Substituent effects in the reaction between acetophenones and polyacrylonitrile radicals

The reactivity of substituted acetophenones towards polyacrylonitrile radical has been correlated with Swain and Luptons field and resonance parameters inclusive of the unique positional weighting factors suggested by Williams and Norrington. From the sign and magnitude of the reaction dependent regression constants, the transition state has been found to be essentially ‘non-polar’ in character.     

Effects of admixtures of potassium bromide on the thermal decomposition of potassium bromate

The effects of admixtures of potassium bromide (2.5% and 5%) on the thermal decomposition of potassium bromate were studied within the temperature range 653–683 K. The fraction decomposed() vs. time (t) relations revealed (i) initial gas evolution, (ii) acceleratory and (iii) decay steps. The data were analysed on the basis of the first-order law with two rate constantsk ₁ andk ₂,k ₁ being the rate constant for the initial, slow first-order process (0.02, 0.26), andk ₂ being the rate constant for the subsequent faster process, holding within the range 0.21 to 0.98. Upon increase of the concentration of added potassium bromide to 5%, the range for the slow and faster processes became 0.01 to 0.16 and 0.1 to 0.98, respectively. At a given temperature,k ₁ increased with increasing bromide concentration, whereask ₂ almost identical for pure potassium bromate and its mixtures (2.5% and 5% bromide).

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Zusammenfassung Im Temperaturbereich von 653–683 K wurde der Einfluß von Beimengen von Kaliumbromid (2,5% und 5%) auf die thermische Zersetzung von Kaliumbromat untersucht. Die Funktion der zersetzten Menge () in Abhängigkeit von der Zeit (t) weist eine anfängliche Gasentwicklung(i), eine beschleunigte(ii) und eine abklingende Stufe(iii) auf. Die Daten wurden auf der Grundlage einer Kinetik erster Ordnung mit den zwei Geschwindigkeitskonstantenk ₁ undk ₂ durchgeführt, wobeik ₁ die Geschwindigkeitskonstante für den einleitenden, langsameren Schritt erster Ordnung ist (0,02, 0,26) undk ₂ die Geschwindigkeitskonstante für den darauffolgenden schnelleren Vorgang mit Werten zwischen 0,21 und 0,98. Bei Erhöhung der Konzentration von Kaliumbromid auf 5% betrug der Bereich für den langsameren und den schnelleren Vorgang 0,01 bis 0,16 bzw. 0,10 bis 0,98. Bei gegebener Temperatur steigtk ₁ mit zunehmender Kaliumbromidkonzentration an, währendk ₂ für reines Kaliumbromat und seine Mischungen mit 2,5% und 5% Kaliumbromid fast identisch bleibt.

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653–683 (2,5 5%) . , . k ₁ k ₂, ( 0,02 0,26), - 0,21–0,98. 5% k ₁ k ₂ , , 0,01–0,16 0,1–0,98. k ₁, , k ₂ , (2,5 5%) .

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The work is dedicated to the memory of the late Prof. S. R. Mohanty.     

Conformational studies on somep-dimethylaminostyryl dyes

PCILO computations have been carried out on the conformations of five p-dimethylaminostyryl dyes derived from quinoline-4 (I), quinoline-2 (II), pyridine-4 (III), pyridine-2 (IV) and benzothiazole (V). The stable conformations of I–IV are found to be nonplanar, while V is almost planar. The results have been explained in terms of various possible steric interactions.     

Elecrochemical Determination of Ethanol by a Palladium Modified Graphene Nanocomposite Glassy Carbon Electrode

Pristine palladium nanoparticles were decorated on graphene nanosheets for the development of a low-cost, nonenzymatic ethanol sensor. The nanocomposite was characterized by ultraviolet–visible absorbance spectroscopy, infrared spectroscopy, and field emission scanning electron microscopy equipped with energy dispersive X-ray spectroscopy. Cyclic voltammetry and chronoamperometry were used to quantify ethanol in alkaline media. A graphene palladium nanocomposite-modified glassy carbon electrode provided a detection limit of 2?mM with a linear dynamic range of 2–210?mM for ethanol determination. The nanocomposite exhibited excellent stability for 100 cyclic voltammetry scans. Ethanol oxidation was performed across a range of temperatures, unlike enzymatic based sensors. Moreover, the catalytic material showed a low activation energy and low onset potentials for the oxidation of ethanol. Interference studies with congeners of ethanol in fermentation chambers showed good selectivity for the analyte. The enhanced catalytic activity for ethanol detection involves the combination of pristine palladium nanoparticles with the enhanced conductivity of graphene.     

Controlling wake turbulence

This Letter introduces a control strategy for taming the wake turbulence behind a cylinder. An angular momentum injection scheme is proposed to synchronize the vertical velocity field. We show that the base suction, wake formation length, absolute instability, and the Kármán vortex street are effectively controlled by the angular momentum injection. A control equation is designed to implement the injection. The Navier-Stokes equations, along with the control equation, are solved. The occurrence of a new recirculation free zone is identified.     

Role of chemical pressure in enhancing the transition temperature (T<Subscript>c</Subscript>) and upper critical field (H<Subscript>c2</Subscript>) in the Y-doped Ce-oxyfluoride superconductor

Structural and superconducting properties of yttrium substituted Ce_1-xY_x(O/F)FeAs superconductors have been investigated for the first time. All the compounds crystallize in the tetragonal ZrCuSiAs structure type. There is a decrease in both the a and c lattice parameters on increasing yttrium substitution (with fixed F content) along with a substantial enhancement of the superconducting transition temperature (T_c) and upper critical field (H_c2) indicating the influence of chemical pressure. Interestingly the maximum T_c (~48 K) was observed for an intermediate composition (Ce_0.5Y_0.5O_0.9F_0.1FeAs) which is higher than either of the parent Y or Ce-compounds, (YO_0.9F_0.1FeAs (~10 K) and Ce(O/F)FeAs (~42 K)). The transition temperature was also found to be nearly independent of the electron -doping introduced by fluoride substitution (0.1 to 0.2 moles per formula unit) indicating the significance of the charge reservoir layer (Ce-O). The yttrium substituted (fluoride free) compositions of the type, Ce_1-xY_xOFeAs were found to be semimetallic like the parent compound CeOFeAs with the shift in the anomaly temperature towards low temperature on substitution of yttrium ions. Hall coefficient and thermopower measurements show an increase in charge carriers (electrons) through Y-doping in fluorine doped CeOFeAs.     

The kinetics of retardation by phenol of the polymerization of acrylonitrile

The present communication discusses the kinetics of the retarding effect of phenol on the polymerization of acrylonitrile initiated by azobisisobutyronitrile (AIBN). The results are treated on the basis of the scheme proposed by Tüdös et al.     

Feasibility and uniqueness of stationary states of nonideal recombinant fermentations?

Summary In recombinant fermentations the plasmid loss probability per generation depends on the specific growth rate, which is related linearly to the dilution rate. A model with this feature and incomplete mixing has been studied analytically for stationary state behavior. While the kinetic parameters place upper limits on the dilution rate for a feasible stationary state in a well-mixed bioreactor, the feasible and nonfeasible regions for an incompletely mixed reactor are separated by either a straight line or a plane, whose position is determined by the mixing conditions.</o:p>