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151.
This paper reports our results for the direct experimental determination of the equilibrium constant for the hydrogen-isotope-exchange
reaction, 1/2D2(g)+HCl(hexOH)=1/2H2(g)+DCl(hexOD), where hexOH isn-hexanol and hexOD isn-hexanol with deuterium substitution in the alcohol function. The reaction was studied in electrochemical double cells without
liquid junction for which the net cell reaction is the above isotope-exchange reaction. The experimentally determined value
of ε° (296.0°K) for this cell is 4.03±0.95 mV (strong electrolyte standard states, mole-fraction composition scale); the value
of the equilibrium constant for the reaction is 1.17±0.05. The contributions of isotope-exchange and transfer effects to the
magnitude of the standard Gibbs energy change for the above reaction and for the analogous reaction 1/2D2(g)+HCl(aq)=DCl(daq)+1/2H2(g) are considered. Our results support the conclusion of Heinzinger and Weston that the formulation of the solvated proton
in water as H3O+, as opposed to H9O4
+, is sufficient for the interpretation of the thermodynamics of hydrogen-isotope-exchange reactions in water. We also find
that the formulation of the solvated proton inn-hexanol as ROH
2
+
is sufficient for the interpretation of our results on the thermodynamics of hydrogen-isotope-exchange inn-hexanol. 相似文献
152.
The cloud point extraction behaviors of lanthanoids(III) (Ln(III) = La(III), Eu(III) and Lu(III)) with and without di(2-ethylhexyl)phosphoric acid (HDEHP) using Triton X-100 were investigated. It was suggested that the extraction of Ln(III) into the surfactant-rich phase without added chelating agent was caused by the impurities contained in Triton X-100. The extraction percentage more than 91% for all Ln(III) metals was obtained using 3.0 × 10−5 mol dm−3 HDEHP and 2.0% (v/v) Triton X-100. From the equilibrium analysis, it was clarified that Ln(III) was extracted as Ln(DEHP)3 into the surfactant-rich phase. The extraction constant of Ln(III) with HDEHP and 2.0% (v/v) Triton X-100 were also obtained. 相似文献
153.
V Parvanova 《Journal of Thermal Analysis and Calorimetry》2006,86(2):443-447
Bi-peroxotitanate
was synthesized by a peroxo method and after thermal decomposition Bi2Ti2O7
was obtained. DTA, TG and DSC curves of Bi2[Ti2(O2)4(OH)6]5H2O were recorded and used to determine
isothermal conditions suitable for obtaining the intermediate samples corresponding
to the phases observed during the thermal decomposition. The samples were
identified by quantitative analysis, IR spectroscopy and X-ray analysis. The
experimental results were used to propose a mechanism of thermal decomposition
of the investigated compound to a nanosized Bi2Ti2O7.
The optimum conditions were also determined for obtaining Bi2Ti2O7,
which is applicable for piezosensors. 相似文献
154.
《Electroanalysis》2006,18(6):587-594
This study describes the direct electron transfer of multi‐copper oxidases, i.e., laccase (from Trametes versicolor) and bilirubin oxidase (BOD, from Myrothecium verrucaria) at multiwalled carbon nanotubes (MWNTs) noncovalently functionalized with biopolymers of cellulose derivatives, i.e., hydroxyethyl cellulose (HEC), methyl cellulose (MC), and carboxymethyl cellulose (CMC). The functionalization of the MWNTs with the cellulose derivatives is found to substantially solubilize the MWNTs into aqueous media and to avoid their aggregation on electrode surface. Under anaerobic conditions, the redox properties of laccase and BOD are difficult to be defined with cyclic voltammetry at either laccase/MWNT‐modified or BOD/MWNT‐modified electrodes. The direct electron transfer properties of laccase and BOD are thus studied in terms of the bioelectrocatalytic activities of the laccase/MWNT‐modified and BOD/MWNT‐modified electrodes toward the reduction of oxygen and found to be facilitated at the functionalized MWNTs. The possible application of the laccase‐catalyzed O2 reduction at the laccase/MWNT‐modified electrode is illustrated by constructing a CNT‐based ascorbate/O2 biofuel cell with the MWNT‐modified electrode as the anode for the oxidation of ascorbate biofuel. 相似文献
155.
The Reaction of SeCl4 with Transition Metal Tetrachlorides. Synthesis and Crystal Structures of (SeCl3)2MCl6 with M = Zr, Hf, Mo, Re The transition metal tetrachlorides ZrCl4, HfCl4 and MoCl4 react with SeCl4 in closed ampoules at temperatures of 140°C to (SeCl3)2MCl6 (M = Zr, Hf, Mo) which are all isotypic and crystallize in the (SeCl3)2ReCl6 structure type (orthorhombic, Fdd2, Z = 8, lattice constants for M = Zr: a = 1165.7(1)pm, b = 1287.2(2)pm, c = 2180.2(2)pm; for M = Hf: a = 1162.9(2)pm, b = 1285.0(2)pm, c = 2178.2(3)pm; for M = Mo: a = 1153.8(1)pm, b = 1267.7(1)pm, c = 2147.4(2)pm). The Cl? ions form a hexagonal closest packing with one fourth of the octahedral holes filled by Se4+ and M4+ in an ordered way. The MCl6 octahedra are regular, the SeCl6 octahedra are distorted with 3 short and 3 long Se? Cl bonds (mean 215 pm and 287 pm). The structures can thus be regarded as built of SeCl3+ and MCl62? ions. Magnetic susceptibility measurements show for M = Zr the expected diamagnetic behavior, for M = Mo and Re paramagnetic behavior according to the Curie-Weiss law with magnetic moments of 2.5 B. M. for M = Mo and 3.7 B. M. for M = Re corresponding to 2 and 3 unpaired electrons respectivly. 相似文献
156.
XRD and XPS are used to study the dispersion state of CuO on ceria surface. The dispersion capacity values of CuO measured
by the two methods are consistent, which are of 1.20 mmol CuO/100 m2 CeO2. In addition, the results reveal that highly dispersed Cu2+ ions are formed at low CuO loadings and that increasing the CuO content to a value higher than its dispersion capacity produces
crystalline CuO after the surface vacant sites on CeO2 are filled. The atomic composition of the outermost layer of the CuO/CeO2 samples has been probed by using static secondary ion mass spectroscopy (SSIMS), and the ratim of Cu/Ce are found to be 0.93
and 0.46 for the 1.22 and 0.61 mmol CuO/CeO2 samples respectively. Temperature-programmed reduction (TPR) profile with two reduction peaks at 156 and 165°C suggests that
the reduction of highly dispersed Cu2+ ions consists of two steps and is easier than that of CuO crystallites, in which the TPR profile has only one reduction peak
at about 249°C. The above experimental results are in good agreement with the prediction of the incorporation model.
Project supported by the National Natural Science Foundation of China. 相似文献
157.
I. V. Ukrainets E. V. Mospanova L. V. Sidorenko 《Chemistry of Heterocyclic Compounds》2007,43(7):863-870
An improved method is reported for the synthesis of a series of 1-hydroxy-3-oxo-5,6-dihydro-3H-pyrrolo[3,2,1-ij]quinoline-2-carboxylic
acid hetarylamides. The antitubercular activity of all of the compounds prepared has been studied. The structure-biological
activity dependence revealed is discussed.
__________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 1023–1033, July, 2007. 相似文献
158.
Contributions to the Chemistry of Phosphorus. 221. Stannyl-Substituted Bicyclo[1.1.0]tetraphosphanes: Formation and properties of R3Sn(H)P4 (R ? CH3, C6H5, c-C6H11, o-C7H7) The unsymmetrically substituted bicyclo[1.1.0]tetraphosphanes Me3Sn(H)P4 ( 1 ), Ph3Sn(H)P4 ( 2 ), (c-Hex)3Sn(H)P4 ( 3 ) and (o-Tol)3Sn(H)P4 ( 4 ) have been obtained by reaction of a solution of (Na/K) HP4 with R3 SnCl (R ? Me, Ph, c-Hex, o-Tol) under proper conditions. The structure of the compounds 1 – 4 , which are only stable in solution, has been elucidated by means of 31P-NMR-spectroscopy. Whereas 3 exists at ?60°C as the exo,endo isomer, 1, 2 and 4 are fluctuating molecules at room temperature and probably invert between the three possible configurational isomers (exo,exo-, exo,endo- and endo,endo-form). 相似文献
159.
3-[(E)-Arylmethylidene]-3,9-dihydropyrrolo[2,1-b]quinazolin-1(2H)-ones were prepared by reaction of quinazolyl-2-propionic acid
hydrochloride with aromatic aldehydes in acetic anhydride in the presence of Et3N. 3-[(E)-Arylmethylidene]-1,2,3,9-tetrahydropyrrolo[2,1-b]quinazolin-1-ols were formed by reduction of the 3-arylidene derivatives
with sodium borohydride in methanol, readily lost water when heated with acids, and were converted into 3-[(E)-arylmethylidene]-3,9-dihydropyrrolo[2,1-b]quinazolines.
__________
Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 463–467, September–October, 2006. 相似文献
160.
Ab initio SCF computations on the intrinsic preferences of the H+, CH
3
+
and C2H
5
+
cations towards the two principal sites of protonation or alkylation on cytosine, N3 or O2, show that this preference undergoes a continuous modification with the increase in size and complexity of the cation. N3 is the preferred site of fixation of H+, O2 the preferred site of C2H
5
+
, while CH
3
+
has no marked preference. The exchange repulsion term of the binding energy appears responsible for the preference of C2H
5
+
for O2.This work was supported by the Ligue Francaise contre le Cancer and the National Foundation for Cancer Research (USA) 相似文献