Thermodynamic stability of CaThF6(cr) by transpiration and e.m.f. techniques

In the present paper, we report the standard molar Gibbs energy of formation for CaThF₆ measured by gas equilibration and e.m.f. methods. The HF(g) vapour pressure over the equilibrium reaction: \({\text{CaThF}}_{6} \left( {\text{cr}} \right) + 2 {\text{H}}_{ 2} {\text{O}}\left( {\text{g}} \right) = {\text{CaF}}_{2} \left( {\text{cr}} \right) + {\text{ThO}}_{2} \left( {\text{cr}} \right) + 4{\text{HF}}\left( {\text{g}} \right)\) has been measured using transpiration technique. The above reaction mechanism has been established employing TG and XRD techniques. A fluoride e.m.f. cell: (−)Pt, CaF₂(cr) + ThOF₂(cr) + CaThF₆(cr) |CaF₂(cr)| NiO(cr) + NiF₂(cr), Pt(+) has been constructed to measure Gibbs energy of formation of CaThF₆ (cr) using CaF₂ (cr) as a solid electrolyte. The isobaric heat capacity \({\text{Cp}}_{\text{m}}^{{\circ }} \left( T \right)\) of the compound has been measured using differential scanning calorimetric technique. Based on the experimental results, thermodynamic functions for CaThF₆ have been generated.

     

Electric field driven fractal growth dynamics in polymeric medium

This paper reports the extension of earlier work (Dawar and Chandra, 2012) [27] by including the influence of low values of electric field on diffusion limited aggregation (DLA) patterns in polymer electrolyte composites. Subsequently, specified cut-off value of voltage has been determined. Below the cut-off voltage, the growth becomes direction independent (i.e., random) and gives rise to ramified DLA patterns while above the cut-off, growth is governed by diffusion, convection and migration. These three terms (i.e., diffusion, convection and migration) lead to structural transition that varies from dense branched morphology (DBM) to chain-like growth to dendritic growth, i.e., from high field region (A) to constant field region (B) to low field region (C), respectively. The paper further explores the growth under different kinds of electrode geometries (circular and square electrode geometry). A qualitative explanation for fractal growth phenomena at applied voltage based on Nernst–Planck equation has been proposed.     

Thermodynamic characterization of chromium tellurate

The standard Gibbs energy of formation of chromium tellurate, Cr₂TeO₆ was determined from the vapour pressure measurement of TeO₂(g) over the phase mixture Cr₂TeO₆(s) + Cr₂O₃(s) in the temperature range 1,183–1,293 K. A thermogravimetry (TG)-based transpiration technique was used for the vapour pressure measurement. This technique was validated by measuring the vapour pressure of CdCl₂(g) over CdCl₂(s). The temperature dependence of the vapour pressure of CdCl₂(g) could be represented as logp (Pa) (±0.02) = 12.06 ? 8616.3/T (K) (734 ? 823 K). A ‘third-law’ analysis of the vapour pressure data yielded a mean value of 185.1 ± 0.4 kJ mol^?1 for the enthalpy of sublimation of CdCl₂(s). The temperature dependence of vapour pressure of TeO₂(g) generated by the incongruent vapourisation reaction, $ {\text{Cr}}_{ 2} {\text{TeO}}_{ 6} (\rm s) \to {\text{Cr}}_{ 2} {\text{O}}_{ 3} (\rm s) + {\text{TeO}}_{ 2} (\rm g) + 1/2\,{\text{O}}_{ 2} (\rm g) $ could be represented as logp (Pa) (±0.04) = 18.57 – 21,199/T (K) (1,183 – 1,293 K). The temperature dependence of the Gibbs energy of formation of Cr₂TeO₆ could be expressed as $ \{ \Updelta G_{\text{f}}^{ \circ } ({\text{Cr}}_{ 2} {\text{TeO}}_{ 6} ,{\text{ s}}){\text{ (kJ}}\,{\text{mol}}^{ - 1} )\pm 4. 0 {\text{\} = }} - 1 6 2 5. 6 { \,+\, 0} . 5 3 3 6\,T({\text{K}}) \, (1{,}183 - 1{,}293\,{\text{K}}). $ A drop calorimeter was used for measuring the enthalpy increments of Cr₂TeO₆ in the temperature range 373–973 K. Thermodynamic functions viz., heat capacity, entropy and Gibbs energy functions of Cr₂TeO₆ were derived from the experimentally measured enthalpy increment values. $ \Updelta H_{{{\text{f}},298\,{\text{K}}}}^{ \circ } ({\text{Cr}}_{ 2} {\text{TeO}}_{ 6} ) $ was found to be ?1636.9 ± 0.8 kJ mol^?1.     

Modal characterisation theorems over special classes of frames

We investigate model theoretic characterisations of the expressive power of modal logics in terms of bisimulation invariance. The paradigmatic result of this kind is van Benthem’s theorem, which says that a first-order formula is invariant under bisimulation if, and only if, it is equivalent to a formula of basic modal logic. The present investigation primarily concerns ramifications for specific classes of structures. We study in particular model classes defined through conditions on the underlying frames, with a focus on frame classes that play a major role in modal correspondence theory and often correspond to typical application domains of modal logics. Classical model theoretic arguments do not apply to many of the most interesting classes-for instance, rooted frames, finite rooted frames, finite transitive frames, well-founded transitive frames, finite equivalence frames-as these are not elementary. Instead we develop and extend the game-based analysis (first-order Ehrenfeucht-Fraïssé versus bisimulation games) over such classes and provide bisimulation preserving model constructions within these classes. Over most of the classes considered, we obtain finite model theory analogues of the classically expected characterisations, with new proofs also for the classical setting. The class of transitive frames is a notable exception, with a marked difference between the classical and the finite model theory of bisimulation invariant first-order properties. Over the class of all finite transitive frames in particular, we find that monadic second-order logic is no more expressive than first-order as far as bisimulation invariant properties are concerned — though both are more expressive here than basic modal logic. We obtain ramifications of the de Jongh-Sambin theorem and a new and specific analogue of the Janin-Walukiewicz characterisation of bisimulation invariant monadic second-order for finite transitive frames.     

Elementary Properties of the Finite Ranks

This note investigates the class of finite initial segments of the cumulative hierarchy of pure sets. We show that this class is first-order definable over the class of finite directed graphs and that this class admits a first-order definable global linear order. We apply this last result to show that FO(<, BIT) = FO(BIT).     

Realization of an advanced nozzle concept for compact chemical oxygen iodine laser

Conventional supersonic chemical oxygen–iodine lasers (SCOIL) are not only low-pressure systems, with cavity pressure of 2–3 Torr and Mach number of approximately 1.5, but also are high-throughput systems with a typical laser power per unit evacuation capacity of nearly 1 J/l, thus demanding high capacity vacuum systems which mainly determine the compactness of the system. These conventional nozzle-based systems usually require a minimum of a two-stage ejector system for realization of atmospheric pressure recovery in a SCOIL. Typically for a 500 W class SCOIL, a first stage requires a motive gas flow (air) of 120 gm/s to entrain a laser gas flow of 3 g/s and is capable of achieving the pressure recovery in the range of 60–80 Torr. On the other hand, the second stage ejector requires 4.5 kg/s of motive gas (air) to achieve atmospheric pressure recovery. An advanced nozzle, also known as ejector nozzle, suitable for a 500 W-class SCOIL employing an active medium flow of nearly 12 g/s, has been developed and used instead of a conventional slit nozzle. The nozzle has been tested in both cold as well as hot run conditions of SCOIL, achieving a typical cavity pressure of nearly 10 Torr, stagnation pressure of approximately 85 Torr and a cavity Mach number of 2.5. The present study details the gas dynamic aspects of this ejector nozzle and highlights its potential as a SCOIL pressure recovery device. This nozzle in conjunction with a diffuser is capable of achieving pressure recovery equivalent to a more cumbersome first stage of the pressure recovery system used in the case of a conventional slit nozzle-based system. Thus, use of this nozzle in place of a conventional slit nozzle can achieve atmospheric discharge using a single stage ejector system, thereby making the pressure recovery system quite compact.     

Electrical transport properties of hydrogen-exposed p-type PbTe films

Hall coefficient and d.c. conductivity measurements were made on p-type PbTe epitaxial films exposed to molecular hydrogen gas at high pressures (100–500 psi) in the temperature range (100–300K). It is found that hydrogen converts p-type films to n-type at a pressure of about 300 psi. The results are explained by assuming that the action of hydrogen is to provide donor electrons.     

The effect of hydrogen on the electrical properties of n-type Pb0.9Cd0.1Te thin films

Measurements of the Hall coefficient and the d.c. conductivity were made on flash evaporated n-type Pb_0.9Cd_0.1Te epitaxial films exposed to molecular hydrogen gas at high pressures (upto 500 psi) in the temperature range 77–300 K. It has been found that the effect of hydrogen on the films is to reduce the concentration of the extrinsic carriers and to increase their mobility. It is believed that hydrogen gas removes cadmium ions and neutral cadmium atoms from these films.     

One-Pot Esterification and Amide Formation via Acid-Catalyzed Dehydration and Ritter Reactions

Esterification of carboxylic acid is achieved using acetonitrile as a water trap. Water liberated during esterification is consumed in cyanide hydrolysis, thereby driving the esterification to completion. Substrates having carboxylic acid and nitrile groups undergo intramolecular dehydration and rehydration to amido esters in the absence of acetonitrile. Cyano acids also undergo esterification and Ritter reaction in one pot when excess alcohol is used. For the first time, we have observed an interesting Ritter reaction of primary alcohols, leading to ester amide product in one pot.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource(s): Full experimental and spectral details.]