1978 ◽  
Vol 56 (15) ◽  
pp. 1970-1984 ◽  
Author(s):  
D. R. Arnold ◽  
C. P. Hadjiantoniou

The electronic absorption and phosphorescence emission spectra and the photochemical reactivity of several methyl-3-benzoylthiophenes (2- and 4-methyl-3-benzoylthiophene (1, 2), 2,5-dimethyl-3-benzoylthiophene (3), and 3-(2-methylbenzoyl)thiophene (4)) have been studied. Partial state diagrams have been constructed. The lowest energy absorption in hexane solution in every case is the carbonyl n → π* transition. The two lowest triplet states of these ketones are close in energy and, in fact, the nature of the emitting triplet (n,π* or π,π*) depends upon the position of methyl substitution and upon the solvent. The photochemical reactions studied include intramolecular hydrogen abstraction (revealed by deuterium exchange in the adjacent methyl group upon irradiation in perdeuteriomethanol solution), photocycloaddition of dimethyl acetylenedicarboxylate to the thiophene ring, and photocycloaddition of isobutylene to the carbonyl group. Generalizations, potentially useful for predicting photochemical reactivity of these and other aromatic ketones are summarized.


1998 ◽  
Vol 37 (4) ◽  
pp. 371-382 ◽  
Author(s):  
Ioannis S. Arvanitoyannis ◽  
Atsuyoshi Nakayama ◽  
Sei-ichi Aiba

Mechanika ◽  
2021 ◽  
Vol 27 (3) ◽  
pp. 201-208
Author(s):  
Mustafa FEKHAR ◽  
Rachid SACI ◽  
Renée GATIGNOL

Thermal buoyancy, induced by injection or by differential heating of a tiny rod is explored to control breakdown in the core of a helical flow driven by the lid rotation of a cylinder. Three main parameters are required to characterize numerically the flow behavior; namely, the rotational Reynolds number Re, the cavity aspect ratio and the Richardson number Ri. Warm injection/rod, Ri > 0, is shown to prevent on-axis flow stagnation while breakdown enhancement is evidenced when Ri < 0. Results revealed that a bubble vortex evolves into a ring type structure which may remain robust, as observed in prior related experiments or, in contrast, disappear over a given range of parameters (Λh, Re, Ri > 0). Besides, the emergence of such a toroidal mode was not found to occur under thermal stratification induced by a differentially heated rod. Moreover, three state diagrams were established which provide detailed flow characteristics under the distinct and combined effects of buoyancy strength, viscous effects and cavity aspect ratio.


2019 ◽  
Vol 57 (2) ◽  
pp. 111-115
Author(s):  
Svetlana E. Pratskova ◽  
◽  
Evgenia S. Nechaeva ◽  

The thermodynamic properties of melts of the Na2O – CaO – Al2O3 system are of considerable interest for metallurgy, technology of ceramic materials, optical fibers. State diagrams CaO – Al2O3, Na2O – Al2O3 have been studied by many researchers and do not have the generally accepted version, and the system Na2O – CaO has not been specifically studied. In the work, thermodynamic modeling of the phase equilibria of the Na2O – CaO – Al2O3 system was carried out within the framework of the generalized theory of “regular” ionic solutions. Equations for the activities of the system components are derived. The energy parameters of the model are determined taking into account melting characteristics and experimental data. The state diagrams of binary systems are constructed using the calculated values of the Gibbs energies for the formation of sodium and calcium aluminates from the corresponding oxides. Using the regression equations of the temperature dependences of the energy parameters of binary melts of the Na2O – CaO – Al2O3 system, the molar mixing functions of the liquid solution раствора G_m^M, H_m^M, S_m^M and the excess thermodynamic functions G^E, H^E, S^E were calculated at 1500-1800 oC. Lime-alumina melts are stable at all temperatures, experiencing negative deviations from ideality. The Gibbs excess energy G^E is negative and in absolute value varies from 5 to 90 kJ/mol. With an increase in the concentration of Al2O3 in the melt and temperature, a tendency toward disorder is clearly manifested: the entropy of the melt mixing changes its sign from “minus” to “plus”. Na2O – Al2O3 melts are formed with an exothermic effect and ordering, and are also stable. They experience strong negative deviations (for G^E) from ideality. However, the situation changes at 55 mol. % Al2O3 and 1700-1800 oС melts of the system are unstable.


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