382 resultados para vapour liquid equilibria


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In this paper the results of a detailed investigation on the metastable phase relations in undercooled as well as rapidly solidified Al---Ge alloys containing 2–50 at.% Ge are reported. Data obtained on the structure and morphology of phases enable us to arrive at the phase relations and transformation processes occurring in undercooled and rapidly quenched melts of this system. These results are explained with the help of a metastable phase diagram consisting of a peritectic and eutectic reaction involving metastable phases.

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We have analyzed the diameters of the liquidliquid coexistence curves of several binary liquid mixtures in search of the critical anomaly predicted by current theories. We find that while the data are consistent with the predicted functional form, the evidence for such an anomaly is not compelling.

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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.

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Proton NMR spectra of 1,3-diazanaphthalene and 1,2,4-triazanaphthalene have been investigated in the nematic phase of three liquid crystals. The spectral analysis provided direct dipole-dipole couplings which have been used to derive the molecular structure. Geometry of the phenyl ring in both the molecules deviates from the regular hexagonal structure. Signs of the order parameter of the largest magnitude are opposite in liquid crystals with positive diamagetic anisotropies.

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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.

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A simple volume dilatometer is described for the precise measurements of volume changes as a function of temperature in liquid mixtures. The expansivity of (cyclohexane + acetic anhydride) in the critical region was measured. The critical solution temperature Tc was approached to within 9 mK. For T > (Tc + 0.3 K), the results results follow both a logarithmic and a power-law behaviour with an exponent ≈ 1/8. But for T < (Tc + 0.3 K), the results seem to be affected possibly by gravity or temperature gradients. In this region, the expected expansivity anomaly is rounded off to a cusp. The expansivity shows a reduced anomaly for off-critical compositions. A discussion of the local extremum and a correlation between negative expansivity and the resistivity anomaly are also given.

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It is shown that cholesteric liquid crystal mixtures can be used as convenient solvents in NMR experiments for the determination of molecular structure. The advantages of such solvents are pointed out. The application is demonstrated for acetonitrile; the value for the HCH bond angle thus determined is 108.8°.

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The efficiency of dephosphorisation is governed by the thermodynamic behaviour of phosphorus and oxygen in molten metal, and P2O5 and FeO in slag. The equilibrium distribution of phosphorus and oxygen, for a wide range of chemical compositions simulating the evolution of slag composition during a typical BOF blow, has been experimentally determined. A mathematical model for estimation of the activity coefficients, as a function of the chemical composition, was also attempted.

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The Raman spectrum of cyclopropane is of great interest in view of the fact that it is the simplest of the cyclic hydrocarbons, and also from the point of view of the structure of the cyclopropane molecule. I have investigated this substance both in the liquid and vapour states and have obtained the following results :

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We study the renormalization group flows of the two terminal conductance of a superconducting junction of two Luttinger liquid wires. We compute the power laws associated with the renormalization group flow around the various fixed points of this system using the generators of the SU(4) group to generate the appropriate parametrization of an matrix representing small deviations from a given fixed point matrix [obtained earlier in S. Das, S. Rao, and A. Saha, Phys. Rev. B 77, 155418 (2008)], and we then perform a comprehensive stability analysis. In particular, for the nontrivial fixed point which has intermediate values of transmission, reflection, Andreev reflection, and crossed Andreev reflection, we show that there are eleven independent directions in which the system can be perturbed, which are relevant or irrelevant, and five directions which are marginal. We obtain power laws associated with these relevant and irrelevant perturbations. Unlike the case of the two-wire charge-conserving junction, here we show that there are power laws which are nonlinear functions of V(0) and V(2kF) [where V(k) represents the Fourier transform of the interelectron interaction potential at momentum k]. We also obtain the power law dependence of linear response conductance on voltage bias or temperature around this fixed point.

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Experimental results for breakdown voltage of sodium vapour measured for the first time using coaxial cylindrical electrodes of fixed gap distance (5 mm) and pressure (corrected to2 0 "C) in the range2 1 to 652 Pa are reported, and are founfdo l ltoow Paschen's Law. The investigations also reveal that V th-Ie characteristics are pressure dependent; the current during the breakdown and the buoifl dc-uurpre nt after a breakdoiws nei ther positive or negative. in spite of the central cylinder being always maintained at a positive potential

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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.