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91.
用从头计算方法对硝基氢(HNO2)体系的异构化及分解反应进行了研究,在6-31G水平上,该化合物异构化为反式来酸的势垒为292kJ/mol,且不易分解为H+NO2或O+HNO。 相似文献
92.
Studies on the complexation of copper(II) by phenolic acids, as ligand models of humic substances were done by potentiometry. The acids under study were: 3,4-dihydroxyhydrocinnamic acid or hydrocaffeic acid (1), 3,4-dihydroxyphenylacetic acid (2) and 3,4-dihydroxybenzoic acid or protocatechuic acid (3). Acidity constants of the ligands and the formation constants of metal-ligand complexes were evaluated by computer programs. The carboxylic group of the phenolic acids has different pKa1 values, being the dissociation constants intrinsically related with the distance between the function and the aromatic nucleus. The results obtained allow concluding that acidity constants of the catechol moiety of the compounds are similar with pKa2 and pKa3 values between 9.47-9.41 and 11.55-11.70. The complexation properties of the three ligands towards copper(II) ion are quite similar, being the species found not different either in nature or stability. Although the model ligands have some structural differences no significant differences were found in their complexation properties towards copper(II). So, it can be postulated that complexation process is intrinsically related with the presence of a catechol group. 相似文献
93.
Computer modelling of the conformational equilibrium of 2-and 2,5,5-substituted 1,3,2-dioxaborinanes
V. V. Kuznetsov O. Yu. Valiakhmetova S. A. Bochkor 《Chemistry of Heterocyclic Compounds》2007,43(12):1577-1581
Empirical, semiempirical, and nonempirical quantum-chemical methods were used to study the conformational equilibrium of 2,5,5-substituted
1,3,2-dioxaborinanes. The sofa invertomers were found to correspond to the local and global minima on the potential energy
surface. The position of the equilibrium between these forms is a function of the substituents at C(5) of the heterocycle.
__________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1860–1865, December, 2007. 相似文献
94.
The actual mobilities and dissociation constants of acidic and basic pharmaceuticals were determined in methanol. Actual mobilities were derived from the dependence of the effective mobilities of the analytes on the pH of the methanolic background electrolyte solution (pH(MeOH)). The pKa values of the pharmaceuticals in methanol (pK(a,MeOH)) were calculated by non-linear curve fitting to the measured mobility values. It was found that the shift in pKa value (when compounds were transferred from water to methanol) increased with the acidity of the analyte. The average pKa shift for compounds exhibiting acidic properties in water was ca. 5.5 units, and the shift for basic compounds about 2 units. As was shown for a mixture of beta-blockers, the calculated actual mobilities and pKa values can be utilised in the optimisation of pH conditions for separation. The practical value of the method was illustrated by the analysis of urine samples. 相似文献
95.
The dissociation of water adsorbed on the surface of NiO was investigated by using the semi-empirical SCF MO method MSINDO.
Simulations were based on embedded cluster models representing the (100) surface, with and without a monatomic step. The angle
formed between the metal adsorption site and the O–H bond associated with water has been found to be critical to the energetics
of the dissociation process. Based on this criterion, it was shown that water dissociation is favorable on the stepped surface,
but highly unlikely on the planar surface. In addition, the activation energy required for water dissociation in a monatomic
NiO step was considerably lower than for dissociation at the planar surface. The high activation energy associated with water
dissociation on the planar surface is attributed to the rigidity of the NiO lattice.
Dedicated to Prof. K. Jug in honor of his 65th birthday 相似文献
96.
The equilibrium in the systems containing a polymer based on dibenzo-18-crown-6 and binary or multicomponent aqueous solutions of NaNO3, KNO3, RbNO3, and AgNO3 was studied. The constants of the sorption of the individual electrolytes from solution into the polymer were determined. Preliminary calculations of the phase composition on sorption of 11 mixtures of electrolytes with a common anion from the data on the equilibria in the systems with one electrolyte are possible.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 464–466, March, 1993. 相似文献
97.
Romero S. Bustamante P. Escalera B. Cirri M. Mura P. 《Journal of Thermal Analysis and Calorimetry》2004,77(2):541-554
Differential scanning calorimetry (DSC), supported by hot stage microscopy, IR spectroscopy and X-ray powder diffractometry,
was used to investigate the characteristics of the solid phases of mefenamic, niflumic, and flufenamic acids and of paracetamol,
before and after equilibration with saturated solutions in different solvents. Mixtures of Lewis base (dioxane and ethyl acetate)
and amphiprotic solvents (ethanol and water) were prepared for evaluating the influence of both nature and polarity of the
solvents. Solid-state analysis performed on the original samples (commercial products) made it possible to establish that
paracetamol, mefenamic acid and flufenamic acid were in their respective Form I. No polymorphic modifications are known for
niflumic acid. Paracetamol, niflumic and mefenamic acids did not show any change after equilibration with the various solvents
or solvent mixtures, regardless of their different chemical nature. In contrast, DSC, IR and X-ray analyses revealed the partial
recrystallization of flufenamic acid into its polymorphic Form III in solid phases at equilibrium with ethanol, ethyl acetate
and their blends, as well as in dioxane-water mixtures containing 30 to 100% dioxane and in ethanol-water mixtures with a
water content less than 50%.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
98.
Alexander V Lebedev Marina V Ivanova Alexander A Timoshin Enno K Ruuge 《Chemphyschem》2007,8(12):1863-1869
The unexpected effects of Ca(2+) on the free-radical chain reactions of dopamine, norepinephrine, isoproterenol, and pyrocatechol oxidation are studied using oxygen consumption measurements, EPR-spectroscopy, UV/VIS spectrophotometry, and by potentiometric titration. It is found that the formation of Ca(2+)-catecholate complexes is accompanied by an increase in the dissociation constants (K(ai) ) of their phenolic hydroxyls. At pH>pK(ai) and in the presence of alkaline-earth metal cations, the rate of catecholate oxidation increases (Ca(2+), Mg(2+)> Sr(2+), Ba(2+)), whereas on addition of Zn ions the rate decreases. The effects of Group II metal cations on catecholate autoxidation are concomitant with a transient increase of the EPR signal for metal-semiquinonate complexes. Therefore, the effects of Ca(2+) and other alkaline-earth metal cations on catecholate autoxidation can be defined as 1) additional deprotonation of catechol OH-groups involved in the formation of M(2+)-catecholate complexes, the latter exceeding catechols in the susceptibility to dioxygen-induced oxidation and 2) formation of relatively stable free-radical intermediates responsible for chain propagation. 相似文献
99.
The stoichiometric solubility constant of eitelite (NaMg
0.5
CO
3
+2H+ ⇄ Na++0.5Mg
2+
+CO
2
(g)+H
2
O, log*K
pso
I
=14.67±0.03 was determined at I=3 m (mol kg−1) (NaClO
4
) and 25°C. The stability of magnesium (hydrogen-)carbonato complexes in this ionic medium was explicitely taken into account.
Consequently, trace activity coefficients of free ionic species, calculated from the Pitzer model with ion-interaction parameters
from the literature, were sufficient for an evaluation of the thermodynamic solubility constants and Gibbs energies of formation
for eitelite (−1039.88±0.60), magnesite (−1033.60±0.40), hydromagnesite (−1174.30±0.50), nesquehonite (−1724.67±0.40), and
brucite (−835.90±0.80 kJ-mol
−1
). The increasing solubilities of nesquehonite and eitelite at higher sodium carbonate molalities were explained by invoking
a magnesium dicarbonato complex (Mg2++2CO
3
2−
⇄ Mg(CO3)
2
2−
, log βz = 3.90 ± 0.08). A set of ion-interaction parameters was obtained from solubility and dissociation constants for carbonic
acid in 1 to 3.5 m NaClO
4
media
which reproduce these constants to 0.02 units in log K. The following Pitzer parameters are consistent with the previously
studied formation of magnesium (hydrogen-)carbonato complexes in 3m NaClO
4
. The model and Gibbs functions of solid phases derived here reproduce original solubility data (−log [H+], [Mg
2+
]
tot
) measured in perchlorate medium within experimental uncertainty.
Presented at the XXII International Conference on Solution Chemistry, July 14–19, 1991, Linz, Austria. 相似文献
100.