Controversy on the Free Energy of Formation of CaO Additional Evidence in Support of Thermochemical Data

The standard free energies of formation of CaO derived from a variety of high-temperature equilibrium measurements made by seven groups of experimentalists are significantly different from those given in the standard compilations of thermodynamic data. Indirect support for the validity of the compiled data comes from new solid-state electrochemical measurements using single-crystal CaF2 and SrF2 as electrolytes. The change in free energy for the following reactions are obtained: CaO + MgF2 --> MgO + CaF2 Delta G degrees = -68,050 -2.47 T(+/-100) J mol(-1) SrO + CaF2 --> SrF2 + CaO Delta G degrees = -35,010 + 6.39 T (+/-80) J mol(-1) The standard free energy changes associated with cell reactions agree with data in standard compilations within +/- 4 kJ mol(-1). The results of this study do not support recent suggestions for a major revision in thermodynamic data for CaO.

High-Pressure Magnetic-Susceptibility Studies of Spin-State Transaction

High-pressure magnetic susceptibility measurements have been carried out on Fe(dipy)2(NCS)2 and Fe(phen)2(NCS)2 in the pressure range 1–10 kbar and tempeature range 80–300 K in order to investigate the factors responsible for the spin-state transitions. The transitions change from first order to second or higher order upon application of pressure. The temperature variation of the susceptibility at different pressures has been analysed quantitatively within the framework of available models. It is shown that the relative magnitudes of the ΔG0 of high-spin and low-spin conversion and the ferromagnetic interaction between high-spin complexes determines the nature of the transition.

Investigating physical properties of solid dosage forms during pharmaceutical processing : Process analytical applications of vibrational spectroscopy

In order to improve and continuously develop the quality of pharmaceutical products, the process analytical technology (PAT) framework has been adopted by the US Food and Drug Administration. One of the aims of PAT is to identify critical process parameters and their effect on the quality of the final product. Real time analysis of the process data enables better control of the processes to obtain a high quality product. The main purpose of this work was to monitor crucial pharmaceutical unit operations (from blending to coating) and to examine the effect of processing on solid-state transformations and physical properties. The tools used were near-infrared (NIR) and Raman spectroscopy combined with multivariate data analysis, as well as X-ray powder diffraction (XRPD) and terahertz pulsed imaging (TPI). To detect process-induced transformations in active pharmaceutical ingredients (APIs), samples were taken after blending, granulation, extrusion, spheronisation, and drying. These samples were monitored by XRPD, Raman, and NIR spectroscopy showing hydrate formation in the case of theophylline and nitrofurantoin. For erythromycin dihydrate formation of the isomorphic dehydrate was critical. Thus, the main focus was on the drying process. NIR spectroscopy was applied in-line during a fluid-bed drying process. Multivariate data analysis (principal component analysis) enabled detection of the dehydrate formation at temperatures above 45°C. Furthermore, a small-scale rotating plate device was tested to provide an insight into film coating. The process was monitored using NIR spectroscopy. A calibration model, using partial least squares regression, was set up and applied to data obtained by in-line NIR measurements of a coating drum process. The predicted coating thickness agreed with the measured coating thickness. For investigating the quality of film coatings TPI was used to create a 3-D image of a coated tablet. With this technique it was possible to determine coating layer thickness, distribution, reproducibility, and uniformity. In addition, it was possible to localise defects of either the coating or the tablet. It can be concluded from this work that the applied techniques increased the understanding of physico-chemical properties of drugs and drug products during and after processing. They additionally provided useful information to improve and verify the quality of pharmaceutical dosage forms

Spin-state equilibria in the LCoO3 system from 59Co NMR

Spin-state equilibria in the whole set of LCoO3 (where L stands for a rare-earth metal or Y) have been investigated with the use of 59Co NMR as a probe for the polycrystalline samples (except Ce) in the temperature interval 110-550 K and frequency range 3- 11.6 MHz. Besides confirming the coexistence of the high-spin—low-spin state in this temperature range, a quadrupolar interaction of ∼0.1 -0.5 MHz has been detected for the first time from 59Co NMR. The NMR line shape is found to depend strongly on the relative magnitude of the magnetic and quadrupolar interactions present. Analysis of the powder pattern reveals two basically different types of transferred hyperfine interaction between the lighter and heavier members of the rare-earth series. The first three members of the lighter rare-earth metals La, Pr (rhombohedral), and Nd (tetragonal), exhibit second-order quadrupolar interaction with a zero-asymmetry parameter at lower temperatures. Above a critical temperature TS (dependent on the size of the rare-earth ion), the quadrupolar interaction becomes temperature dependent and eventually gives rise to a first-order interaction thus indicating a possible second-order phase change. Sm and Eu (orthorhombic) exhibit also a second-order quadrupolar interaction with a nonzero asymmetry parameter ((η∼0.47)) at 300 K, while the orthorhombic second-half members (Dy,..., Lu and Y) exhibit first-order quadrupolar interaction at all temperatures. Normal paramagnetic behavior, i.e., a linear variation of Kiso with T-1, has been observed in the heavier rare-earth cobaltites (Er,..., Lu and Y), whereas an anomalous variation has been observed in (La,..., Nd)CoO3. Thus, Kiso increases with increasing temperature in PrCoO3 and NdCoO3. These observations corroborate the model of the spin-state equilibria in LCoO3 originally proposed by Raccah and Goodenough. A high-spin—low-spin ratio, r=1, can be stabilized in the perovskite structure by a cooperative displacement of the oxygen atoms from the high-spin towards the low-spin cation. Where this ordering into high- and low-spin sublattices occurs at r=1, one can anticipate equivalent displacement of all near-neighbor oxygen atoms towards a low-spin cobalt ion. Thus the heavier LCoO3 exhibits a small temperature-independent first-order quadrupolar interaction. Where r<1, the high- and low-spin states are disordered, giving rise to a temperature-dependent second-order quadrupolar interaction with an anomalous Kiso for the lighter LCoO3.

59Co NMR studies of the spin-state equilibria in rare-earth cobaltites

Hyperfine interaction parameters reveal differences in the nature of spin-state equilibria in the lighter and heavier rare-earth cobaltites; the crystal-field parameter is lower in the lighter cobaltites. Temperature variation of the quadrupolar coupling constant is also more marked in the lighter rare-earth cobaltites, with NdCoO3 showing evidence for a structural phase transition.

Calorimetric, infrared and ESR studies of the plastically crystalline state of organic compounds

Enthalpy changes of the crystal-plastic and plastic-liquid transitions are related to the temperature range of stability of the plastic phase. Thermodynamics of the plastic state of binary mixtures have been examined. Infrared correlation times, τc, and activation energies have been measured for a few molecules in the plastic state. Molecular tumbling times, τt, have also been measured employing ESR spectra of a spin-probe. Plots of log τc(τt) 1/T are continuous through the plastic-liquid transition. Activation energies for molecular motion seem to vary in the same direction as the ΔH of the plastic-crystal transition. Infrared correlation times of solute molecules in binary solutions in the plastic and the liquid states show interesting variations with solute concentration.

Enhanced ionic conduction in dispersed solid electrolyte systems CaF2---Al2O3 and CaF2---CeO2

Dispersions of Al2O3 as well as CeO2 in CaF2 are found to enhance the conductivity of CaF2. Both these systems are biphasic and the electrical conduction in them is purely ionic in nature. At 650 K the increase in the ionic conductivity of the dispersed solid electrolyte system CaF2---Al2O3 is by about two orders of magnitude in relation to the conductivity of the host electrolyte CaF2, whereas for the CaF2---CeO2 system it is about three orders of magnitude. Some aspects of the increase in the ionic conductivities of CaF2---Al2O3 and CaF2---CeO2 electrolytes can be explained by a recent theoretical model. It is proposed that a substantial enhancement in the vacancy concentration of CaF2, brought about by the attraction of F− ions to the surface of Al2O3 (or CeO2), is responsible for the low temperature increase in the ionic conductivity of CaF2.

Determination of the thermodynamic properties of xMgO + (1 x)MnO (s, sln) from a solid-electrolyte galvanic cell in the temperature range 1163 to 1318 K

The thermodynamic activities of MgO in the NaCl-type solid solutions which can exist in xMgO + (1 x)MnO have been determined in the temperature range 1163 to 1318 K from a solid-state galvanic cell incorporating MgF2 as the solid electrolyte. The activities of MnO have been calculated by a graphical Gibbs-Duhem integration method. The activities of both the components exhibit positive deviations from ideality over the entire composition range. The excess molar enthalpies are found to be positive. Further, xMgO + (1 - x)MnO does not conform to regular-solution behaviour. The origin of the excess thermodynamic properties is discussed in relation to the cationic size disparity and the crystal-field effects.

A Conjecture Concerning Transformation Of A Supercooled Hard-Sphere Liquid To A Metastable Disordered Solid

It is conjectured that the hard sphere system has several distinct solid phases, all but one of which are metastable. The bifurcation theory analysis of freezing is extended to the description of the transition between a supercooled liquid and a disordered solid by defining a restricted phase space for the disordered solid. This approach leads to the prediction of a first order transition between a supercooled hard sphere fluid and a disordered metastable hard sphere solid. The results of the calculation are in qualitative agreement with the results of Woodcock's molecular dynamics computer simulations. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.

An infrared spectroscopic study of the phase transitions of crystalline aromatic donor-acceptor complexes involving a pseudoplastic state

Variable temperature i.r. spectroscopic studies of weak pi-donor-pi-acceptor complexes in the crystalline state indicate that the complexes undergo order-disorder transitions, the disorder being caused by molecular motion. Thermodynamic data on the phase transitions along with the spectral data suggest that the high-temperature crystalline forms of the complexes are likely to be pseudoplastic.

Lead-acid batteries for partial-state-of-charge applications

2 V/40 Ah valve-regulated lead-acid (VRLA) cells have been constructed with negative plates employing carbon black as well as an admixture of carbon black fumed silica as additives in negative active material for partial-state-of-charge (PSoC) applications. Electrical performance of such cells is compared with conventional 2 V/40 Ah VRLA cells for PSoC operation. Active material utilization has been found to be higher for carbon-black fumed-silica mixed negative plates while formation is faster for cells with carbon-black mixed negative plates. Both faradaic efficiency and percentage capacity delivered have been found to be higher for cells with carbon-black + fumed-silica mixed negative plates. However, a high self-discharge rate is observed for cells with carbon-black + fumed-silica mixed negative plates.

A Magnetic Susceptibility Study of Spin-state Transitions in Rare-earth TrioxocobaItates( III)

Rare-earth trioxocobaltates(lll), Ln[CoO,], with Ln = Pr, Nd, Tb, Dy. and Yb exhibit low-spin to high-spin transitions of cobalt characterised by a maximum in the Ax-l against temperature plots where Ax is the cobalt contribution to the magnetic susceptibility. The susceptibility behaviour is distinct from that of La[CoO,] which shows a plateau in the x-I-T curve accompanied by a structural transition. The temperature at which the AX- I-T curve shows a maximum increases with the decrease in the size of the rare-earth ion. The susceptibility behavior of solid solutions of La,,Nd,CoO, has been investigated to see how the behaviour characteristic of Nd[CoO,] changes to that of La[CoO,].

An investigation of solid adamantane by a modified isothermal-isobaric ensemble Monte Carlo simulation

Isothermal-isobaric ensemble Monte Carlo simulation studies of adamantane have been carried out at different temperatures. Thermodynamic properties and radial distribution functions calculated by employing a simple potential model based on sitesite interactions show good agreement with experiment and suggest that the solid is orientationally disordered at high temperatures.

Electrical transport in the perovskite solid solution LaNi1-xCoxO3

We have studied the resistivity and thermopower of the solid solution LaNi1-xCoxO3 in the temperature range 1.4K-300K. Effect of interaction and localization are seen in the low temperature transport data for x<0.55. A negative anomaly in the thermopower has been observed at low temperature for 0.1state transtion in Co ions.

The effect of rapid solidification on the order-disorder transformation in iron-based alloys

The effect of rapid solidification on the ordering reaction in Fe---Si and Fe---Al alloys has been reported. It is shown that rapid solidification can influence the ordering reaction in alloys with higher critical ordering temperatures. For ordering reactions at lower temperatures, the effect is similar to that of solid-state quenching. Different factors influencing the ordering reactions and domain structures during rapid solidification of iron-based alloys are discussed.