Thermodynamic Stability of Potassium-beta-Alumina

The activity of K sub 2 O in a mixture of alpha -alumina and potassium beta -alumina has been determined using a solid state galvanic cell in the temperature range 600-1000K. The cell is written such that the right hand electrode is positive. The solid electrolyte consisted of a dispersion of alpha -alumina ( approx 15 vol.%) in a matrix of K beta -alumina. The emf of the cell was found to be reversible and to vary linearly with temperature. From the emf and auxiliary data on In sub 2 O sub 3 and K sub 2 O from the literature, the activity of K sub 2 O in the two-phase mixture is obtained. The standard free energy of formation of K beta -alumina from component oxides is given. Graphs.

Weak consistency of read-only transactions: A tool to improve concurrency in heterogeneous locking protocols

Three different types of consistencies, viz., semiweak, weak, and strong, of a read-only transaction in a schedule s of a set T of transactions are defined and these are compared with the existing notions of consistencies of a read-only transaction in a schedule. We present a technique that enables a user to control the consistency of a read-only transaction in heterogeneous locking protocols. Since the weak consistency of a read-only transaction improves concurrency in heterogeneous locking protocols, the users can help to improve concurrency in heterogeneous locking protocols by supplying the consistency requirements of read-only transactions. A heterogeneous locking protocol P' derived from a locking protocol P that uses exclusive mode locks only and ensures serializability need not be deadlock-free. We present a sufficient condition that ensures the deadlock-freeness of Pprime, when P is deadlock-free and all the read-only transactions in Pprime are two phase.

Antarctic ice shelf melting and its impact on the global sea ice-ocean system

Earth s ice shelves are mainly located in Antarctica. They cover about 44% of the Antarctic coastline and are a salient feature of the continent. Antarctic ice shelf melting (AISM) removes heat from and inputs freshwater into the adjacent Southern Ocean. Although playing an important role in the global climate, AISM is one of the most important components currently absent in the IPCC climate model. In this study, AISM is introduced into a global sea ice-ocean climate model ORCA2-LIM, following the approach of Beckmann and Goosse (2003; BG03) for the thermodynamic interaction between the ice shelf and ocean. This forms the model ORCA2-LIM-ISP (ISP: ice shelf parameterization), in which not only all the major Antarctic ice shelves but also a number of minor ice shelves are included. Using these two models, ORCA2-LIM and ORCA2-LIM-ISP, the impact of addition of AISM and increasing AISM have been investigated. Using the ORCA2-LIM model, numerical experiments are performed to investigate the sensitivity of the polar sea ice cover and the Antarctic Circumpolar Current (ACC) transport through Drake Passage (DP) to the variations of three sea ice parameters, namely the thickness of newly formed ice in leads (h0), the compressive strength of ice (P*), and the turning angle in the oceanic boundary layer beneath sea ice (θ). It is found that the magnitudes of h0 and P* have little impact on the seasonal sea ice extent, but lead to large changes in the seasonal sea ice volume. The variation in turning angle has little impact on the sea ice extent and volume in the Arctic but tends to reduce them in the Antarctica when ignored. The magnitude of P* has the least impact on the DP transport, while the other two parameters have much larger influences. Numerical results from ORCA2-LIM and ORCA2-LIM-ISP are analyzed to investigate how the inclusion of AISM affects the representation of the Southern Ocean hydrography. Comparisons with data from the World Ocean Circulation Experiment (WOCE) show that the addition of AISM significantly improves the simulated hydrography. It not only warms and freshens the originally too cold and too saline bottom water (AABW), but also warms and enriches the salinity of the originally too cold and too fresh warm deep water (WDW). Addition of AISM also improves the simulated stratification. The close agreement between the simulation with AISM and the observations suggests that the applied parameterization is an adequate way to include the effect of AISM in a global sea ice-ocean climate model. We also investigate the models capability to represent the sea ice-ocean system in the North Atlantic Ocean and the Arctic regions. Our study shows both models (with and without AISM) can successfully reproduce the main features of the sea ice-ocean system. However, both tend to overestimate the ice flux through the Nares Strait, produce a lower temperature and salinity in the Hudson Bay, Baffin Bay and Davis Strait, and miss the deep convection in the Labrador Sea. These deficiencies are mainly attributed to the artificial enlargement of the Nares Strait in the model. In this study, the impact of increasing AISM on the global sea ice-ocean system is thoroughly investigated. This provides a first idea regarding changes induced by increasing AISM. It is shown that the impact of increasing AISM is global and most significant in the Southern Ocean. There, increasing AISM tends to freshen the surface water, to warm the intermediate and deep waters, and to freshen and warm the bottom water. In addition, increasing AISM also leads to changes in the mixed layer depths (MLD) in the deep convection sites in the Southern Ocean, deepening in the Antarctic continental shelf while shoaling in the ACC region. Furthermore, increasing AISM influences the current system in the Southern Ocean. It tends to weaken the ACC, and strengthen the Antarctic coastal current (ACoC) as well as the Weddell Gyre and the Ross Gyre. In addition to the ocean system, increasing AISM also has a notable impact on the Antarctic sea ice cover. Due to the cooling of seawater, sea ice concentration and thickness generally become higher. In austral winter, noticeable increases in sea ice concentration mainly take place near the ice edge. In regards with sea ice thickness, large increases are mainly found along the coast of the Weddell Sea, the Bellingshausen and Amundsen Seas, and the Ross Sea. The overall thickening of sea ice leads to a larger volume of sea ice in Antarctica. In the North Atlantic, increasing AISM leads to remarkable changes in temperature, salinity and density. The water generally becomes warmer, more saline and denser. The most significant warming occurs in the subsurface layer. In contrast, the maximum salinity increase is found at the surface. In addition, the MLD becomes larger along the Greenland-Scotland-Iceland ridge. Global teleconnections due to AISM are studied. The AISM signal is transported with the surface current: the additional freshwater from AISM tends to enhance the northward spreading of the surface water. As a result, more warm and saline water is transported from the tropical region to the North Atlantic Ocean, resulting in warming and salt enrichment there. It would take about 30 40 years to establish a systematic noticeable change in temperature, salinity and MLD in the North Atlantic Ocean according to this study. The changes in hydrography due to increasing AISM are compared with observations. Consistency suggests that increasing AISM is highly likely a major contributor to the recent observed changes in the Southern Ocean. In addition, the AISM might contribute to the salinity contrast between the North Atlantic and North Pacific, which is important for the global thermohaline circulation.

Thermodynamic properties of RhO2

A solid-state electrochemical cell, with yttria-stabilized zirconia as the electrolyte and pure O-2 gas at 0.1 MPa as the reference electrode, has been used to measure the oxygen chemical potential corresponding to the equilibrium between beta-Rh2O3 and RhO2 in the temperature range from 850 to 1050K. Using standard Gibbs energy of formation of beta-Rh2O3 available in the literature and the measured oxygen potential, the standard Gibbs free energy of formation of RhO2 is derived as a function of temperature: Delta G(f)degrees(RhO2)(+/- 71)/J mol(-1) = 238,418 + 179.89T Using an estimated value of Delta C-p degrees; for the formation reaction of RhO2 from its elements, the standard enthalpy of formation, standard entropy and isobaric heat capacity of RhO2 at 298.15 K are evaluated: Delta H-f degrees (298.15 K)(+/- 164)/kJ mol(-1) = -244.94, S degrees (298.15 K)(+/- 3.00)/J mol(-1) K-1 = 45.11 and C-p degrees(298.15 K)(+/- 2.6)1mol(-1) K-1 =64.28. (C) 2010 Elsevier B.V. All rights reserved.

Thermodynamic properties of the system toluene — 1, 1, 1-trichloroethane

Data on molar excess enthalpy on mixing at 298.15 K and 308.15 K, vapor-liquid equilibrium, latent heats of vaporization at 91.444 kPa and vapor pressures for the system toluene – 1, 1, 1-trichloroethane are presented. A simple adiabatic calorimeter designed for molar excess enthalpy measurements is described, tested and used. On présente, dans le cas du système toluène – 1, 1, 1-trichloréthane, des résultats relatifs aux grandeurs suivantes: a) enthalpie molaire d'excès à 298.15 K et 308.15 K; b) équilibre liquid-vapeur; c) chaleurs latentes de vaporisation à une pression absolue de 91.444 kP; d) pressions de vapeur. On décrit un calorimètre adiabatique simple, conçu pour mesurer l'enthalpie molaire d'excès, dont on a fait l'essai.

Thermodynamic properties of the systems benzene-chloroethanes

This paper presents the experimental data on vapor-liquid equilibrium and heats of mixing of mixtures of benzene with 1, e-dichloroethane, 1, l, 1 -trichloroethane, and lt1,2,2-tetrachloroethane.A literature survey revealed that the heats of mixing of benzene-l,2-dichloroethane have been studied and Table I shows the extent of study on this system.

Thermodynamic Properties of Niobium Oxides

Thermodynamic properties of three oxides of niobium have been measured using solid state electrochemical cells incorporating yttria-doped thoria (YDT) as the electrolyte in the temperature range T = (1000 to 1300) K. The standard Gibbs energies of formation of NbO, NbO2, and NbO2.422 from the elements can be expressed as: Delta(f)G(NbO)(o) +/- 547/J . mol(-1) = -414 986 + 86.861(T/K) Delta(f)G(NbO2)(o) +/- 548/J . mol(-1) = -779 864 + 164.438(T/K) Delta(f)G(NbO2.422)(o) +/- 775/J . mol(-1) = -911 045 + 197.932(T/K) The results are discussed in comparison with thermodynamic data reported in the literature. The new results refine data for NbO and NbO2 presented in standard data compilations. There are no data in thermodynamic compilations for NbO2.422 (Nb12O29). In the absence of the heat capacity and enthalpy of formation measurements, only the Gibbs energy of formation of NbO2.422 can be assessed. The free energy of formation of stoichiometric Nb2O5 is evaluated on the basis of measurements on NbO2.422 and information available in the literature on phase boundary compositions and isothermal variation of nonstoichiometric parameter with oxygen potential for Nb2O5-x. The results suggest a minor revision of data for Nb2O5. A minimum in the Gibbs energy of mixing for the system Nb-O occurs in the nonstoichiometric domain of Nb2O5-x with x = 0.036.

Thermodynamic properties of strontium titanates Sr2TiO4, Sr3Ti2O7, Sr4Ti3O10, and SrTiO3

The chemical potentials of SrO in two-phase fields (TiO2 + SrTiO3) (SrTiO3 + Sr4Ti3O10) (Sr4Ti3O10 + Sr3Ti2O7) and (Sr3Ti2O7 + Sr2TiO4) of the pseudo-binary system (SrO + TiO2) have been measured in the temperature range (900 to 1250) K relative to pure SrO as the reference state using solid-state galvanic cells incorporating single crystal SrF2 as the electrolyte The cells were operated under pure oxygen at ambient pressure The standard Gibbs free energies of formation of strontium titanates SrTiO3 Sr4Ti3O10 Sr3Ti2O7 and Sr2TiO4 from their component binary oxides were derived from the reversible electromotive force (EMF) of the cells For the formation of the four compounds from their component oxides TiO2 with rutile structure and SrO the standard Gibbs free energy changes are given by Delta G((ox))(SrTiO3) +/- 89/(J mol(-1)) = -121878 + 3 881(T/K) Delta G((ox))(Sr4Ti3O10) +/- 284/(J mol(-1)) = -409197 + 14 749(T/K) Delta G((ox))(Sr3Ti2O7) +/- 190/(J mol(-1)) = -285827 + 10 022(T/K) Delta G((ox))(Sr2TiO4) +/- 110/(J mol(-1))= -159385 + 3 770(T/K) The reference state for solid TiO2 is the rutile form The results of this study are in good agreement with Gibbs free energy of formation data reported in the literature for SrTiO3 but differ significantly with data for Sr4Ti3O10 For Si3Ti2O7 and Si2TiO4 experimental measurements are not available in the literature for direct comparison with the results obtained in this study (C) 2010 Elsevier Ltd All rights reserved

Phase relationships in the system Ni-W-O and thermodynamic properties of NiWO,

The phase diagram of the Ni-W-O system at 1200 K was established by metallographic and X-ray identification of the phases present after equilibration at controlled oxygen potentials. The oxygen partial pressures over the samples were fixed by metered streams of CO+CO2 gas mixtures. There was only one ternary oxide, nickel tungstate (NiWO4), in the Ni-W-O system at a total pressure of 1 atm, and this compound decomposed to a mixture of Ni+WO2.72 on lowering the oxygen potential. The Gibbs' free energy of formation of NiWO4 was determined from the measurement of the e.m.f. of the solid oxide galvanic cell, Pt, Ni+NiWO4+WO2.72/CaO-ZrO2/Ni+NiO, Pt and thermodynamic properties of tungsten and nickel oxides available in the literature. For the reaction, NiO(s)+WO3(s)rarrNiWO4(s) DeltaG°=–10500–0.708 T (±250) cal mol–1.

A Thermodynamic Proposal for the Exposition of Critically and other Subtle Features in Self-Deflagrating Ammonium Perchlorate Systems

A first comprehensive investigation on the deflagration of ammonium perchlorate (AP) in the subcritical regime, below the low pressure deflagration limit (LPL, 2.03 MPa) christened as regime I$^{\prime}$, is discussed by using an elegant thermodynamic approach. In this regime, deflagration was effected by augmenting the initial temperature (T$_{0}$) of the AP strand and by adding fuels like aliphatic dicarboxylic acids or polymers like carboxy terminated polybutadiene (CTPB). From this thermodynamic model, considering the dependence of burning rate ($\dot{r}$) on pressure (P) and T$_{0}$, the true condensed (E$_{\text{s,c}}$) and gas phase (E$_{\text{s,g}}$) activation energies, just below and above the surface respectively, have been obtained and the data clearly distinguishes the deflagration mechanisms in regime I$^{\prime}$ and I (2.03-6.08 MPa). Substantial reduction in the E$_{\text{s,c}}$ of regime I$^{\prime}$, compared to that of regime I, is attributed to HClO$_{4}$ catalysed decomposition of AP. HClO$_{4}$ formation, which occurs only in regime I$^{\prime}$, promotes dent formation on the surface as revealed by the reflectance photomicrographs, in contrast to the smooth surface in regime I. The HClO$_{4}$ vapours, in regime I$^{\prime}$, also catalyse the gas phase reactions and thus bring down the E$_{\text{s,g}}$ too. The excess heat transferred on to the surface from the gas phase is used to melt AP and hence E$_{\text{s,c}}$, in regime I, corresponds to the melt AP decomposition. It is consistent with the similar variation observed for both the melt layer thickness and $\dot{r}$ as a function of P. Thermochemical calculations of the surface heat release support the thermodynamic model and reveal that the AP sublimation reduces the required critical exothermicity of 1108.8 kJ kg$^{-1}$ at the surface. It accounts for the AP not sustaining combustion in the subcritical regime I$^{\prime}$. Further support for the model comes from the temperature-time profiles of the combustion train of AP. The gas and condensed phase enthalpies, derived from the profile, give excellent agreement with those computed thermochemically. The $\sigma _{\text{p}}$ expressions derived from this model establish the mechanistic distinction of regime I$^{\prime}$ and I and thus lend support to the thermodynamic model. On comparing the deflagration of strand against powder AP, the proposed thermodynamic model correctly predicts that the total enthalpy of the condensed and gas phases remains unaltered. However, 16% of AP particles undergo buoyant lifting into the gas phase in the `free board region' (FBR) and this renders the demarcation of the true surface difficult. It is found that T$_{\text{s}}$ lies in the FBR and due to this, in regime I$^{\prime}$, the E$_{\text{s,c}}$ of powder AP matches with the E$_{\text{s,g}}$ of the pellet. The model was extended to AP/dicarboxylic acids and AP/CTPB mixture. The condensed ($\Delta $H$_{1}$) and gas phase ($\Delta $H$_{2}$) enthalpies were obtained from the temperature profile analyses which fit well with those computed thermochemically. The $\Delta $H$_{1}$ of the AP/succinic acid mixture was found just at the threshold of sustaining combustion. Indeed the lower homologue malonic acid, as predicted, does not sustain combustion. In vaporizable fuels like sebacic acid the E$_{\text{s,c}}$ in regime I$^{\prime}$, understandably, conforms to the AP decomposition. However, the E$_{\text{s,c}}$ in AP/CTPB system corresponds to the softening of the polymer which covers AP particles to promote extensive condensed phase reactions. The proposed thermodynamic model also satisfactorily explains certain unique features like intermittent, plateau and flameless combustion in AP/ polymeric fuel systems.

A thermodynamic protocol for explaining subcriticality and other subtle features in self-deflagrating solids

A novel universal approach to understand the self-deflagration in solids has been attempted by using basic thermodynamic equation of partial differentiation, where burning mte depends on the initial temperature and pressure of the system. Self-deflagrating solids are rare and are reported only in few compounds like ammonium perchlorate (AP), polystyrene peroxide and tetrazole. This approach has led us to understand the unique characteristics of AP, viz. the existence of low pressure deflagration limit (LPL 20 atm), hitherto not understood sufficiently. This analysis infers that the overall surface activation energy comprises of two components governed by the condensed phase and gas phase processes. The most attractive feature of the model is the identification of a new subcritical regime I' below LPL where AP does not burn. The model is aptly supported by the thermochemical computations and temperature-profile analyses of the combustion train. The thermodynamic model is further corroborated from the kinetic analysis of the high pressure (1-30 atm) DTA thermograms which affords distinct empirical decomposition rate laws in regimes I' and 1 (20-60 atm). Using Fourier-Kirchoff one dimensional heat transfer differential equation, the phase transition thickness and the melt-layer thickness have been computed which conform to the experimental data.

Betwixt kinetic and thermodynamic control:'Pseudo-Thermodynamic control'

A third mechanistic category of organic reactions, conceptually in-between kinetic and thermodynamic control, needs to be recognized, in order to obtain a proper mechanistic description of certain highly important organic reactions, but also to avoid controversy. In fact, an instance of debatable conclusions having been reached is already known. The term �pseudo-thermodynamic control� is proposed for this newly-defined category, which would include any reaction in which intermediates along different routes mutually interconvert. The new category would thus encompass a very large number of reactions, many of them of great utility.

Consistency limits behavior of bentonites exposed to sea water

This article examines the changes in interparticle forces brought about on prolonged contact (1 year period) of a bentonite clay with artificial seawater. The study is undertaken with the purpose of identifying the physico-chemical factors that impart a nonswelling character to smectite clays deposited in marine environments. Results show that equilibration of the bentonite clay with artificial seawater (total pore salinity approximately 42 gL-1) for a 1 year period does not lead to any mineralogical changes in the clay specimens; however, their exchangeable cation positions become prominently dominated by magnesium ions. The consistency limits of the seawater-equilibrated bentonite was determined on stepwise leaching to lower salinities. The predominance of diffuse double-layer repulsion forces in the pore salt concentration range of 42 gL-1 to 1.1 gL-1 caused an increase in the liquid limits of the seawater-equilibrated bentonite specimens on reducing the salinity in the corresponding range (42 gL-1 to 1.1 gL-1). The attraction forces, however, prevail over the repulsion forces at salt concentrations <1.1 gL-1 and cause a decrease in liquid limit of the clay specimens with reduction in pore salinity, which is typical of nonswelling clays. The attraction forces cause aggregation of the clay unit layers into domains that break down on sodium saturation of the clay specimens. It is inferred that the physico-chemical factors responsible for the nonswelling character of the seawater-equilibrated bentonite specimens at pore salt concentrations below 1.1 gL-1 are inadequate to explain the nonswelling character of smectite-rich Ariake marine clays. The lower consistency limits of the Ariake marine clays in comparison to the nonswelling character, seawater-equilibrated bentonite specimens is attributed to a relative deficiency of interparticle forces in the Ariake marine clay.