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161.
The NaF-AlF(3) system with additions of CaF(2) and MgF(2) has been studied with Raman and vapor pressure measurements for 3 >/= CR (NaF/AlF(3) molar ratio) >/= 1 and up to 50 mol % additive. The results show that the binary melt can be described using the two equilibria AlF(6)(3)(-) = AlF(6)(2)(-) + F(-) and AlF(5)(2)(-) = AlF(4)(-) + F(-) with equilibrium constants 0.25 and 0.05, respectively, at 1293 K. Both reactions have positive reaction enthalpies. The first equilibrium is strongly shifted to the right resulting in a melt mixture with very low AlF(6)(3)(-) concentrations even at the Na(3)AlF(6) composition. Evidence for nonideal mixing of anions was found. For the ternaries, models based on Raman data are presented and compared with vapor pressure measurements. Good agreement is observed when association between the additives, CaF(2) or MgF(2), with the AlF(5)(2)(-) ions in the melt was considered. This association could be experimentally observed through a band broadening and a slight shift in the AlF(5)(2)(-) band frequency. Our vapor pressures and Raman data both indicate that MgF(2) clearly acts as an acid when added to NaF-AlF(3) melts of any composition. When CaF(2) is added, a slight decrease of vapor pressure occurs. Raman data indicate a decrease of AlF(4)(-) concentration, corresponding to a dissociation of CaF(2) with liberation of F(-) ions. All these results are, however, very much dependent on the initial melt composition. These data are explained in terms of acid-base, dilution, and association reactions of the solute with the solvent. 相似文献
162.
Bernard W. TaylorIII Arthur J. Keown Allen G. Greenwood 《The Journal of the Operational Research Society》1983,34(5):379-390
The decision-making process involved in the procurement of military weapon systems, although quite critical and complex, still encompasses the basic characteristics of a capital budgeting problem. Given a number of expenditure items and a limited budget, it is desired to procure those weapon systems that will achieve the goals and objectives of the government and/or military in the most efficient manner. Since these objectives are typically numerous and diverse, traditional decision-making techniques are not applicable. As such, integer goal programming is suggested as a technique to be employed to determine the number of military aircraft to be procured, given conflicting expenditure, budget and effectiveness goals. This method is demonstrated via a case example in which the solution results are presented. 相似文献
163.
The nonintercalative binding of an aliphatic and an aromatic bisguanylhydrazone (BGH) to the minor groove of double-stranded (dA-dT)
n
oligomers is investigated by means of theoretical computations. The preferred binding arrangements of both BGHs are stabilized by a number of H-bonding interactions with sites O2(T), N3(A) and o1 on the two strands, and require limited conformational rearrangements of the BGHs around their C-C single bonds. The intermolecular interaction energy is larger with the aliphatic BGH than with the aromatic one. The energy difference is, however, considerably reduced when the oligomer is lengthened: it passes from 16.1 kcal/mole at the heptamer level, to 7.9 kcal/mole at the undecamer level and to 4.6 kcal/mole when each strand of the undecamer is flanked with a complementary complete helical turn of phosphates, on both the 3 and 5 termini.The interaction energies of the BGHs with water molecules in the first hydration shell are, however, also larger with the aliphatic BGH, than with the aromatic BGH. This energy difference is further enhanced when one considers also the water molecules in the second shell. It becomes greater than the difference in the interaction energy of the two BGHs with (dA-dT)
n
for large values of n. When the dehydration energy of BGHs is taken into account the overall energy balance is then more favorable for the interaction of the aromatic than of the aliphatic BGH with the polynucleotide. This last conclusion is in agreement with experimental results. 相似文献
164.
165.
166.
Dickson JL Binks BP Johnston KP 《Langmuir : the ACS journal of surfaces and colloids》2004,20(19):7976-7983
Stable carbon dioxide-in-water emulsions were formed with silica nanoparticles adsorbed at the interface. The emulsion stability and droplet size were characterized with optical microscopy, turbidimetry, and measurements of creaming rates. The increase in the emulsion stability as the silica particle hydrophilicity was decreased from 100% SiOH to 76% SiOH is described in terms of the contact angles and the resulting energies of attachment for the silica particles at the water-CO(2) interface. The emulsion stability also increased with an increase in the particle concentration, CO(2) density, and shear rate. The dominant destabilization mechanism was creaming, whereas flocculation, coalescence, and Ostwald ripening played only a minor role over the CO(2) densities investigated. The ability to stabilize these emulsions with solid particles at CO(2) densities as low as 0.739 g/mL is particularly relevant in practical applications, given the difficulty in stabilizing these emulsions with surfactants, because of the unusually weak solvation of the surfactant tails by CO(2). 相似文献
167.
Jack E. Baldwin Robert M. Adlington Bernard J. Rawlings Richard H. Jones 《Tetrahedron letters》1985,26(4):485-488
Practical procedures for the resolution of racemic modification of (1, 2)-and (1, 2)-1-amino-2-ethylcyclopropane-1-carboxylic acid ,,(1, 2)- and (1, 2)-1-amino-2-methylcyclopropane-1-carboxylic acid ,, and (1, 2)- and (1, 2)-1-amino-2-methylcyclopropane-1-carboxylic acid , are described; the structures as ,, and were confirmed by X-ray-crystallographic methods. 相似文献
168.
Bernard Chantegrel Abdel-Ilah Nadi Suzanne Gelin 《Journal of heterocyclic chemistry》1985,22(4):1127-1128
A series of 3-alkenyl-4-oxo-6,7-dihydro-4H-pyrano[3,4-d]isoxazole derivatives was prepared by reaction of hydroxylamine with 4,5-dioxo-2,3,7,8-tetrahydro-4H,5H-pyrano[4,3-b]pyran derivatives. 相似文献
169.
Jean-Marie Bessiere Bernard Boutevin Lena Sarraf 《Journal of polymer science. Part A, Polymer chemistry》1988,26(12):3275-3295
The stereoselectivity of the addition step and the transfer step of the radical telomerization of methyl methacrylate with thiophenol has been studied by determining the structure and the amount of each isomer by 1H-NMR. We found, in this case, that the addition step gave preferentially a diad r and that the transfer step gave preferentially a diad m. On the other hand, the tacticity observed for higher telomers is preferentially syndiotactic, similar to that of the poly(methyl methacrylate) prepared by radical initiation. The propagation process for radical telomerization obeys, as for the radical polymerization, Bernoulli's statistics. 相似文献
170.
Diels-Alder adducts were formed in the lead tetraacetate oxidations of substituted cyclic hydrazides of furan, pyridazine and pyrrole dicarboxylic acids in the presence of 1,3-cyclo-hexadiene or 1,3-cyclopentadiene. The products resulting were furo[3,4-g]pyridazino[1,2-a]-pyridazine-6,10-diones, pyridazino[4,5-g]pyridazino[1,2-a]pyridazine-6,11-diones, and pyrrolo-[3,4-g]pyridazino[1,2-a]pyridazine-6,10-diones, respectively. Some hydrogenations and ring opening reactions were studied. 相似文献