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101.
The exces enthalpies of solution of some primary and secondary alcohols in aqueous sodium dodecylsulfate micellar solutions were measured and the results were explained by considering the distribution of alcohols between aqueous and micellar phases. The distribution constant and the enthalpy of transfer (and the standard free energy and entropy of transfer) were obtained. The thermodynamic parameters for the transfer of secondary alcohols from the aqueous to the sodium dodecylsulfate (NaDS) micellar phase differ slightly from those of the corresponding primary alcohols. For both series of alcohols the additivity rule holds for free energies of transfer whereas enthalpies and entropies display convex curves. The present data are compared to those for the transfer of the same solutes from the aqueous to the dodecyldimethylamine oxide (DDAO) and dodecyltrimethylammonium bromide (DTAB) micellar phases. The role of the hydrophilic interactions between the OH group and the micelles' head groups is formulated. The thermodynamics of the branched methyl group were determined. Furthermore, the thermodynamics of solvation of primary alcohols in water, in NaDS micelles, and in octane have been calculated using reference states based on the assumption that the empty space around alcohols in the initial and final states is the same. It is shown that the solvation of alcohols in NaDS micellar phase is enthalpy driven and that the thermodynamic properties of solvation vs. the length of the alcohol tail is the same for water and NaDS micelles whereas it is different for octane. A possible explanation for this difference is that the alkyl chain of alcohols folds in octane. 相似文献
102.
E. M. Telles J. C. S. Moraes A. Scalabrin D. Pereira G. Carelli C. A. Massa A. Moretti F. Strumia 《International Journal of Infrared and Millimeter Waves》1995,16(12):2233-2248
We used a Stark-Optoacoustic cell and hybrid waveguide resonators to perform an Infrared and Far Infrared Stark Spectroscopy study on some transitions of13CD3OH. Different behaviours of the transitions in the presence of a d.c. electric field were observed. The Stark splittings of six FIR laser lines ranging from 34 to 136 MHz/kVcm–1 were determined. The analysis of the behaviour of the IR and FIR transitions in the presence of the external electric fields gives important and exclusive information on the levels involved in the transitions.Work Supported by FAPESP, CNPq, FAEP - Brazil, and CNR - Italy. 相似文献
103.
The electrochemical and in-situ surface-enhanced Raman spectroscopy (SERS) techniques were used to investigate the electrooxidation behavior of methanol in acidic, neutral and alkaline media at a Pt-Ru nanoparticle modified glassy carbon (Pt-Ru/GC) electrode. The results showed that methanol could be dissociated spontaneously at the Pt-Ru/GC electrode to produce a strongly adsorbed intermediate, CO. It was found that CO could be oxidized more easily in the alkaline medium than in the acidic and neutral media. The peak potential of methanol oxidation was shifted from 0.663 and 0.708 V in the acidic and neutral media to -0.030 V in the alkaline medium, which is due to that the adsorption strength of CO on the Pt surface in the alkaline medium is weaker than that in the acidic and neutral media. The final product of the methanol oxidation is CO2. However, in the alkaline medium, CO2 produced would form CO3^2- and HCO3^- resulting in the decrease in the alkaline concentration and then in the decrease in the performance of DMFC. Therefore, the performance of the alkaline DMFC is not Stable. 相似文献
104.
Jihong Cheng 《Journal of solid state chemistry》2004,177(1):126-133
LaGaO3 perovskites doped with Sr or Ba at the La site and Mg at the Ga site were prepared by solid-state reaction or sol-gel method and characterized. Enthalpies of formation from constituent oxides at 298 K were determined by high-temperature oxide melt solution calorimetry. Energetic trends are discussed in terms of defect chemistry. As oxygen deficiency increases, formation enthalpies define three trends, LaGa1−yMgyO3−δ (LGM), La1−xSrxGa1−yMgyO3−δ (LSGM), and La1−xBaxGa1−yMgyO3−δ (LBGM). They become less exothermic with increasing doping, suggesting a dominant destabilization effect from oxygen vacancies. The endothermic enthalpy of vacancy formation is 275±37, 166±18 and 138±12 kJ/mol of VO·· for LGM, LBGM and LSGM, respectively. Tolerance factor and ion size mismatch also affect enthalpies. In terms of energetics, Sr is the best dopant for the La site and Mg for the Ga site, supporting earlier studies, including oxygen ion conductivity and computer modeling. 相似文献
105.
利用吡啶吸附-IR,NH3吸附-脱附,原位热重积炭,DSC等技术并结合甲基环己烷(MCH)脱氢活性试验,研究了K2O对工业Pt-Sn/Al2O3催化剂的表面酸性及MCH脱氢稳定性的影响,结果表明,K2O能有效地调变催化剂的表面酸性,降低其表面酸中心特别是强酸中心的数目;MCH脱氢反应的积炭量随K2O含量的增加而减少,但催化剂的高温脱氢稳定性与K2O含量并不完全呈顺变关系,K2O含量应严格控制,当K 相似文献
106.
The presence of trace metals in car fuels plays an important role in the engine maintenance. In addition, these metals contribute for the environmental contamination in big cities and their control is necessary. Square Wave Stripping Voltammetry (SWSV) is a very sensitive technique for elemental trace determination and was applied for ethanol fuel analysis. The first studies were done searching for the best conditions for copper determination in alcoholic medium, utilizing gold electrodes. During these studies, the possibility of the simultaneous determination of copper and lead in the same experiment was observed. Two procedures for the analysis of these metals were adopted: The direct quantification of metals in alcohol–water mixtures and a second way that involves the evaporation of the organic solvent and re-suspension of the ions with water+electrolyte. Good recovery values were obtained for synthetic samples spiked with known amounts of metals. The results obtained for the two methods were in good agreement. The detection limits for copper and lead in 75% ethanol–water ratio solution were calculated as 120 and 235 ng l−1, respectively, for 15-min deposition time. 相似文献
107.
A set of seven bituminous coal chars has been characterised by IR spectroscopy (FTIR), thermogravimetry (TG) and elemental analysis. FTIR study provided suitable information to establish differences between coal samples according to their chemical compositions. The reactivity of these samples was also studied and correlated with the coal parameters of mean vitrinite reflectance, fuel ratio and H/C ratio. The data suggest that reactivity as determined can be correlated with the mean vitrinite reflectance, fuel ratio and H/C ratio (0.90). The order of reactivity of samples were; Amasra (S1) (R m= 0.65)>Azdavay (S4) (R m=0.99)»Armutcuk (S2) (R m=0.81)»Acenta (S3) (R m=0.92)>Ac2l2k (S6) (R m=1.11) Cay (S5) (R m=1.03)>Sogutozu (S7) (R m=2.14). 相似文献
108.
改进型甲醇合成催化剂NC208的催化特性 总被引:2,自引:0,他引:2
采用TPD、XRD、BET和H2S中毒试验等方法,对比研究三组份(Cu-Zn-Al)甲醇合成催化剂C207和添加少量金属氧化物的改进型催化剂NC208.结果表明,工作态NC208催化剂表面Cu+/Cu0的比值和价态稳定性大于C207. 相似文献
109.
Transition metal oxide doped lanthanum gallates, La0.9Sr0.1Ga0.8M0.2O3 (where M=Co, Mn, Cr, Fe, or V), are studied as mixed ionic-electronic conductors (MIECs) for electrode applications. The
electrochemical properties of these materials in air and in H2 are characterized using impedance spectroscopy, open cell voltage measurement, and gas permeation measurement. Three single
cells based on La0.9Sr0.1Ga0.8 Mg0.2O3 (LSGM) electrolyte (1.13 to 1.65 mm thick) but with different electrode materials are studied under identical conditions
to characterize the effectiveness of the lanthanum gallate-based MIECs for electrode applications. At 800 °C, a single cell
using La0.9Sr0.1- Ga0.8Co0.2O3 as the cathode and La0.9Sr0.1Ga0.8Mn0.2O3 as the anode shows a maximum power density of 88 mW/cm2, which is better than that of a cell using Pt as both electrodes (20 mW/cm2) and that of a cell using La0.6Sr0.4CoO3 (LSC) as the cathode and CeO2-Ni as the anode (61 mW/cm2) under identical conditions. The performance of LSGM-based fuel cells with MIEC electrodes may be further improved by reducing
the electrolyte thickness and by optimizing the microstructures of the electrodes through processing.
Received: 9 January 1998 / Accepted: 1 May 1998 相似文献
110.
《Surface and interface analysis : SIA》2003,35(3):251-255
From large‐scale production, two monocrystalline silicon solar cells of different quality, i.e. ISC = 3.0 A (good cell) and ISC = 1.6 A (bad cell), have been studied by XPS combined with 4 keV Ar+ depth profiling. Depth profiling was carried out through the anti‐reflection coating (TiO2), the passivation layer (SiO2) and up into the phosphorus‐doped silicon bulk. At the solar cell surface the elemental composition is similar for both cells, although the bad one presents slightly more carbon, phosphorus and lead but less silver than the good one. During profiling, carbon and silver could be followed by XPS. It was found that the carbon content is distinguishably higher in the bad cell than in the good one. Furthermore, it was found that silver atoms have not diffused in the same way in both cells. Only the good cell presents silver atoms up into the silicon bulk. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献