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51.
Apparent molal heat capacities
of some piperidine, morpholine, and piperazine derivatives in aqueous solution have been determined by adiabatic calorimetry
in the temperature range 20–55°C and in the molality range 0.2–1m. Comparison of experimental
values with those calculated through group contributions, found for monofunctional compounds, indicates strong interactions
between the hydrophilic centers. An interpretation is given of the possible mechanism of this interaction. Also, values of
ΔC
p
for the addition reaction of proton to nitrogen centers of mono- and bifunctional organic compounds are examined. 相似文献
52.
从(-)-(1S,2R,4S)-5,6-二亚甲基双环[2.2.1]庚-2-醇(I)和(-)-(1S,2S,4S)-5,6-二亚甲基双环[2.2.1]庚-2-醇(Ⅱ)出发,合成了它们的醚类和取代苯甲酸酯类光学纯的衍生物。通过[α]D测定和构型分析,发现它们是含有3个手性碳(C1,C2和C4)的桥环化合物,其旋光性与构型的关系均符合可极化度多级圆球不对称性模型。 相似文献
53.
54.
Cuadros-Rodríguez L Almansa-López EM García-Campaña AM González-Casado A Egea-González FJ Garrido-Frenich A Martínez-Vidal JL 《Talanta》2005,66(4):1063-1072
The use of the recovery term has presented some confusion in Analytical Chemistry. Recent IUPAC recommendations propose to distinguish between two terms: recovery or recovery factor, ℜ, and apparent recovery, ℜ*. Apparent recovery includes recovery factor and a new recovery term proposed in this paper, named calibration recovery, ℜC, which depends of the type of systematic error due to the matrix effect (constant and/or proportional) and is related to the applied calibration methodology. This paper highlights the dependence of the calibration recovery on the sample analyte concentration and, for extension, of the apparent recovery, defines the recovery profile, and makes evident the need to determine a “fit for purpose” analyte concentration interval to comply with a regulated recovery requirements. An approach to estimate the calibration recovery and its associated uncertainty in relation to the above-mentioned dependence is presented. The usefulness of the proposed methodology has been shown in the quantification of a pesticide by GC-ECD for assessing dermal exposure. 相似文献
55.
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
56.
Using velocity map ion imaging technique, the photodissociation of n-C4H9Br in the wavelength range 231–267 nm was studied. The results and our ab initio calculations indicated that the absorption of n-C4H9Br in the investigated region originated from the excitations to the lowest three repulsive states, as assigned as 1A″, 2A′ and 3A′ in Cs symmetry. Dissociations occurred on the PES surfaces of the three states, terminating in C4H9+Br (2P3/2) or C4H9 + Br* (2P1/2) as two channels, and being impacted by an avoided crossing between the PES surfaces of the 2A′ and 3A′ states. The transition dipole to the 1A″ state was perpendicular to the symmetry plane, so perpendicular to the C–Br bond. The transitions to the 3A′ state was polarized parallel to the symmetry plane, and also parallel to the C–Br bond. While the transition dipole to the 2A′ state was in the symmetry plane, but formed an angle of about 53.1° with the C–Br bond. We have also determined the avoided crossing probabilities, which affected the relative fractions of the individual pathways, for the photolysis of n-C4H9Br near 234 nm and 267 nm. 相似文献
57.
杂原子Y分子筛的二次合成及其吸附脱硫性能 总被引:13,自引:0,他引:13
采用液-固相同晶取代反应制备了骨架含Ga的Y型分子筛, 并对其吸附脱硫性能进行了研究. 在室温, 空速为7 h−1的条件下, 镓化Y型分子筛([Ga]AlY)处理噻吩、四氢噻吩、4,6-二甲基二苯并噻吩(4,6-DMDBT)正壬烷溶液(硫含量500 μg•g−1), 每克吸附剂吸附硫的量分别为7.7、17.4、14.5 mg. 采用密度泛函理论(DFT)中的广义梯度近似方法(GGA)计算各分子中硫原子上的电荷数, 噻吩中硫原子的电荷数为−0.159, 而4,6-DMDBT和四氢噻吩分别为−0.214、0.298. 四氢噻吩和4, 6-DMDBT中硫原子上的电子密度大于噻吩中硫原子上的电子密度, 这就使得四氢噻吩和4,6-DMDBT中的硫原子与吸附位间的作用会远大于噻吩中的硫原子与吸附位间的作用, 吸附容量必然会大很多. 采用[Ga]AlY处理抚顺石油二厂的催化裂化汽油(硫含量:299 μg•g−1), 每克吸附剂处理2.1 mL汽油时, 处理后汽油的硫含量为54.8 μg•g−1, 说明[Ga]AlY对汽油脱硫有一定的效果. 相似文献
58.
烃类选择氧化在石油化工中极其重要.近二十多年来,随着石油化工原料逐步从烯烃、芳烃等不饱和烃向资源丰富和价格相对低廉的烷烃的转化,研究烷烃的氧化活化和定向转化来取代相应的烯烃和芳烃工艺具有非常重要的学术意义和工业价值.因而,烷烃的选择活化和氧化得到了世界范围内的 相似文献
59.
Teng-Kuei Yang Dong-Sheng Lee Tsung-Fan Teng Ting-Ting Jong Mei-Yueh Chien 《中国化学会会志》1991,38(4):401-403
Introducing two chiral auxiliaries, sulfoxide and menthol, into an acrylate would have either matched or mismatched pair systems. The presence of chiral menthol in α-sulfinylacrylates can change the diastereoselectivity from 24% d.e. to a single diastereomer by manipulation of the double asymmetric strategy. 相似文献
60.
V. Maleev M. SemenovV. Kashpur T. BolbukhA. Shestopalova D. Anishchenko 《Journal of Molecular Structure》2002,605(1):51-61
The aim of this paper is to summarize the original results concerned with the elucidation of the role of water environment in the formation of different structures of polyribocytidylic acid (poly(rC)), depending on the pH, temperature and ion content. To solve this problem, we studied the hydration of poly(rC)-K+ in films differing in water content, by methods of infrared spectroscopy and piezogravimetry, and in solution, using the dielectric measurements at a wavelength of 7.6 mm (extremely high frequencies — EHF). The experimental results were confirmed by a Monte Carlo simulation of the interaction between water molecules and single-strand and double-strand poly(rC) fragments in clusters of 800 water molecules. A model of hydration of double-strand complex of poly(rC)+-poly(rC) has been proposed based on our results and the known X-ray parameters of the complex. The obtained results and proposed structure of poly(rC)+-poly(rC) suggest that, the stabilization of this complex occurs due to intra- and inter-chain water bridges, together with the hydrogen bonds between neutral and protonated cytosines in pairs. 相似文献