Investigations of the Nature of Critical Line Very Close to a Double Critical Point

The curvature of the line of critical points in a reentrant ternary mixture is determined by approaching the double critical point (DCP) extremely closely. The results establish the continuous and quadratic nature of this line. Out study encompasses as small a loop size (ΔT) as 663 mK. The DCP is realized when ΔT becomes zero.

Perturbation of critical solution temperatures by impurity doping

An expression is developed for the variation of the critical solution temperature of a binary liquid system when a third component (dopant) is added, using an extension of the regular solution theory. The model can be used for UCST, LCST and for closed loop systems and has the correct features in the limiting cases.

The influence of lone-pair repulsions on C–C bond lengths: a critical evaluation of the experimental and theoretical evidence

X-Ray structural data, as well as semiempirical and ab initio molecular orbital calculations, reveal no systematic and substantial difference between the C–C bond lengths of cis and trans 1,2-diketones. Additional results on various conformations of 1,2-diimines and 1,2-dithiones follow the same pattern. Therefore, lone-pair repulsions cannot be implicated in the observed lengthening of C–C bonds in isatin and several related molecules. Conjugation in these systems occurs peripherally avoiding the participation of the central C–C bond. Negative hyperconjugative interaction between the oxygen lone pairs and the adjacent C–C σ* orbital is suggested to be the principal reason for the relatively long C–C bond in diketones. This effect is found in both the cis and trans conformations.

Impurity effects on the critical behaviour of the electrical resistance of binary liquid mixtures

The electrical resistance of the binary liquid system cyclohexane + acetic anhydride is measured, in the critical region, both in the pure mixture and when the mixture is doped with small amounts (≈ 100 ppm) of H2O/D2O impurities.T c was approached to aboutt=3×10−6 wheret=(T −T c )/T c . The critical exponentb ≈ 0.35 in the fit of the resistance data to the equationdR/dT ∼t −b does not seem to be affected appreciably by the impurities. There is a sign reversal ofdR/dt in the non-critical region. Binary liquid systems seem to violate the universality of the critical resistivity.

Critical resistivity in impurity doped binary liquid mixtures

The electrical resistance of the critical binary liquid system C6H12+(CH3CO)2O is measured both in the pure form and when the system is doped with small amounts (≈ 100 ppm) of H2O impurities. Near Tc, the resistance varies as dR/dT = A1+A2 (T-Tc)-b with b ≈ 0.35. Neither the critical exponent b nor the amplitude ratio A1/A2 are affected by the impurities. A sign reversal of dR/dT is noticed at high temperatures T much greater-than Tc.

Critical phenomena in electrical resistance of binary liquids: A study of the frequency dependence

The electrical resistance is measured in two binary liquid systems CS2 + CH3NO2 and n-C7H16 + CH3OH in the critical region as a function of frequency from 10 Hz to 100 kHz. The critical exponent b ≈ 0.35 in the singularity of dR/dT α (T - Tc)−b near Tc has no appreciable dependence upon the frequency. Thus any contribution from dielectric dispersion to the critical resistivity is not appreciable. The universal behaviour of the dR/dT anomaly does not seem to be followed in binary liquid systems.

A critical re-examination and a revised phase diagram of La1-xSrxCoO3

We report the results of a comprehensive study on dc magnetization, ac susceptibility, and the magnetotransport properties of the La1-xSrxCoO3(0 <= x <= 0.5) system. At higher Sr doping (x >= 0.18), the system exhibits Brillouin-like field cooled magnetization (M-FC). However, for x < 0.18, the system exhibits a kink in the M-FC, a peak at the intermediate field in the thermoremnant magnetization and a non-saturating tendency in the M-H plot that all point towards the characteristic of spin glass behavior. More interestingly, dc magnetization studies for x < 0.18 do not suggest the existence of ferromagnetic correlation that can give rise to an irreversible line in the spin glass regime. The ac susceptibility study for x > 0.2 exhibits apparently no frequency dependent peak shift around the ferromagnetic transition region. However, a feeble signature of glassiness is verified by studying the frequency dependent shoulder position in chi `' (T) and the memory effect below the Curie temperature. But, for x < 0.18, the ac susceptibility study exhibits a considerable frequency dependent peak shift, time dependent memory effect, and the characteristic spin relaxation time scale tau(0) similar to 10(-13) s. The reciprocal susceptibility versus temperature plot adheres to Curie-Weiss behavior and does not provide any signature of preformed ferromagnetic clusters well above the Curie temperature. The magnetotransport study reveals a cross over from metallic to semiconducting-like behavior for x <= 0.18. On the semiconducting side, the system exhibits a large value of magnetoresistance (upto 75%) towards low temperature and it is strongly connected to the spin dependent part of the random potential distribution in the spin glass phase. Based on the above observations, we have reconstructed a new magnetic phase diagram and characterized each phase with associated properties.

A High Pressure Study of the Phase Diagram and the Critical Exponent β of Binary Liquid Systems

The pressure dependence of critical parameters xc, Tc, and β have been analysed in four systems namely cyclohexane + acetic anhydride, n-heptane + acetic anhydride, methanol + n-heptane, and carbon disulphide + acetonitrile. The separation temperature was found to increase linearly with pressure the value of dTc/dP being 28 mK, 11 mK, 22 mK, and 25 mK respectively. These are in fair agreement with earlier measurements available for two systems. For the methanol + n-heptane system dTc/dP is apparently not consistent with the value predicted from the specific heat and thermal expansion data.Die Druckabhängigkeit der kritischen Parameter xc, Tc und β ist in den vier Systemen Cyclohexan + Essigsäureanhydrid, n-Heptan + Essigsäureanhydrid, Methanol + n-Heptan und Schwefelkohlenstoff + Acetonitril analysiert worden. Es wurde gefunden, daß die kritische Temperatur linear mit dem Druck ansteigt. Die Werte für dTc/dP betragen 28 mK, 11 mK, 22 mK und 25 mK. Sie sind in guter überein-stimmung mit früheren Messungen an zweien dieser Systeme. Für Methanol + n-Heptan stimmt der Wert für dT/dP offensichtlich nicht mit Werten, die mit Hilfe von Daten für die spezifische Wärme und die thermische Ausdehnung vorhergesagt wurden, überein.

Observation of the doubling of critical exponents in reentrant phase transitions

Electrical resistance (R) measurements are reported for ternary mixtures of 3-methylpyridine, water and heavy water as a function of temperature (T) and heavy water content in total water. These mixtures exhibit a limited two-phase region marked by a loop size (ΔT) that goes to zero as the double critical point (DCP) is approached. The measurements scanned the ΔT range 1.010°C less-than-or-equals, slant ΔT less-than-or-equals, slant 77.5°C. The critical exponent (θ), which signifies the divergence of ∂R/∂T, doubles within our experimental uncertainties as the DCP is reached very closely.

Continuous ordering below the tricritical point: A critical test for the kinetic pathway in Fe-12at.% Si alloy

A critical test has been presented to establish the nature of the kinetic pathways for the decomposition of Fe-12 at.% Si alloy below the metastable tricritical point. The results, based on the measurements of saturation magnetization, establish that a congruent ordering from B2 --> D0(3) precedes the development of a B2 + D0(3) two-phase field, consistent with the predictions in 1976 of Allen and Cahn.

Critical Reappraisal of Colloidal Activity of Clays

Soil properties and their behavior, apart from stress history, are influenced markedly by physicochemical characteristics of the constituent clay and nonclay minerals and their relative proportions. Atterberg limits and Skempton’s colloidal activity, which are simple quantitative parameters, reflect the composite effects of the soil constituents and their interactions with pore fluid. Micromechanistic interpretations of these parameters have been provided in this paper. It has been shown that, in general, the liquid limit of fine-grained soils reflects the physicochemical potential and that each of the factors of Skempton’s colloidal activity are interdependent. It has been illustrated that property correlations with colloidal activity, as well as with Atterberg limits, result in involved interrelationships due to the interdependence of the parameters.

Critical Reappraisal of Colloidal Activity of Clays

Soil properties and their behavior, apart from stress history, are influence markedly by physicochemical characteristics of the constituent clay and nonclay minerals and their relative proportions. Atterberg limits and Skempton's colloidal activity, which are simple quantitative parameters, reflect the composite effects of the soil constituents and their interactions with pore fluid. Micromechanistic interpretations of these parameters have been provided in this paper. It has been shown that, in general, the liquid limit of fine-grained soils reflects the physicochemical potential and that each of the factors of Skempton's colloidal activity are interdependent. It has been illustrated that property correlations with colloidal activity, as well as with Atterberg limits, result in involved interrelationships due to the interdependence of the parameters.

Energy efficiencies of end-use devices in an electro-metallurgical industry: A critical study

The inefficient use of energy in a large number of industries is slowly developing into a major energy crisis in the already power-starved Karnataka State, India. This study attempts to bring out the present inefficient pattern of energy use in an electro-metallurgical industry. It also brings out the considerable scope for energy conservation, especially by increasing the efficiency of the end-use devices used. This concept, when extended to other industries, wherein increasing efficiency of the end-use devices would provide the desired end results with small energy input. This, in turn, would result in a slower rate of energy growth as well as saving in energy use.

Behaviour of the curve of critical exponents near and away from a double critical point

To investigate the nature of the curve of critical exponents (as a function of the distance from a double critical point), we have combined our measurements of the osmotic compressibility with all published data for quasibinary liquid mixtures. This curve has a parabolic shape. An explanation of this result is advanced in terms of the geometry of the coexistence dome, which is contained in a triangular prism.