Sulfonation of arylamines: Part 12. Kinetics of thermal decomposition of dimethylanilinium sulfates

Three dimethylanilinium sulfates (DMAS) have been prepared and characterised by elemental and spectral studies. Thermal decomposition of these salts has been studied by TG and simultaneous TG-DTG technique and kinetic parameters were evaluated from both dynamic and isothermal TG data using mechanism based kinetic equations. The thermal decomposition pathways have also been suggested and it has been found that DMAS salts give dimethyl aminobenzenesulfonic acids (DMABSA) via solid state reaction. The primary step in the thermal decomposition involves proton transfer followed by sulfonation.This revised version was published online in November 2005 with corrections to the Cover Date.     

Investigation of nu(N-H) and nu(C-N) stretching modes of propylamine (C3H7NH2) in a binary system C3H7NH2 + CH3OH via concentration dependent Raman study and ab initio calculations

Raman spectra of propylamine (C3H7NH2) and its binary mixtures, C3H7NH2 + CH3OH with varying mole fractions of the reference system, C3H7NH2, C were recorded in two widely apart wavenumber regions, 3100-3600 cm(-1) and 1225-1325 cm(-1). In the former region, the two Raman bands at approximately 3305 and approximately 3326 cm(-1), obtained after the line shape analysis, which were assigned to symmetric nu(N-H) and anti-symmetric nu(N-H) stretching modes, respectively, show a downshift upon dilution. However, whereas the nu(N-H) anti-symmetric mode shows a shift of 18.6 cm(-1), the nu(N-H) symmetric mode shows a much smaller shift (5.7 cm(-1)) between neat liquid and high dilution, C = 0.1. This aspect has been explained using the optimized geometries calculated employing ab initio theory (MP2 level) for the neat C3H7NH2 and its different hydrogen-bonded complexes. The linewidth versus concentration plot for the nu(N-H) anti-symmetric stretching mode, however exhibits a distinct maxima at C = 0.4, which has been explained as a slight departure from the concentration fluctuation model. In the latter region, a symmetric peak is observed, which corresponds to nu(C-N) stretching mode, which shows an upshift upon dilution and an almost linear concentration dependence. This has also been explained in terms of the parameters obtained from the optimized geometries of the different hydrogen-bonded complexes.     

Thermodynamic Properties of Crystalline Cellulose Allomorphs Studied with Dispersion-Corrected Density Functional Methods

The phonon properties and thermodynamics of four crystalline cellulose allomorphs, Iα, Iβ, II, and III1, have been investigated using dispersion-corrected density functional theory (DFT). In line with experimental findings, the free energy differences between the studied cellulose allomorphs are small, less than 1 kJ/mol per atom. The calculated specific heat at constant volume (Cv) has been compared with the available experimental data in the temperature range 10–300 K. Quasiharmonic approximation has been employed to study thermodynamics and specific heat at constant pressure (Cp). For the studied temperature range of 10–400 K, the specific heat of all cellulose allomorphs shows very similar behavior. The calculated and experimental specific heat agree well at low temperatures below 100 K, but the deviation between theory and experiment increases with temperature. This may be due to increasing phonon anharmonicity as the temperature increases.     

On the occurrence of polytypism in single crystal CdTe thin films

Cadmium telluride thin films have been found to exhibit polytypism. The polytypes are formed when the as grown amorphous CdTe thin films undergo amorphous to crystalline transformation. The transformed single crystal regions correspond to different polytypes. Besides the well known zinc blende type 3 C cubic phase and less often found wurtzite type 2 H phase, four new polytypes (5 H, 6 H, 6 R and 15 R) the only ones known to-date have been found in the present investigation. In addition to the new polytypes, a new structural variant has also been found. This has the same ‘c’ parameter as that of the 2 H phase but has its ‘a’ lattice parameter as ‘a₀ \documentclass{article}\pagestyle{empty}\begin{document}$ a_{\rm o} \sqrt {3} $\end{document}’ (a₀ being the common lattice parameter of the polytypes). A feasible mechanism making the formation of polytypes intelligible has been suggested.     

Influence of divalent ions on composition and viscoelasticity of polyelectrolyte complexes

The addition of monovalent salts to polyelectrolyte complexes (PECs) comprising oppositely charged polyelectrolytes results in diminishing propensity for complexation, leading to complexes with higher water contents and lower moduli. However, the corresponding influence of multivalent ions on polyelectrolyte complexation has not yet been explored beyond enhanced screening effects. Here, we elucidate the significant impact of the valency of the salt cation on the composition, ion partitioning, and viscoelasticity of charge-matched PECs comprising sodium salt of poly(acrylic acid) and poly(allylamine hydrochloride). Notably, preferential partitioning of divalent cations (Ca²⁺ and Sr²⁺) into the complexes is observed, in stark contrast to the depletion of monovalent ions (Na⁺) from the complexes. Concomitantly, electrostatic bridging of polyanion chains by divalent ions is found to hinder their relaxation, manifesting as a non-monotonic evolution of the shear moduli of the complexes with increasing divalent salt concentrations. Relatedly, a failure of time-salt and time-ionic strength superposition approaches in presence of divalent ions is demonstrated, highlighting the nontrivial influence of these ions on chain relaxation behavior.     

Pressure induced phase transitions in Ga1 − x In x P

We have theoretically investigated the effect of pressure on the structural stability of GaP?:?InP mixed system. The three-body-potential (TBP) model has been used. The TBP model consists of long-range as well as short-range interactions; the long-range part includes the modified Coulomb force as well as a three-body term; the short-range part in TBP defines the van der Waals and overlap repulsive interactions. We observe a pressure-induced structural phase transformation from ZnS (B3) to NaCl (B1) type phase in Ga _1?x In _x P. Our calculated transition pressures for the initial GaP and final InP compound semiconductors are in good agreement with other reported data.     

Autonomously Propelled Motors for Value‐Added Product Synthesis and Purification

A proof‐of‐concept design for autonomous, self‐propelling motors towards value‐added product synthesis and separation is presented. The hybrid motor design consists of two distinct functional blocks. The first, a sodium borohydride (NaBH₄) granule, serves both as a reaction prerequisite for the reduction of vanillin and also as a localized solid‐state fuel in the reaction mixture. The second capping functional block consisting of a graphene–polymer composite serves as a hydrophobic matrix to attract the reaction product vanillyl alcohol (VA), resulting in facile separation of this edible value‐added product. These autonomously propelled motors were fabricated at a length scale down to 400 μm, and once introduced in the reaction environment showed rapid bubble‐propulsion followed by high‐purity separation of the reaction product (VA) by the virtue of the graphene–polymer cap acting as a mesoporous sponge. The concept has excellent potential towards the synthesis/isolation of industrially important compounds, affinity‐based product separation, pollutant remediation (such as heavy metal chelation/adsorption), as well as localized fuel‐gradients as an alternative to external fuel dependency.     

Induced twisted-grain-boundary phases in the binary mixtures of a cholesteric and a nematic compound

Thermodynamical, optical-texture and dielectric studies have been performed to study the phase diagram of the binary system of 5-cholesten-3β-ol-octanoate and 4-n-nonyloxybenzoic acid. It is observed that low concentrations of 5-cholesten-3β-ol-octanoate (2–30?mol?%) in 4-n-nonyloxybenzoic acid induce a mean-field phase diagram derived by Renn within the framework of the chiral Chen–Lubenski model. Various optical textures of the twisted-grain-boundary (TGB) phases under different conditions of molecular anchoring have been observed. Weak transitions related to the TGB phases have been detected by temperature dependent dielectric spectroscopy.