A critical assessment of the standard molar gibbs free energy of formation of NiWO4

Three independent studies have been reported on the free energy of formation of NiWO4. Results of these measurements are analyzed by the �third-law� method, using thermal functions for NiWO4 derived from both low and high temperature heat capacity measurements. Values for the standard molar enthalpy of formation of NiWO4 at 298·15 K obtained from �third-law� analysis are compared with direct calorimetric determinations. Only one set of free energy measurements is found to be compatible with calorimetric enthalpies of formation. The selected value for ?f H m 0 (NiWO4, cr, 298·15 K) is the average of the three calorimetric measurements, using both high temperature solution and combustion techniques, and the compatible free energy determination. A new set of evaluated data for NiWO4 is presented.

Metal-Free Deprotection of Terminal Acetonides by Using tert-Butyl Hydroperoxide in Aqueous Medium

Employing aqueous tert-butyl hydroperoxide (70%) as an inexpensive reagent a useful methodology for the regioselective and chemoselective deprotection of terminal acetonide groups in aqueous medium is developed. A variety of acetonide derivatives on reaction with aqueous tert-butyl hydroperoxide in water:tert-butanol (1:1) furnish the corresponding acetonide deprotected diols in good yields. A large number of acid labile protecting functional groups and other functional moieties were found to be unaffected under the conditions employed for the present deprotection. This method has been successfully applied to sugar derivatives.

Role of free valences and spin densities on the migrating atom in location of saddle points in radical-exchange reactions

The principle of the conservation of bond orders during radical-exchange reactions is examined using Mayer's definition of bond orders. This simple intuitive approximation is not valid in a quantitative sense. Ab initio results reveal that free valences (or spin densities) develop on the migrating atom during reactions. For several examples of hydrogen-transfer reactions, the sum of the reaction coordinate bond orders in the transition state was found to be 0.92 +/- 0.04 instead of the theoretical 1.00 because free valences (or spin densities) develop on the migrating atom during reactions. It is shown that free valence is almost equal to the square of the spin density on the migrating hydrogen atom and the maxima in the free valence (or spin density) profiles coincide (or nearly coincide) with the saddle points in the corresponding energy profiles.

Solubilization of n-decane into n-decyl-polyoxyethylene surfactants: A cavity forming free energy based model

The present paper reports the results of a theoretical study of the forces and factors driving the solubilization of n-alkane solubilizates into the micellar core of some non-ionic surfactants, based on a micellar model which includes the cavity forming free energy as a component of micellization. The solubilizate is n-decane and the non-ionic surfactants considered are n-decyl-polyoxyethylene surfactants. The extent of solubilization, i.e. the mole fraction of the solubilizate within the core has been calculated. The results indicate that the incorporated solubilizate has more translational and rotational degrees of freedom as compared to those of the tail parts of the surfactants present in the core. This drives the total free energy of aggregation after solubilization into a more favourable direction. The results are in fair agreement with the experimental results.

The unusual formation of methyl alpha-(5,6-dimethoxycarbonyl-2,3-dimethoxyazepin-7-ylidene)-alpha-[5-methoxycarbonyl-2,3-dimethoxypyrid-6-yl)acetate during the pyrolysis of ''azido-meta-hemipinate'' - First example of a reaction involving a concomitant ring expansion and ring extrusion

he ortho methoxycarbonyl substituent constitutes a sole exception in the ring closure reactions of ortho substituted aryl azides, as it provides no rate acceleration to this reaction. Pyrolysis of ''azido-meta-hemipinate'', an aryl azide containing such a substituent, led us to the title compound, a new azepinylidenepyridylacetic ester, whose structure has been established unambiguously by a single crystal X-ray diffraction study. This is the first report of a reaction involving both a ring expansion to an azaheptafulvalene and a ring extrusion to a pyridyl ring residue.

Time scales for transitions between free-energy minima of a dense hard-sphere system

Time scales associated with activated transitions between glassy metastable states of a free-energy functional appropriate for a dense hard-sphere system are calculated by using a new Monte Carlo method for the local density variables. In particular, we calculate the time the system, initially placed in a shallow glassy minimum of the free-energy, spends in the neighborhood of this minimum before making a transition to the basin of attraction of another free-energy minimum. This time scale is found to increase as the average density is increased. We find a crossover density near which this time scale increases very sharply and becomes longer than the longest times accessible in our simulation. This time scale does not show any evidence of increasing with sample size

Exact free-surface flows for shallow-water equations .2. the compressible case

Exact free surface flows with shear in a compressible barotropic medium are found, extending the authors' earlier work for the incompressible medium. The barotropic medium is of finite extent in the vertical direction, while it is infinite in the horizontal direction. The ''shallow water'' equations for a compressible barotropic medium, subject to boundary conditions at the free surface and at the bottom, are solved in terms of double psi-series, Simple wave and time-dependent solutions are found; for the former the free surface is of arbitrary shape while for the latter it is a damping traveling wave in the horizontal direction, For other types of solutions, the height of the free surface is constant either on lines of constant acceleration or on lines of constant speed. In the case of an isothermal medium, when gamma = 1, we again find simple wave and time-dependent solutions.

Free convection in power-law fluids near a three-dimensional stagnation point

Numerical results are presented for the free-convection boundary-layer equations of the Ostwald de-Waele non-Newtonian power-law type fluids near a three-dimensional (3-D) stagnation point of attachment on an isothermal surface. The existence of dual solutions that are three-dimensional in nature have been verified by means of a numerical procedure. An asymptotic solution for very large Prandtl numbers has also been derived. Solutions are presented for a range of values of the geometric curvature parameter c, the power-law index n, and the Prandtl number Pr.

Thermal expansion of irradiated polyvinyl chloride from 10 K to 340 K

The coefficient of thermal expansion is measured for irradiated Polyvinyl Chloride (PVC) from 10K to 340K. The samples of PVC are irradiated, up to 500 Mrad in steps of 100 Mrad, in air at room temperature by using Co gamma rays with a dose rate of 0.3 Mrad/h. The PVC is an amorphous sample which is confirmed by X-ray diffraction. The coefficient of thermal expansion is found to decrease with radiation dose from 10K to 110K and it increaseswith radiation dose from 110K to 340K. The results are explained on the basis of radiation induced degradation of the sample.

Fluctuation-dissipation relation for nonlinear Langevin equations

It is shown that the fluctuation-dissipation theorem is satisfied by the solutions of a general set of nonlinear Langevin equations with a quadratic free-energy functional (constant susceptibility) and field-dependent kinetic coefficients, provided the kinetic coefficients satisfy the Onsager reciprocal relations for the irreversible terms and the antisymmetry relations for the reversible terms. The analysis employs a perturbation expansion of the nonlinear terms, and a functional integral calculation of the correlation and response functions, and it is shown that the fluctuation-dissipation relation is satisfied at each order in the expansion.

Effect of Strain Rate on Ductile-to-Brittle Transition Temperature of a Free-Standing Pt-Aluminide Bond Coat

The ductile-to-brittle transition temperature (DBTT) of a free-standing Pt-aluminide (PtAl) bondcoat was determined using the microtensile testing method and the effect of strain rate variation, in the range 10(-5) to 10(-1) s(-1), on the DBTT studied. The DBTT increased appreciably with the increase in strain rate. The activation energy determined for brittle-to-ductile transition, suggested that such transition is most likely associated with vacancy diffusion. Climb of aOE (c) 100 > dislocations observed in analysis of dislocation structure using a transmission electron microscope (TEM) supported the preceding mechanism.

Some results on the reconstruction problems. p-claw-free, chordal, and p4-reducible graphs

A claw is an induced subgraph isomorphic to K-1,K-3. The claw-point is the point of degree 3 in a claw. A graph is called p-claw-free when no p-cycle has a claw-point on it. It is proved that for p greater than or equal to 4, p-claw-free graphs containing at least one chordless p-cycle are edge reconstructible. It is also proved that chordal graphs are edge reconstructible. These two results together imply the edge reconstructibility of claw-free graphs. A simple proof of vertex reconstructibility of P-4-reducible graphs is also presented. (C) 1995 John Wiley and Sons, Inc.

Thermal expansion studies of substituted CTP derivatives

Several new Na, Y and Zr substituted derivatives of Ca-0.5 Ti-2(PO4)(3) (CTP) have been synthesized. These derivatives retain the hexagonal structure of the parent (CTP) compound with minor changes in lattice parameters. Linear thermal expansion coefficients (alpha) have been obtained using a high sensitivity dilatometer.

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.