 4.0T (±4000) J/mol where solid platinum and liquid alkaline earth metals are selected as the standard states. The relatively large error estimates reflect the uncertainties in the auxiliary thermodynamic data used in the calculation. Because of the strong interaction between platinum and alkaline earth metals, it is possible to reduce oxides of Group ILA metals by hydrogen at high temperature in the presence of platinum. The alkaline earth metals can be recovered from the resulting intermetallic compounds by distillation, regenerating platinum for recycling. The platinum-slag-gas equilibration technique for the study of the activities of FeO, MnO, or Cr2O3 in slags containing MgO, CaO, or BaO is feasible provided oxygen partial pressure in the gas is maintained above that corresponding to the coexistence of Fe and “FeO.”

Differential response of cholesterol based pyrimidine systems with oxyethylene type spacers to gelation and mesogen formation in the presence of alkali metal ions

A new series of lipophilic cholesteryl derivatives of 2,4,6-trichloro-pyrimidine-5-carbaldehyde has been synthesized. Oxyethylene spacers of variable lengths were inserted between the hydrogen bonding promoting pyrimidine core and the cholesteryl tail in order to understand their effect on the selfassembly of these compounds. Only compound 1a with the shortest spacer formed a gel in organic solvents such as n-butanol and n-dodecane. While other members (1b and c) having longer spacers led to sol formation and precipitation in n-butanol and n-dodecane respectively. The self-assembly phenomena associated with the gelation process were investigated using temperature-dependent UVVis and CD-spectroscopy. The morphological features of the freeze-dried gels obtained from different organic solvents were examined by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The solid phase behaviours of these molecules and their associated alkali metal ion complexes were explored using polarized optical microscopy (POM) and differential scanning calorimetry (DSC). The molecular arrangements in the xerogel and in the solid state were further probed using a wide-angle Xray diffraction (WAXD) technique. Analysis of the wide-angle X-ray diffraction data reveals that this class of molecules adopts a hexagonal columnar organization in the gel and in the solid state. Each slice of these hexagonal columnar structures is composed of a dimeric molecular-assembly as a building block. Significant changes in the conformation of the oxyethylene chains could be triggered via the coordination of selected alkali metal ions. This led to the production of interesting metal ion promoted mesogenic behaviour.

Energetics of rare earth manganese perovskites A1-xA ' xMnO3 (A = La, Nd, Y and A ' = Sr, La) systems

High temperature reaction calorimetry using molten lead berate as solvent has been used to study the thermochemistry of NdMnO3, YMnO3, La1-xSrxMnO3 (with 0 < x < 0.5), and Ln(0.5)Ca(0.5)MnO(3) (with Ln = La, Nd, Y), The enthalpies of formation of these multicomponent oxides from their binary constituents have been calculated from the measured enthalpy of drop solution, The energetic stability of the perovskite depends on the size of the A cation, The enthalpy of formation of YMnO3 (smallest A cation) is more endothermic than those of NdMnO3 and LaMnO3. The energetics of the perovskite also depends on the oxidation state of the B site's ions. In the La1-xSrxMnO3 system, the energetic stability of the structure increases with the Mn4+/Mn3+ ratio, The new values of the enthalpies of oxidations, with reliable standard entropies, were used to plot the phase stability diagram of the lanthanum-manganese-oxygen system in the temperature range 300-1100 K, The LaMnO3/MnO phase boundary evaluated in this study agrees with the one published by Atsumi et nl. calculated from thermogravimetric and conductivity measurements.

Effect Of Directionality Of Grinding Marks On Friction And Formation Of Transfer Layer

Surface texture influences friction and transfer layer formation during sliding. In the present investigation, basic studies were conducted using inclined pin-on-plate sliding tester to understand the effect of directionality of surface grinding marks of hard material on friction and transfer layer formation during sliding against soft materials. 080 M40 steel plates were ground to attain different surface roughness with unidirectional grinding marks. Then pins made of soft materials such as pure Al, pure Mg and Al-Mg alloy were slid against the prepared steel plates. Grinding angle (i.e., the angle between direction of sliding and grinding marks) was varied between 0 degrees and 90 degrees in the tests. Experiments were conducted under both dry and lubricated conditions on each plate in ambient environment. It was observed that the transfer layer formation and the coefficient of friction, which has two components adhesion and plowing - depend primarily on the directionality of grinding marks of the harder mating surface, and independent of surface roughness of the harder mating surface. For the case of pure Mg, stick-slip phenomenon was observed under dry condition for all grinding angles and it was absent upto 20 degrees grinding angles under lubricated condition. However, for the case of Al, it was observed only under lubricated conditions for angles exceeding 20 degrees. As regards the alloy, namely, Al-Mg alloy, it, was absent in both conditions. For the case of pure Mg and Al, it was observed that the amplitude of stick-slip motion primarily depends on plowing component of friction. The grinding angle effect on coefficient of friction was attributed to the variation of plowing component of friction with grinding angle.

Magnetic Field Induced Instabilities In Localized Two-Dimensional Electron Systems

The results of extensive transport studies in localized regime of mesoscopic two-dimensional electron systems (2DES) with varying disorder are presented. A quick overview of previously achieved result is given. The main focus is on the observation of density dependent instabilities manifested by strong resistance oscillations induced by high perpendicular magnetic fields B-perpendicular to. While the amplitude of the oscillations is strongly enhanced with increasing B-perpendicular to, their position in electron density remains unaffected. The temperature dependence of resistivity shows a transition from an activated behaviour at high temperature to a saturated behaviour at low T. In the positions of resistance minima, the T dependence can even become metal-like (d rho/dT > 0). The activation energies obtained from the high T behaviour exhibit a formation of plateaux in connection with the resistance oscillations when analyzed as a function of electron density. We suggest the interplay between a strongly interacting electron phase and the background disorder as a possible explanation for our observation.

Spectroscopic studies on n-donor + σ-acceptor systems: Alkylthioureas and thiocarbanilides

The donor-acceptor interactions of alkylthioureas and thiocarbanilides with halogens have been investigated in detail employing electronic and infra-red spectroscopy. Various correlations of the spectroscopic and thermodynamic data have been presented. Alkylthioureas are by far the strongest donors known, and give high equilibrium constants (10,000-40,000 l. mole-1) and enthalpies of formation (9-18 kcal mole-1). The perturbation of the various vibrational frequencies due to charge transfer have also been studied. Hydrogen bonding of thioureas with hydroxylic compounds have been reported.

Spectrophotometric and potentiometric investigations of copper (II)-Ethanolamine complexes - Part III. diethanolamine (Gaussian analysis of electronic spectra in mono and diethanolamine systems)

Spectrophotometric and potentiometric investigations have been carried out on copper-diethanolamine system. Job plots at 900, 900 and 580 mμ have indicated the formation of CuD++, CuD2++ and CuD3++. The n- pA curves obtained indicate the formation of CuD++, CuD2++, CuD3++, CuDOH+, CuD2OH+ and CuD3OH+. The n- pA curves have been analyzed to obtain the stability constants of these complexes. Absorption curves of pure complexes have been computed by a graphical method. Gaussian analysis of the absorption curves of pure and hydroxy complexes show the presence of a second band, indicating that the structure is that of a distorted octahedron.

Generation of Cationic Two-Coordinate Group-13 Ligand Systems by Spontaneous Halide Ejection: Remarkably Nucleophile-Resistant (Dimethylamino)borylene Complexes

Spontaneous ejection of chloride from a three-coordinate boron Lewis acid can be effected by employing very electron rich metal substituents and leads to the formation of a sterically unprotected terminal (dimethylamino)borylene complex that has a short metal-boron bond and remarkable resistance to attack by nucleophilic and protic reagents.

Systems Analysis of Tank Irrigation: II. Delayed Start and Water Deficit

Tank irrigation systems in the semiarid regions of India are discussed in this paper. To optimize the grain yield of rice, it is essential to start the agricultural operations in the second week of July so that favorable climatic conditions will prevail during flowering and yield formation stages. Because of low inflow during the initial few weeks of the crop season, often farmers are forced to delay planting until sufficient sowing rain and inflow have occurred or to adopt deficit irrigation during this period. The delayed start affects the grain yield, but will lead to an improved irrigation efficiency. A delayed start of agricultural operations with increased irrigation efficiency leads to the energy resources becoming critical during the peak requirement week, particularly those of female labor and animal power. This necessitates augmenting these resources during weeks of their peak use, either by reorganizing the traditional methods of cultivation or by importing from outside the system.

Trends in the stability of ternary oxides: Systems M-Pb-O (M = Ca, Sr, Ba)

Recent experimental investigations of phase equilibria and thermodynamic properties of the systems M-Pb-O, where M = Ca, Sr or Ba, indicate a regular increase in thermodynamic stability of ternary oxides, MPbO3 and M2PbO4, with increasing basicity of the oxide of the alkaline-earth metal. Number of stable interoxide compounds at 1100 K in the systems M-Pb-O (M = Mg, Ca, Sr, Ba) increases in unit increments from Mg to Ba. In this paper, experimentally determined standard Gibbs energies of formation of M2PbO4 (M = Ca, Sr, Ba) and MPbO3 (M = Sr, Ba) from their component binary monoxides and oxygen gas are combined with an estimated value for CaPbO3 to delineate systematic trends in thermodynamic stability of the ternary oxides. The trends are interpreted using concepts of tolerance factor and acid-base interactions. All the ternary oxides in these systems contain lead in the tetravalent state. The small Pb4+ ions polarize the surrounding oxygen ions and cause the formation of oxyanions which are acidic in character. Hence, the higher oxidation state of lead is stabilized in the presence of basic oxides of alkaline-earth group. A schematic subsolidus temperature-composition phase diagram is presented for the system BaO-PbO-O-2 to illustrate the change in oxidation states in binary and ternary oxides with temperature.