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51.
Min-Hsien Liu Cheng Chen Yaw-Shun Hong Chuan-Wen Liu 《Theoretical chemistry accounts》2005,113(1):35-41
Calculation methods, based on hybrid density-functional theory with the basis sets of B3LYP/ 6-311+G (2d, p)//B3LYP/6-31G(d, p)and B3LYP/6-31+G(d)//B3LYP/6-31G(d, p), were applied to determine the thermodynamic characteristics of various energetic nitro compounds. A parametric modification equation and the least-squares approach were used to identify 21 of the energetic research compounds. The atomization energies of these 21 compounds have an average relative error of 0.21–0.25% of the experimental values. The enthalpy (H f) and the Gibbs energy (G f) of formation have mean absolute errors of 10.8–11.4 kJ/ mol (2.6–2.7 kcal/mol) and 10.0–10.3 kJ/mol (2.4 kcal/ mol), respectively. The enthalpy and the Gibbs energy of formation obtained exceed those in the literature obtained by semiempirical calculations. The calibrated least-squares parameters and parametric equations were used to predict H f and G f for the five newly developed energetic nitro compounds for further applications.Acknowledgements. The authors would like to thank the National Science Council of the Republic of China for financial support of this work under grant no. NSC-91-2113-M-014-003. The National Center for High-Performance Computing providing the computation facility is also acknowledged. 相似文献
52.
C. Christov S. Petrenko C. Balarew V. Valyashko 《Monatshefte für Chemie / Chemical Monthly》1994,125(12):1371-1382
Summary The standard method ofPitzer for predicting the solubility isotherms of systems in which solid phases with a constant composition crystallize is applied to cases when mixed crystals are formed. The four-component carnallite type systems RbCl-CsCl-MgCl2-H2O, RbCl-KCl-MgCl2-H2O, and RbCl-RbBr-MgCl2-MgBr2-H2O and the corresponding subsystems are thermodynamically simulated at 25°C. It is established that the solubility diagrams consist of crystallization regions of the simple saltsMX,MX, MgX
2·6H2O, and MgX2·6H2O and of the corresponding carnallite type double salts with the composition 1:1:6. A method of calculation of the integralGibbs energy of mixingG
mix(s) of crystals formed in water-salt systems has been proposed. The results on the systems RbCl-KCl-H2O, RbCl-RbBr-H2O, and MgCl2-MgBr2-H2O are compared with experimental data from the literature and with values calculated using various models.
Thermodynamische Simulation von Vierkomponentensystemen des Carnallit-Types
Zusammenfassung DiePitzer-Methode zur Voraussage der Löslichkeitsisothermen in Mehrstoffsystemen, in welchen feste Phasen mit konstanter Zusammensetzung auskristallisieren, wurde auch für Fälle angewendet, bei denen sich Mischkristalle bilden. Die Vierstoffsysteme RbCl-CsCl-MgCl2-H2O, RbCl-KCl-MgCl2-H2O und RbCl-RbBr-MgCl2-MgBr2-H2O, aus welchen Carnallit-Typ-Mischkristalle auskristallisieren, und die dazugehörigen Dreistoff-Randsysteme wurden bei 25°C simuliert. Man stellt fest, daß die Löslichkeitsdiagramme sowohl Kristallisationsbereiche der einfachen SalzeMX,M'X, MgX 2·6H2O und MgX 2·6H2O als auch der entsprechenden carnallitartigen Doppelsalze mit der Zuzammensetzung 1:1:6 umfassen. Eine Methode zur Berechnung derGibbs-EnergieG mix(s) für die in Wasser-Salz-Systemen gebildeten Mischkristalle wird vorgeschlagen. Die für die Systeme RbCl-KCl-H2O, RbCl-RbBr-H2O und MgCl2-MgBr2-H2O erhaltenen Ergebnisse werden mit experimentellen Literaturdaten und Resultaten von Berechnungen aufgrund verschiedener Modelle verglichen.相似文献
53.
Kyoungmoo Koh Kohji Ohno Yoshinobu Tsujii Takeshi Fukuda 《European Polymer Journal》2004,40(12):2665-2670
Copper-mediated atom transfer radical polymerization (ATRP) of a protected silanol group-holding methacrylate, methacryloxypropyltrimethoxysilane (MOPS), was investigated. In a dry condition using carefully distilled solvent and monomer, the polymerization proceeded in a living fashion providing a low-polydispersity polymer with a predicted molecular weight. The ATRP in conjunction with the sequential monomer addition of methyl methacrylate (MMA) and MOPS afforded a block copolymer of the type PMMA-b-poly(MMA-r-MOPS). The heat treatment of a solution of the block copolymer in the presence of a catalytic amount of ammonia gave a polymeric core-shell nanoparticle with a shell of PMMA moieties and a core of the poly(MMA-r-MOPS) blocks cross-linked via the condensation of the trimethoxysilane groups of the MOPS moieties. 相似文献
54.
Rybachenko V. I. Schroeder G. Chotii K. Yu. Lenska B. Kovalenko V. V. Red'ko A. N. 《Theoretical and Experimental Chemistry》2003,39(6):359-363
We have studied the rate of 15 reactions of acyl transfer from O-acyl salts of 4-dimethylaminostyryl-4-pyridine N-oxide to 4-morpholinopyridine and 4-dimethylaminopyridine N-oxides in acetonitrile solutions. Analysis of the results based on the Shaik – Pross approach and the Marcus equation shows that if the structure of the acyl group is varied, then the reactivity is determined by such parameters as the resonance interaction in the transition state (B) or the internal barrier (G
0) of the reaction. 相似文献
55.
The chemical reactivity of the [1,2,3]triazolo[1,5-a]- and [1,5-c]-pyrimidinium salts towards morpholine, water and sodium methoxide have been studied. Among others, new 1-aza and 2-azabutadienes substituted by a [1,2,3]-triazole ring were obtained in the course of the opening of the positively charged pyrimidine ring. 相似文献
56.
Glutamic acid (H2glu) and its lithium, sodium
and ammonium monosalts were submitted to thermal analysis using thermogravimetry
(TG) and differential thermal analysis (DTA). The main goal of these studies
was to compare the relative thermal stability and to evaluate the effect of
the counter ion in the thermal decomposition pathways. Salts were obtained
by direct neutralization of the purified acid with LiOH, NaOH or NH4OH
and were characterized by elemental analysis (C, H and N) and IR spectroscopy.
Decomposition occurred after conversion to the pyroglutamic acid or the respective
pyroglutamates and ammonium salt loosing NH3 being
converted to H2glu before decomposition. 相似文献
57.
Two-dimensional infrared (2D IR) correlation spectroscopy was applied to study the structural changes occurring in the decomposition of PHEA-co-MMA/SiO2. Complicated absorption spectral changes were observed in the heating process. 2D IR analysis indicates that during heating, covalent bonds, (Si-O-C), between the polymer and the inorganic moiety were formed, which was the main factor in the improvement in thermal properties of the hybrids such as the decomposition temperatures (Td). The thermal stability of the hybrids was also studied by solid-state 29Si MAS NMR spectroscopy and TGA tests. Their results complemented each other well. 相似文献
58.
Thepyrimidinesasaclassareknowntopossessextraordinarybiologicalpropertiesthataregenerallydistinguishedqualitativelybytheirapplicationsinpesticide,herbicide,bactericide,andmedicineinter-mediates犤1犦.Asurveyoftheseapplicationsandanum-beroftherelatedvariationsthataredevelopedrecent-ly,suchastheextraordinaryeffectiveherbicideofsulfonylsulfourea,revealsthebroadbiologicalimpor-tancejustbecauseofthewideoccurrenceofpyrimi-dinesringsystemsinthesemolecules犤2犦.Ithasbeenshownthatthemedicineintermediates… 相似文献
59.
The reactions of β-naphthol with 5-diazoimidazoles and imidazolyl-5-diazonium salts containing chemically different carboxamide
groups in position 4 were studied. Heterocyclization of 4-arylcarbamoyl-5-(2-hydroxynaphthylazo)imidazoles formed in these
reactions was investigated. The presence of the NH fragment in the amide group prevents this process, the reaction giving
instead 3-substituted 3,7-dihydroimidazo[4,5-d][1,2,3]triazin-4-ones, which is due to reversibility of C-azo coupling. Methods for modification of 1-ethoxycarbonyl group in the naphtho[2,1-e]imidazo[5,1-c][1,2,4]triazine system were developed and used to prepare substituted carboxamides inaccessible by other routes.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1208–1213, July, 2006. 相似文献
60.
Petr Zuman 《Microchemical Journal》2002,72(3):241-250
Applications of chromatographic and atomic absorption methods are compared with those of electroanalytical techniques. The limitations of electroanalytical procedures and their advantages, such as speed, sensitivity and speciation are discussed. Among applications of polarography and voltammetry to a solution of basic problems, attention has been paid to the possibility to distinguish the degree of conjugation (e.g. of compounds containing the grouping CNNC), to a contribution to understanding of solution chemistry of mitomycin C and to processes involved in the reduction of cephalosporins. Among practical applications, the possibility to analyze suspensions, which can be carried out without separation offers advantages. Examples are interactions in suspensions of bile salts in the presence of metal (II) ions, adsorptions of various pesticides and other toxic materials on lignin and the possibility to follow alkaline cleavage of lignin in buffers pH 8-12 at 25 °C. Most of these studies would not be possible to carry out using other techniques. 相似文献