Cerimetry in non-aqueous media - Oxidation of oxalic acid through the intermediate formation of ceric oxalate

It was found that ceric oxalate is an intermediate product in the oxidation of oxalic acid by ammonium hexanitrato cerate in solvents such as acetonitrile, and a mixture of acetonitrile and glacial acetic acid. Conditions for the formation of ceric oxalate and its decomposition into carbon dioxide and cerous oxalate have been studied. An analytical method for the estimation of oxalic acid in non-aqueous media has been evolved based on this reaction.

Structure of the hydrogen-bonded water molecule in crystals

A correlation of the structural data on IS hydrates obtained by x-ray diffraction, neutron diffraction, and proton magnetic resonance reveals that when a water molecule is hydrogen bonded into a crystal structure and the angle subtended at the donor water oxygen by the acceptor atoms deviates from the vapor H-O-H angle, bent hydrogen bonds are formed in preference to distortion of the H-O-H angle. Theoretical justification for this result is obtained from energy considerations by calculating the energy of formation of bent hydrogen bonds on the basis of the Lippincott-Schroeder potential function model for the hydrogen bond and the energy of deformation of the H-O-H angle from spectroscopic force constants.

Evaluation of solute-solvent interactions from solvent blue-shifts of n → π* transitions of C=O, C=S, NO2 and N=N groups: hydrogen bond energies of various donor-acceptor systems

Effects of non-polar, polar and proton-donating solvents on the n → π* transitions of C=O, C=S, NO2 and N=N groups have been investigated. The shifts of the absorption maxima in non-polar and polar solvents have been related to the electrostatic interactions between solute and solvent molecules, by employing the theory of McRAE. In solvents which can donate protons the solvent shifts are mainly determined by solute-solvent hydrogen bonding. Isobestic points have been found in the n → π* bonds of ethylenetrithio-carbonate in heptane-alcohol and heptane-chloroform solvent systems, indicating the existence of equilibria between the hydrogen bonded and the free species of the solute. Among the different proton-donating solvents studied water produces the largest blue-shifts. The blue-shifts in alcohols decrease in the order 2,2,2-trifluoroethanol, methanol, ethanol, isopropanol and t-butanol, the blue-shift in trifluoroethanol being nearly equal to that in water. This trend is exactly opposite to that for the self-association of alcohols. It is suggested that electron-withdrawing groups not merely decrease the extent of self-association of alcohols, but also increase the ability to donate hydrogen bonds. The approximate hydrogen-bond energies for several donor-acceptor systems have been estimated. In a series of aliphatio ketones and nitro compounds studied, the blue-shifts and consequently the hydrogen bond energies decrease with the decrease in the electron-withdrawing power of the alkyl groups. It is felt that electron-withdrawing groups render the chromophores better proton acceptors, and the alcohols better donors. A linear relationship between n → π* transition frequency and the infrared frequency of ethylenetrithiocarbonate has been found. It is concluded that stabilization of the electronic ground states of solute molecules by electrostatic and/or hydrogen-bond interactions determines the solvent shifts.

Studies in bubble formation - IV: bubble formation at porous discs

Bubble formation from porous discs submerged in liquids of different physical properties has been investigated. It is found the number of sites effective for bubble formation is much smaller than the total potentially available sites. The number of effective sites is found to be a function of the surface tension, viscosity, and density of the liquid and the gas flow rate through the disc. A model proposed on the basis of bubble formation from an isolated nozzle and the close packed arrangement of the formed bubbles, explains the phenomenon adequately. © 1970.

A unified approach to bubble and drop formation

An approach, starting with the bubble formation model of Khurana and Khumar, has been presented, which is found to be reasonably applicable to the formation of both bubbles and drops from single submerged nozzles. The model treats both the phenomena jointly as the formation of a dispersed phase entity resulting from injection, whose size depends upon operating parameters and physical properties.

Reaction of benzisoxazolium cations with cyclic β-diketones

Reaction of 2-ethylbenzisoxazolium fluoborate (III) with dimedone, dihydroresorcinol, 2-methyldihydroresorcinol and 2-methylcyclopentane-1,3-dione in the presence of base leads to the formation of amides VIII, XI, X and XIII respectively, via the benzoketoketenimine intermediate (IX) and an intramolecular migration. The 7-hydroxy-2-ethylbenzisoxazolium salt (IV) gives the amide (XIV) by double migration. Amides VIII, XI, X and XIII undergo intramolecular Michael reaction to furnish the benzoxazinones (XVI, XVIII, XVII and XXVI). Stereochemistry of this addition is discussed and the conformation in which the CN bond at C-1′ is attached equatorially to the cyclohexanone ring is assigned to the Spirans (XX, XXX and XXVIII). Effect of acids and bases on the amide (VIII) and the spiran (XVI) is described.

Potential functions for hydrogen bond interactions - IV. Minimum Energy Conformation of the α-Helical Structure of PoIy-L-Alanine

Making use of the empirical potential functions for peptide NH .. O bonds, developed in this laboratory, the relative stabilities of the rightand left-handed α-helical structures of poly-L-alanine have been investigated, by calculating their conformational energies (V). The value of Vmin of the right-handed helix (αP) is about - 10.4 kcal/mole, and that of the left-handed helix (αM) is about - 9.6 kcal/mole, showing that the former is lower in energy by 0.8 kcal/mole. The helical parameters of the stable conformation of αP are n ∼ 3.6 and h ∼ 1.5 Å. The hydrogen bond of length 2.85 Å and nonlinearity of about 10° adds about 4.0 kcal/ mole to the stabilising energy of the helix in the minimum enregy region. The energy minimum is not sharply defined, but occurs over a long valley, suggesting that a distribution of conformations (φ{symbol}, ψ) of nearly the same energy may occur for the individual residues in a helix. The experimental data of a-helical fibres of poly-L-alanine are in good agreement with the theoretical results for αP. In the case of proteins, the mean values of (φ{symbol}, ψ) for different helices are distributed, but they invariably occur within the contour for V = Vmin + 2 kcal/mole for αP.

What should I think; How should I feel? : The balancing of personal experiences and social norms in the outgroup attitude formation of youth

The present study focused on the associations between the personal experiences of intergroup contact, perceived social norms and the outgroup attitudes of Finnish majority and Russian-speaking minority youth living in Finland. The theoretical background of the study was derived from Allport s (1954) theory of intergroup contact (i.e., the contact hypothesis), social psychological research on normative influences on outgroup attitudes (e.g., Rutland, 2004; Stangor and Leary, 2006) and developmental psychological research on the formation of explicit (deliberate) and implicit (automatically activated) outgroup attitudes in adolescence (e.g., Barrett, 2007; Killen, McGlothlin and Henning, 2008). The main objective of the study was to shed light on the role of perceived social norms in the formation of outgroup attitudes among adolescents. First, the study showed that perceived normative pressure to hold positive attitudes towards immigrants regulated the relationship between the explicit and implicit expression of outgroup attitudes among majority youth. Second, perceived social norms concerning outgroup attitudes (i.e., the perceived outgroup attitudes of parents and peers) affected the relationship between intergroup contact and explicit outgroup attitudes depending on gender and group status. Positive social norms seem to be especially important for majority boys, who need both pleasant contact experiences and normative support to develop outgroup attitudes that are as positive as girls attitudes. The role of social norms is accentuated also among minority youth, who, contrary to majority youth with their more powerful and independent status position, need to reflect upon their attitudes and experiences of negative intergroup encounters in relation to the experiences and attitudes of their ingroup members. Third, the results are indicative of the independent effects of social norms and intergroup anxiety on outgroup attitudes: the effect of perceived social norms on the outgroup attitudes of youth seems to be at least as strong as the effect of intergroup anxiety. Finally, it was shown that youth evaluate intergroup contact from the viewpoint of their ingroup and society as a whole, not just based on their own experiences. In conclusion, the outgroup attitudes of youth are formed in a close relationship with their social environment. On the basis of this study, the importance of perceived social norms for research on intergroup contact effects among youth cannot be overlooked. Positive normative influences have the potential to break the strong link between rare and/or negative personal contact experiences and negative outgroup attitudes, and norms also influence the relationship between implicit and explicit attitude expression.

Atmospheric particle formation in spatially and temporally varying conditions

Atmospheric particles affect the radiation balance of the Earth and thus the climate. New particle formation from nucleation has been observed in diverse atmospheric conditions but the actual formation path is still unknown. The prevailing conditions can be exploited to evaluate proposed formation mechanisms. This study aims to improve our understanding of new particle formation from the view of atmospheric conditions. The role of atmospheric conditions on particle formation was studied by atmospheric measurements, theoretical model simulations and simulations based on observations. Two separate column models were further developed for aerosol and chemical simulations. Model simulations allowed us to expand the study from local conditions to varying conditions in the atmospheric boundary layer, while the long-term measurements described especially characteristic mean conditions associated with new particle formation. The observations show statistically significant difference in meteorological and back-ground aerosol conditions between observed event and non-event days. New particle formation above boreal forest is associated with strong convective activity, low humidity and low condensation sink. The probability of a particle formation event is predicted by an equation formulated for upper boundary layer conditions. The model simulations call into question if kinetic sulphuric acid induced nucleation is the primary particle formation mechanism in the presence of organic vapours. Simultaneously the simulations show that ignoring spatial and temporal variation in new particle formation studies may lead to faulty conclusions. On the other hand, the theoretical simulations indicate that short-scale variations in temperature and humidity unlikely have a significant effect on mean binary water sulphuric acid nucleation rate. The study emphasizes the significance of mixing and fluxes in particle formation studies, especially in the atmospheric boundary layer. The further developed models allow extensive aerosol physical and chemical studies in the future.

Polarographic and redox potential studies on copper(I) and copper(II) and their complexes. Part III. Copper (I and II)-ethylene diamine and edta complexes and theory of formation of step reduction waves in cupric copper systems

Polarographic and redox potential measurements on the cupric and cuprous complexes of ethylenediamine and EDTA have been carried out. From the ratio of the stability constants of the cupric and cuprous complexes, and the stability constant of the cupric complex, the stability constant of the cuprous-ethylenediamine complex is obtained. In the case of the EDTA complex it has been possible to obtain only βic/β2ous from the equilibrium concentrations of the cuprous and cupric complexes and the disproportionation constant. The inequalities for the appearance of step reduction waves have been given. The values of the stability constants of the cupric and cuprous complexes determined by the polarographic-redox potential method have been used to explain the appearance of step reduction waves in some systems and the non-appearance in other systems.

Effect of directionality of unidirectional grinding marks on friction and transfer layer formation of Mg on steel using inclined scratch test

Surface topography has been known to play an important role in the friction and transfer layer formation during sliding. In the present investigation, EN8 steel flats were ground to attain different surface roughness with unidirectional grinding marks. Pure Mg pins were scratched on these surfaces using an Inclined Scratch Tester to study the influence of directionality of surface grinding marks on coefficient of friction and transfer layer formation. Grinding angle (i.e., the angle between direction of scratch and grinding marks) was varied between 0 degrees and 90 degrees during the tests. Experiments were conducted under both dry and lubricated conditions. Scanning electron micrographs of the contact surfaces of pins and flats were used to reveal the surface features that included the morphology of the transfer layer. It was observed that the average coefficient of friction and transfer layer formation depend primarily on the directionality of the grinding marks but were independent of surface roughness on the harder mating surface. In addition, a stick-slip phenomenon was observed, the amplitude of which depended both on the directionality of grinding marks and the surface roughness of the harder mating surface. The grinding angle effect on the coefficient of friction, which consists of adhesion and plowing components, was attributed to the variation of plowing component of friction. (c) 2006 Elsevier B.V. All rights reserved.

Generation of Cationic Two-Coordinate Group-13 Ligand Systems by Spontaneous Halide Ejection: Remarkably Nucleophile-Resistant (Dimethylamino)borylene Complexes

Spontaneous ejection of chloride from a three-coordinate boron Lewis acid can be effected by employing very electron rich metal substituents and leads to the formation of a sterically unprotected terminal (dimethylamino)borylene complex that has a short metal-boron bond and remarkable resistance to attack by nucleophilic and protic reagents.

Template-Assisted Sol-Gel Synthesis of Nanocrystalline BaTiO3

Nanocrystalline perovskite barium titanate with an average particle size less than similar to 10 nm is produced using sol-gel route involving ligand-assisted templating. BaTiO3 is obtained by the controlled hydrolysis and condensation reaction of barium acetate (Ba(CH3COO)(2)) with titanium tetra chloride (TiCl4) in the reverse micelles of dodecylamine (DDA) which is used as the template. Our attempts to produce mesoporous BaTiO3 have resulted in the formation of nanocrystalline BaTiO3. The synthesis of nanostructured BaTiO3 is carried out using the ligand-assisted templating approach which proceeds through the sol-gel route. Dodecylamine is used as the template. The sol-gel process in general presents inherent advantages because the nanostructure of the desired materials can be controlled together with their porous structure. Ligand-assisted templating approach involves the formation of covalent bond between the inorganic analogue and the template. Ba(CH3COO)(2) and TiCl4 are used as barium-source and titanium-source respectively. The reaction between Ba(CH3COO)(2) and TiCl4 is found to take place deliberately on the pre-assembled species which acts as the template or occurring with in them which in turn will lead to the generation of the desired nanoscale structure (nanopores or nanoparticles).