Effect of wall alignment in a very short rotating annulus

This paper reports numerical results of the study of effects of cylinders wall alignment in a small aspect ratio Taylor–Couette system. The investigation concerns bifurcations of steady vortical structures when the cylindrical walls defining the gap are not perfectly parallel. The imperfection is introduced by opening the outer fixed cylinder with a certain angle with regard to the vertical to form a tapered very short liquid column and keeping the inner rotating cylinder wall vertical. The numerical results obtained for the velocity components have revealed that bifurcation from a particular mode to another one occurs at a range of specific values of the inclination angle of the outer cylinder. The band width of the angle at which bifurcation occurred depended on the Reynolds number Re and was found to become narrower as Re increased. It is shown that geometrically broken symmetry can yield flow symmetry for specific combinations of geometrical and dynamical parameters.     

Optical rotatory dispersion and vacuum ultraviolet circular dichroism of poly[(R)-oxypropylene]

The circular dichroism (CD) spectrum of poly[(R)-oxypropylene] in a number of solvents has been measured in the vacuum ultraviolet region. Two CD bands were measured for cyclohexane, acetonitrile, and trifluoroethanol solutions. The CD spectrum was extended to 140 nm and three bands were measured in a 1,1,1,3,3,3-hexafluoro-2-propanol solution. The similarity of these four CD spectra in sign, shape, and intensity confirm that poly[(R)-oxypropylene] has similar conformations in all solvents studied, even though the optical rotatory dispersion (ORD) in the visible region is positive for the cyclohexane solution but negative for the alcohol solutions. A Kronig–Kramers transform of the two CD bands observed for the cyclohexane solution accounts for the observed positive ORD spectrum. In contrast, a third large and negative CD band centered below 160 nm is necessary to account for the negative ORD spectra observed for the alcohol solutions. Apparently the anomalous sign variation of the ORD curves observed in the visible region is due to subtle changes in the interplay of a large number of CD bands. Solvent interaction, observed as a blue shift of the first two CD bands for the alcohol solutions, could produce the subtle changes necessary to change the sign of the ORD curve in the visible region. The first two CD bands of poly[(R)-oxypropylene] are tentatively assigned as n? σ^* and the third as an n? 3s.     

Reactivity of n-Butyllithium[sbnd]CH3OCH2CH2OLi System as Catalyst for Copolymerization of Styrene with 1,3-Butadiene

The reactivity of n-butyllithium-CH₃OCH₂CH₂OLi in toluene (System A) in styrene-butadiene copolymerization reaction was found to be similar to that of the catalyst system n-butyllithium-poly(propylene oxide), which formed copolymers containing more styrene units than the feed monomer ratio at early stage of polymerization. Metalation reaction of toluene to produce benzyllithium was observed to take place in System A. Relative reactivity of each of chemical species present in System A was measured in the reactiom with butadiene, styrene, and 1,1-diphenylethylene, in connection with initiation and propagation reactions of copolymerization. From this study a living end anion possessing larger conjugated system was concluded to be more reactive toward monomers possessing larger conjugated system.     

Extraction of nickel in the presence of ammonia with β-diketones containing phenyl and alkyl groups

The extraction of nickel chelates with β-diketones containing either alkyl or phenyl groups was examined in the absence and in the presence of ammonia in the aqueous solution, in order to define the effect of substituents and the coordinating effect of ammonia on the extraction. In the extraction of nickel chelates in the presence of ammonia, the extracted species were identified to be [NiA₂(NH₃)₂] (A: β-diketone anion) and ammonia acts both as adduct-forming in the organic phase and as a masking reagent in the aqueous phase.     

1H- and13 C-NMR Studies of Polymerization of 2,3-Dideuteromethyloxirane with Zinc Dialkoxide

The deuterium-decoupled 100 MHz ¹H-NMR spectra of 2,3-dideuteromethyloxirane and its polymer prepared with a lattice-disordered zinc dialkoxide were analyzed with consideration of the deuterium isotope effects on proton chemical shifts. The results of ¹H- and ^l3C-NMR studies indicated that the initiator for methyloxirane polymerization catalyzed by the diethylzinc-alcohol system was a lattice-disordered zinc dialkoxide, from the aspect of stereoregularity of the polymers obtained.     

Surface phase behavior of di-n-tetradecyl hydrogen phosphate in Langmuir monolayers at the air-water interface

Surface phase behavior of di-n-tetradecyl hydrogen phosphate, DTP, has been studied by measuring pi-A isotherms with a film balance and observing monolayer morphology with a Brewster angle microscopy (BAM) at different temperatures. A generalized phase diagram, which shows a triple point for gas (G), liquid-expanded (LE) and liquid-condensed (LC) phases at about 32 degrees C, is constructed for the amphiphile. Below the triple point, a first-order G-LC phase transition has been shown to occur, whereas a first-order G-LE phase transition followed by another first-order LE-LC transition has been found to take place at a temperature above the triple point. The amphiphile shows the fingering LC domains with uniform brightness indicating the presence of untilted molecules. The domain shapes are independent of the change in temperature and compression rate. The existence of similar fingering domains over a wide range of temperature is rather uncommon in the monolayer systems and is considered to be due to the restricted movement of the molecules incorporating into the LC phase. Because the two-alkyl chains are directly attached to two covalent bonds of the phosphate head group, the rearrangement of the molecules, which is an essential condition for the circular domain formation, needs the movement of the whole molecules including the hydration sphere. The difficulty related to such a movement of the molecules causes fingering domains, which are independent of external variables.