Studies on phosphorus oxychloride and aluminium chloride complex

1. Anhydrous aluminium chloride reacts with phosphorus oxychloride to give a complex with a composition AlCl3.2 POCl3 which can be prepared in the form of a free flowing powder. 2. The phosphorus oxychloride-aluminium chloride complex in nitrobenzene dissociates into AlCl3.POCl3 and POCl3 as indicated by the cryoscopic measurements. 3. The solution of the complex in nitrobenzene has a higher specific conductivity than the corresponding electrical conductivities of individual components. Similar higher electrical conductance is observed when the two components are mixed in nitrobenzene in different proportions. 4.When a solution of anhydrous aluminium chloride in nitrobenzene is titrated conductometrically against a solution of phosphorus oxychloride in nitrobenzene, a limiting value in the conductivity is reached at point corresponding to the molecular composition, the components in the ratio of 1:2 AlCl3: POCl3 in solution. 5. The absorption maxima of the complex in nitrobenzene solution differ from the absorption maximum of the individual components.

Polarisation studies on the Raman spectra of cubic crystals - Part I. Sodium chlorate

neral expressions have been derived for the intensities of the three classes of Raman lines namely totally symmetric A, doubly degenerate E and triply degenerate F, in the case of cubic crystals under the following conditions. The direction of the incident beam which is polarised with its electric vector inclined at an angle α to the normal to the scattering plane makes an angle Θ with one of the cubic axes of the crystal. The transversely scattered light is analysed by a double image prism with its principal axes inclined at angle β to the normal to the scattering plane, which is horizontal. For incident unpolarised light and Θ=22 1/2°, and the scattered light being analysed by a double image prism rotated through 45° from the position when its principal axes are vertical and horizontal ρ{variant} for A lines is equal to one, for E lines >1 and for F lines <1. This gives a method of classifying the Raman lines of a cubic crystal in a single setting. The results have been experimentally verified in sodium chlorate.

Pressure dependence of chlorine nuclear quadrupole resonance in sodium chlorate

The pressure dependence of the chlorine NQR frequency in NaClo3 has been investigated up to 20 k bar hydrostatic pressure. A distinct break in slope in the pressure dependence of the resonance frequency is observed near 11 k bar. This is attributed to a phase transition reported earlier by Bridgman in this pressure region.

Aspects of tautomerism. Part 16. Influence of the y-keto function on the reactions of sulphonic acids

Reaction of sodium 2-formylbenzenesulphonate (1) with thionyl chloride or phosphorous pentachloride gives a mixture of pseudo (2) and normal (3) sulphonyl chlorides. Whereas ammonium 2-carboxybenzenesulphonate (6) gives only the normal sulphonyl chloride (7) on reaction with thionyl chloride, a mixture of normal (7) and pseudo (8) isomers are formed on reaction with phosphorous pentachloride. Sodium 2-benzoylbenzenesulphonate (15), on the other hand, gives the corresponding normal sulphonyl chloride (16) on reaction with both of the reagents mentioned above. Based on these observations it is concluded that γ-keto sulphonic acids are amenable to the influence of γ-carbonyl group as in the case of γ-keto carboxylic acids but to a lesser extent. © 1989 Indian Academy of Sciences.

Increasing ionic conductivity of polymer-sodium salt complex by addition of a non-ionic plastic crystal

Ionic conductivity and other physico-chemical properties of a soft matter composite electrolyte comprising of a polymer-sodium salt complex and a non-ionic plastic crystal are discussed here. The electrolyte under discussion comprises of polyethyleneoxide (PEO)-sodium triflate (NaCF3SO3) and succinonitrile (SN). Addition of SN to PEO-NaCF3SO3 resulted in significant enhancement in ionic conductivity. At 50% SN concentration (with respect to weight of polymer), the polymer-plastic composite electrolyte room temperature (= 25 degrees C) ionic conductivity was similar to 1.1 x 10(-4) Omega(-1) cm(-1), approximately 45 times higher than PEO-NaCF3SO3. Observations from ac-impedance spectroscopy along with X-ray diffraction, differential scanning calorimetry and Fourier transform inrared spectroscopy strongly suggest the enhancement in the composite is ionicconductivity due to enhanced ion mobility via decrease in crystallinity of PEO. The free standing composite polymer-plastic electrolytes were more compliable than PEO-NaCF3SO3 thus exhibiting no detrimental effects of succinonitrile addition on the mechanical stability of PEO-NaCF3SO3. We propose that the exploratory PEO-NaCF3SO3-SN system.discussed here will eventually be developed as a prototype electrolyte.for sodium-sulfur batteries capable of operating at ambient and.sub-ambient conditions. (C) 2010 Elsevier B.V. All rights reserved.

Ultrasonic measurement of the elastic constants of sodium p-nitrophenolate dihydrate single crystals

Sodium p-nitrophenolate dihydrate single crystals possess excellent nonlinear optical properties such that they can be used for optical second-harmonic generation. It belongs to the orthorhombic system with the space group Ima2. Slow evaporation or slow cooling techniques can be used to grow good optical quality single crystals from supersaturated solution. All the nine elastic constants of this crystal have been measured using an ultrasonic technique. Samples for measurements have been cut along desired crystallographic axes and the pulse echo overlap technique has been used to measure longitudinal and shear ultrasonic wave velocities along appropriate symmetry directions in the crystal. The McSkimin Delta t criterion has been applied to determine the round trip travel time accurately, from which the nine elastic constants have been evaluated. Temperature variation of selected elastic constants in a limited range have also been measured and reported.

A New Method for the Preparation of Sulphuryl Chloro Fluoride

It has been observed that a suspension of sodium fluoride in boiling acetonitrile could be used for the preparation of fluorine compounds such as silicon tetrafluoride [1], thiophosphoryl fluoride [2], sulphur tetrafluoride [3,4], and fluorocyclophosphazenes [5]. This method, when adopted for the fluorination of sulphuryl chloride [6], it is observed that a mixture of sulphuryl fluoride and sulphuryl chloro fluoride is obtained. On the other hand, when lead fluoride is substituted for sodium fluoride, pure sulphuryl chloro fluoride is evolved. Based on this observation, a new method has been standardised for the preparation of a pure sample of sulphuryl chlorofluoride by fluorinating sulphuryl chloride by lead fluoride in acetonitrile medium.

REACTION OF THIOPHOSPHORYL FLUORIDE AND THIOPHOSPHORYL CHLORIDE WITH DIMETHYL SULPHOXIDE

Solid complexes of thiophosphoryl fluoride and thiophosphoryl chloride with dimethyl sulphoxide (DMSO) have been prepared and characterized.

Reaction of Thiophosphoryl Fluoride and Thiophosphoryl Chloride with Dimethyl Sulphoxide

Solid complexes of thiophosphoryl fluoride and thiophosphoryl chloride with dimethyl sulphoxide (DMSO) have been prepared and characterized.

Proton-bifurcated C-H center dot center dot center dot(O,O) hydrogen bonds in 2,3-dichloro-6-nitrobenzylaminium chloride

In the crystal structure of the title salt, C7H7Cl2N2O2+ center dot Cl-, the chloride anions participate in extensive hydrogen bonding with the aminium cations and indirectly link the molecules through multiple N+-H center dot center dot center dot Cl- salt bridges. There are two independent molecules in the asymmetric unit, related by a pseudo-inversion center. The direct intermolecular coupling is established by C-H center dot center dot center dot O, C-H center dot center dot center dot Cl and C-Cl center dot center dot center dot Cl- interactions. A rare three-center (donor bifurcated) C-H center dot center dot center dot (O,O) hydrogen bond is observed between the methylene and nitro groups, with a side-on intramolecular component of closed-ring type and a head-on intermolecular component.

A molecular dynamics study of cage-to-cage migration in sodium Y zeolite: role of surface-mediated diffusion

The details of cage-to-cage migration have been obtained from an analysis of the molecular dynamics trajectory of a probe adsorbate. It is observed that particles utilize the region within a radius of 2 angstrom from the window center but with diffusion taking place predominantly at 1.6 angstrom from the window center and a potential energy of nearly -12 kJ/mol. A barrier of about 0.5 kJ/mol is observed for surface-mediated diffusion. Surprisingly, for diffusion without surface mediation for a particle going from one cage center to another, there is an attractive well near the window instead of a barrier. At low adsorbate concentrations and room temperature, the predominant mode for cage-to-cage migration is surface-mediated diffusion. The analysis suggests that particles slide along the surface of the inner walls of the alpha-cages during migration from one cage to another.