Structures of some unusual types of organic compounds

Structures of a variety of compounds isolated in reactions and elucidated with the help of spectral (uv,ir,nmr and mass) data, have been discussed. In a few cases, the assigned structures were confirmed by x-ray crystal structure analysis.

A simple method of estimating the detonation velocity from chemical composition of organic explosives

A simple yet fairly accurate method of calculating the ideal detonation velocity of an organic explosive from a knowledge of the chemical composition alone is proposed. The method is based on the concept that the energetics of a stoichiometrically balanced fuel-oxidizer system is a function of the total oxidizing or reducing valences of the composition. A combination of the valences in the form of Image , where R and P are, respectively, the reducing and oxidizing valences and MW is the molecular weight, has been found to be linearly related to the detonation velocity of the expolosive. The predicting capacity of the method has been found to be superior to other methods in the literature.

Mechanism of adsorption effects on electrode kinetics: Part I: Selection rules in the case of low coverage by molecular surfactants

It is shown that the effect of adsorption of inert molecules on electrode reaction rates is completely accounted for, by introducing into the rate equation, adsorption-induced changes in both the effective electrode area as well as in the electrostatic potential at the reaction site with an additional term for the noncoulombic interaction between the reactant and the adsorbate. The electrostatic potential at the reaction site due to the adsorbed layer is calculated using a model of discretely-distributed molecules in parallel orientation when adsorbed on the electrode with an allowance for thermal agitation. The resulting expression, which is valid for the limiting case of low coverages, is used to predict the types of molecular surfactants that are most likely to be useful for acceleration and inhibition of electrode reactions.

ALWIN-Algorithmic Wiswesser Notation System for Organic Compounds

ALWIN, a new chemical notation system for organic compounds, based on the Wiswesser Line Notation, is described. Procedures and rules are given for constructing ALWIN for acyclic structures and cyclic structures, vi.?., benzene and Its derivatives, monocyclic, bicyclic, polycyclic, perifused, splro, bridged ring, and ring of rlngs systems. A new method called "tessellation" is introduced for the topological descrlptlon of fused and spiro ring systems. Also new concepts are introduced for describing bridged ring and ring of rlngs systems.

Microscopic modelling of adsorption and the generalised surface layer hypothesis

Two- and three-state models for the adsorption of organic compounds at the electrodelelectrolyte interface are proposed. Different size requirements, if any, for the neutral molecule and the adsorbing solvent are also considered. It is shown how the empirical, generalised surface layer (GSL) relationship (between the potential difference and the electrode charge) formulated by Damaskin et a / . can be understood at the molecular level.

Ultralow noise field-effect transistor from multilayer graphene

We present low-frequency electrical resistance fluctuations, or noise, in graphene-based field-effect devices with varying number of layers. In single-layer devices, the noise magnitude decreases with increasing carrier density, which behaved oppositely in the devices with two or larger number of layers accompanied by a suppression in noise magnitude by more than two orders in the latter case. This behavior can be explained from the influence of external electric field on graphene band structure, and provides a simple transport-based route to isolate single-layer graphene devices from those with multiple layers. ©2009 American Institute of Physics

Charge transfer complexes of crown ethers with neutral organic gyama-acceptor, 2-dicyanoethylene 1,3-indane dione

The interaction of benzo-15-crown-5, dibenzo-18-crown-6 and dibenzo-24-crown-8 with 2-dicyanoethylene 1,3-indane dione in CH2Cl2 has been described in terms of the formation of 1 : 1 molecular complexes. The magnitude of association constants and thermodynamic parameters indicate cooperative interactions of oxygens with the acceptors. The 1H and 13C NMR spectra of the complexes show that gyama-gyama interactions are a major source of ground state stabilization in these complexes.

Selectivity in the Interaction of Electron Donor and Acceptor Molecules with Graphene and Single-Walled Carbon Nanotubes

Interaction of electron donor and acceptor molecules with graphene samples prepared by different methods as well as with single-walled carbon nanotubes (SWNTs) has been investigated by isothermal titration calorimetry (ITC). The ITC interaction energies of the graphene samples and SWNTs with electron acceptor molecules are higher than those with electron donor molecules. Thus, tetracyanoethylene (TCNE) shows the highest interaction energy with both graphene and SWNTs. The interaction energy with acceptor molecules varies with the electron affinity as well as with the charge-transfer transition energy for different aromatics. Metallic SWNTs interact reversibly with electron acceptor molecules, resulting in the opening of a gap.

Solubility of chloramine in organic liquids

Abstract is not available.

A Comparative Study of Electrochemical Kinetic Parameters by the Potential Step Method. Electrode Reactions of CyDTA and EDTA Complexes of Cu(II) at DME

By using the same current-time (I-t) curves, electrochemical kinetic parameters are determined by two methods, (a) using the ratio of current at a given potential to the diffusion-controlled limiting current and (b) curve fitting method, for the reduction of Cu(II)–CyDTA complex. The analysis by the method (a) shows that the rate determining step involves only one electron although the overall reduction of the complex involves two electrons suggesting thereby the stepwise reduction of the complex. The nature of I-t curves suggests the adsorption of intermediate species at the electrode surface. Under these circumstances more reliable kinetic parameters can be obtained by the method (a) compared to that of (b). Similar observations are found in the case of reduction of Cu(II)–EDTA complex.

Dielectric and Electron Spin Resonance Spectroscopic Studies of Glassy Crystalline States of Organic Compounds

Dielectric studies of the glassy crystalline states of cyclohexanol, cyclohexanone, and camphor obtained by upercooling the plastic crystalline phase demonstrate the presence of characteristic a- and p-relaxations. The parameters of the a-relaxation fit the Vogel-Tammann-Fulcher (VTF) equation. ESR spin-probe studies of the glassy crystalline phase of cyclohexanol show that there is a marked decrease in the correlation time above the glasslike transition temperature. The present studies suggest the similarity between glassy crystals having long-range orientational disorder and glasses which are known to betra nslationally disordered.

Kinetics of hydrogen evolution on a stainless steel electrode

The kinetic parameters for the hydrogen evolution reaction on a stainless steel substrate have been obtained from a study of the steady-state polarization curves as well as the galvanostatic transients. The high Tafel slope obtained in the steady-state polarization measurements was ascribed to the presence of an oxide film present on the surface of the stainless steel electrode.

Dielectric properties of Li2O-3B(2)O(3) glasses

The frequency and temperature dependences of the dielectric constant and the electrical conductivity of the transparent glasses in the composition Li2O-3B(2)O(3) were investigated in the 100 Hz-10 MHz frequency range. The dielectric constant and the loss in the low frequency regime were electrode material dependent. Dielectric and electrical relaxations were, respectively, analyzed using the Cole-Cole and electric modulus formalisms. The dielectric relaxation mechanism was discussed in the framework of electrode and charge carrier (hopping of the ions) related polarization using generalized Cole-Cole expression. The frequency dependent electrical conductivity was rationalized using Jonscher's power law. The activation energy associated with the dc conductivity was 0.80 +/- 0.02 eV, which was ascribed to the motion of Li+ ions in the glass matrix. The activation energy associated with dielectric relaxation was almost equal to that of the dc conductivity, indicating that the same species took part in both the processes. Temperature dependent behavior of the frequency exponent (n) suggested that the correlated barrier hopping model was the most apposite to rationalize the electrical transport phenomenon in Li2O-3B(2)O(3) glasses. These glasses on heating at 933 K/10 h resulted in the known nonlinear optical phase LiB3O5.

Mechanisms of molecular doping of graphene: A first-principles study

Doping graphene with electron donating or accepting molecules is an interesting approach to introduce carriers into it, analogous to electrochemical doping accomplished in graphene when used in a field-effect transistor. Here, we use first-principles density-functional theory to determine changes in the electronic-structure and vibrational properties of graphene that arise from the adsorption of aromatic molecules such as aniline and nitrobenzene. Identifying the roles of various mechanisms of chemical interaction between graphene and a molecule, we bring out the contrast between electrochemical and molecular doping of graphene. Our estimates of various contributions to shifts in the Raman-active modes of graphene with molecular doping are fundamental to the possible use of Raman spectroscopy in (a) characterization of the nature and concentration of carriers in graphene with molecular doping, and (b) graphene-based chemical sensors.

Novel organic-inorganic composite polymer-electrolyte membranes for DMFCs

Organic-inorganic composite membranes comprising Nation with inorganic materials such as silica, mesoporous zirconium phosphate (MZP) and mesoporous titanium phosphate (MTP) are fabricated and evaluated as proton-exchange-membrane electrolytes for direct methanol fuel cells (DMFCs). For Nation-silica composite membrane, silica is impregnated into Nation matrix as a sol by a novel water hydrolysis process precluding the external use of an acid. Instead, the acidic nature of Nation facilitates in situ polymerization reaction with Nation leading to a uniform composite membrane. The rapid hydrolysis and polymerization reaction while preparing zirconia and titania sols leads to uncontrolled thickness and volume reduction in the composite membranes, and hence is not conducive for casting membranes. Nafion-MZP and Nafion-MTP composite membranes are prepared by mixing pre-formed porous MZP and MTP with Nation matrix. MZP and MTP are synthesised by co-assembly of a tri-block co-polymer, namely pluronic-F127, as a structure-directing agent, and a mixture of zirconium butoxide/titanium isopropoxide and phosphorous trichloride as inorganic precursors. Methanol release kinetics is studied by volume-localized NMR spectroscopy (employing ``point resolved spectroscopy'', PRESS), the results clearly demonstrating that the incorporation of inorganic fillers in Nation retards the methanol release kinetics under osmotic drag. Appreciable proton conductivity with reduced methanol permeability across the composite membranes leads to improved performance of DMFCs in relation to commercially available Nafion-117 membrane.