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1.
The influence of sodium fluoride additives on the physicochemical properties of glasses in the Na2O-B2O3 systems is investigated. The introduction of sodium fluoride into the Na2O · 2B2O3 and Na2O · 3B2O3 glasses leads to an increase in the electric conductivity. The temperature-concentration dependence of the electric conductivity has been investigated. It is shown that, in glasses of the NaF-Na2O · 2B2O3 system, an increase in the volume concentration of sodium ions from 2.4 × 10−2 to ∼3 × 10−2 mol/cm3 is accompanied by an insignificant decrease in the activation energy Eσ from 1.44 to 1.38 eV and a sharp (by a factor of ∼30) increase in the electric conductivity. In glasses of the NaF-Na2O · 3B2O3 system, an increase in the concentration of sodium ions from 1.8 × 10−2 to ∼2.3 × 10−2 mol/cm3 brings about an increase in the electric conductivity by a factor of approximately 100 and an increase in Eσ from 1.6 to 1.83 eV. A further increase in the concentration of sodium ions (up to 2.5 × 10−2 mol/cm3) virtually does not affect the electric conductivity and Eσ. At the same concentration of sodium ions (∼2.46 × 10−2 mol/cm3) in the 9.8NaF · 90.2[Na2O · 2B2O3] and 57.1NaF · 42.9[Na2O · 3B2O3] glasses, the electric conductivity and the activation energy are considerably higher in the glass with a larger fluorine content. The regularities revealed are interpreted in the framework of the microinhomogeneous glass structure.  相似文献   

2.
The influence of sodium fluoride additives on the physicochemical properties of glasses in the Na2O-B2O3 systems is investigated. The introduction of sodium fluoride into the Na2O · 2B2O3 and Na2O · 3B2O3 glasses leads to an increase in the electric conductivity. The temperature-concentration dependence of the electric conductivity has been investigated. It is shown that, in glasses of the NaF-Na2O · 2B2O3 system, an increase in the volume concentration of sodium ions from 2.4 × 10−2 to ∼3 × 10−2 mol/cm3 is accompanied by an insignificant decrease in the activation energy Eσ from 1.44 to 1.38 eV and a sharp (by a factor of ∼30) increase in the electric conductivity. In glasses of the NaF-Na2O · 3B2O3 system, an increase in the concentration of sodium ions from 1.8 × 10−2 to ∼2.3 × 10−2 mol/cm3 brings about an increase in the electric conductivity by a factor of approximately 100 and an increase in Eσ from 1.6 to 1.83 eV. A further increase in the concentration of sodium ions (up to 2.5 × 10−2 mol/cm3) virtually does not affect the electric conductivity and Eσ. At the same concentration of sodium ions (∼2.46 × 10−2 mol/cm3) in the 9.8NaF · 90.2[Na2O · 2B2O3] and 57.1NaF · 42.9[Na2O · 3B2O3] glasses, the electric conductivity and the activation energy are considerably higher in the glass with a larger fluorine content. The regularities revealed are interpreted in the framework of the microinhomogeneous glass structure.  相似文献   

3.
The kinetic model of asymmetric reduction of 3-oxo-3-phenylpropionic acid ethyl ester using Saccharomyces cerevisiae CGMCC No.2266 with 10% glucose as co-substrate to realize the regeneration of NADPH was established. The effect factors on reduction, the type and the content of co-substrate and coenzyme, and the changes of the substrate and product content vs. time during the reaction process were investigated. The results indicate that 10% glucose can increase the reaction conversion from 23.0% to 98.4% and NADPH is reducer. The reduction process conforms with sequence mechanisms. The model parameters are as follows: v m =5.0×10−4 mol·L−1·h−1, k1=1.5×10−6 mol·L−1·h−1, k2=3.0×10−3 mol·L−1·h−1. The kinetic model is in good agreement with the experimental data.  相似文献   

4.
The surface compositions of crude by-product polyolefin wax (wax K) from a naphtha cracking unit, fractionated commercial paraffin wax (wax J) and their blend (wax M) were compared, under various conditions, by using FT-IR. Then a practical criterion was theoretically derived by back-of-the-envelope-calculation to estimate the diffusivity for the surface enrichment of hydrophilic functional groups. The hydrophobicity in terms of chemical structure and functional groups was altered by changing the environment as well as by blending wax K with wax J. The surface properties of wax J and wax M turned out more hydrophobic than that of wax K within the experimental period of water-submerged condition, even though the structure and functional groups on the surfaces of all waxes under ambient atmospheric condition are extremely similar. Thus the blend of wax M behaved unlike wax K but similarly to wax J in terms of alteration of hydrophobicity. Such values of diffusivity as 1.35×10−11 cm2/s and 1.96×10−11 cm2/s are established for wax J and wax M, respectively, under 1 day water-submerged condition. Furthermore, under 1 week water-submerged condition, the values of their diffusivity for wax J, wax K and wax M are estimated as 3.06×10−12 cm2/s, 7.23×10−11 cm2/s and 1.50×10−11 cm2/s, respectively. The obtained values of diffusivity are consistent, in terms of the order of magnitude, with the value of diffusion coefficient of 5.75×10−11 cm2/s obtained, using a very complicated empirical-formula, by Chen et al. for the investigation of surface-modifier enrichment. Thus, the suggested criterion may be very useful and practically applied to clarify the process of surface enrichment from general polymer-blends.  相似文献   

5.
Sodium metaborate tetrahydrate (NaB(OH)4·2H2O) was synthesized by reaction of anhydrous borax (Na2O·2B2O3) with sodium hydroxide (NaOH) under conditions at 90 °C for 150 min. The structure was characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Scanning electron microscope (SEM) and Thermogravimetric (TG) analyses. Moreover, dehydration kinetics of NaB(OH)4·2H2O was carried out under non-isothermal conditions and the Coats-Redfern method was applied to analyze the TG data for calculation of activation energies (E a ) and pre-exponential factors (k o ) for different heating rates. It was determined that dehydration of sodium metaborate tetrahydrate occurred in five steps. According to the Coats-Redfern non-isothermal model, E a and k o were calculated as 50.89 kJ/mol and 26×104 min−1 for region I, 18.51 kJ/mol and 0.87×103 min−1 for region II, 15.72 kJ/mol and 0.52×103 min−1 for region III, 4.37 kJ/mol and 0.04×103 min−1 for region IV and 37.42 kJ/mol and 8.56×103 min−1 for region V, respectively.  相似文献   

6.
Dipyridamole [2,6-bis-diethanolamino-4,8-dipiperidinopyrimido-(5,4-d) pyrimidine], a well known platelet aggregation inhibitor, shows powerful hydroxyl radical scavenging activity by inhibiting OH-dependent salicylate and deoxyribose degradation. Steady-state competition kinetics experiments with deoxyribose were carried out to evaluate the second-order rateconstant for the reaction between hydroxyl radical and dipyridamole. OH· radicals were generated either by a Fenton-type reaction or by X-ray irradiation of water solutions. A second-order rate constant k(Dipyridamole+OH·) of 1.72±0.11×1010M−1 s−1 and of 1.54±0.15×1010 M−1 s−1 was measured by Fenton chemistry and by radiation chemistry, respectively. Mannitol was used as an internal standard for hydroxyl radicals in steady-state competition experiments with deoxyribose. A rate constant k(Mannitol+OH·) of 1.58±0.13×109 M−1 s−1 and 1.88±0.14×109 M−1 s−1 was measured in the Fenton model and in the water radiolysis system, respectively. Both these rate constants are in good agreement with the published data obtained by the “deoxyribose assay” and by pulse radiolysis.  相似文献   

7.
By doping the core of a triplex quartz optical fibre with P2O5, GeO2, and B2O3, it is possible to reduce its temperature sensitivity (TS) from 7·10−6K−1 to (4–5)·10−6K−1. The same decrease in TS can be obtained by doping the third layer with TiO2. The doping level in both cases should be 30–40 mole%. The TS of an optical fibre greater than 80 μm in diameter is almost not a function of random changes in the diameter. For a liquid-crystalline polymer cladding above a fixed value, the TS of the fibre is weakly dependent on the change in the thickness. Moscow State Textile University. Translated fromKhimicheskie Volokna, No. 5, pp. 48–49, Setember–October, 1999.  相似文献   

8.
Pristine activated carbon (AcC) was oxidized by H2O2 under ultrasonic conditions. Compared with pristine AcC, the H2O2-oxidized AC possesses higher accumulation ability to trace levels of Cd2+. Based on this, a highly sensitive, simple and rapid electrochemical method was developed for the determination of Cd2+. In 0.01 mol L−1 HClO4 solution, Cd2+ was effectively accumulated at the surface of H2O2-oxidized AcC modified paste electrode, and then reduced to Cd under −1.10 V. During the following potential sweep from −1.10 to −0.50 V, reduced Cd was oxidized and a sensitive stripping peak appears at −0.77 V. The stripping peak current of Cd2+ changes linearly with concentration over the range 5.0 × 10−8 to 5.0 × 10−6 mol L−1. The limit of detection was found to be 3.0 × 10−8 mol L−1 for 2-min accumulation. Finally, this new sensing method was successfully used to detect Cd2+ in waste water samples.  相似文献   

9.
High pyroelectric performance around human body temperature is essential for ultra-sensitive infrared detectors of medical systems. Herein, toward human health monitoring, composite ceramics (1-x)Pb0.99Nb0.02[(Zr0.57Sn0.43)0.94Ti0.06]0.98O3/xAl2O3 (x = 0, 0.1, and 0.2) were designed. A metastable ferroelectric (FE) phase was induced in the anti-FE matrix by the Al2O3 component-induced internal stress, and in turn FE-anti-FE phase boundary was constructed. The ceramics at x = 0.2 exhibit high pyroelectric coefficient with p = 10.9 × 10−4 C·m−2·K−1 and figures of merit with current responsivity Fi = 6.23 × 10−10 m·V−1, voltage responsivity Fv = 12.71 × 10−2 m2·C−1, and detectivity Fd = 7.03 × 10−5 Pa−1/2 around human body temperature. Moreover, the enhanced pyroelectric coefficients exist in a broad operation temperature range with a large full width at half maximums of 18.5°C and peak value of 29.2 × 10−4 C·m−2·K−1 at 48.2°C. The designed composite ceramic is a promising candidate for infrared thermal imaging technology of noncontact human health monitoring system.  相似文献   

10.
A novel photocatalytic deposition method for the preparation of a thin tubular palladium membrane is presented in this paper. The membrane is prepared on a porous asymmetric TiO2 support by photocatalytic reaction of palladium ion, followed by electroless plating. Gas permeation results show that the membrane exhibits increased hydrogen permeance with the increase of temperature. The hydrogen permeance and selectivity to nitrogen at 773 K are about 1.43×l0−6 mol m−2 s−1 Pa−1 and 17, respectively, when the pressure in the feed side is 0.1 MPa. The activation energy of hydrogen permeation is 11.06 kJ/mol at the temperature range of 573–773 K.  相似文献   

11.
A study was made of the conversion of single spherical coal particles of diameter 1–5 mm in a supercritical H2O/O2 fluid with an oxygen mass fraction of 0–6.6% in a semibatch reactor at a pressure of 30 MPa and a temperature of 673–1023 K. A decrease in the particle mass was observed in two parallel processes: gasification of coal with water and oxidation of coal with oxygen. An activation energy 19 ± 7 kJ/mole and a pre-exponential factor 10−2±0.4 sec−1 were obtained under the assumption of zero order for the concentration H2O and an Arrhenius dependence for the rate of gasification with water. The oxidation with oxygen at a temperature above 780 K was found to be limited by the rate of O2 diffusion to the coal organic matter. Below 780 K, the rate of heterogeneous oxidation with oxygen is described by a first-order reaction for the concentration of O2 and a zero-order reaction for the concentration of H2O with an activation energy of 150 ± 27 kJ/mole and a pre-exponential factor of 107.6±1.9 cm3/(g · sec). __________ Translated from Fizika Goreniya i Vzryva, Vol. 44, No. 2, pp. 23–31, March–April, 2008.  相似文献   

12.
Under the conditions of phase transfer catalysis and nitrobenzene as the solvent, the halogen-exchange fluorination of 2,6-dichlorobenzaldehyde using KF as fluorinating agent was studied. The kinetics was investigated and the reaction rate constants were obtained under the optimum conditions of n(KF):n(2,6-dichlorobenzaldehyde): n(Ph4PBr):n(acetone-furan crown ether) = 4:1:0.1:0.05 and temperatures of 433 K, 443 K, 453 K and 463 K. The results illustrated the activation energy of the first and the second step is 4.57 × 104 J·mol−1 and 3.53 × 104 J·mol−1, respectively. The pre-exponential factor is 4.50 × 105 h−1 and 1.08 × 104 h−1, respectively. Thus a reliable kinetics data could be obtained for further research. __________ Translated from Chemical Engineering (China), 2007, 35(8): 33–36 [译自: 化学工程]  相似文献   

13.
Summary The inorganic–organic hybrid [VIV 4O10VV 2O4] (C6H14N2)·H2O polymeric framework was prepared under mild hydrothermal conditions from a mixture of DABCO and V2O5 in deionized water with a 1:1:450 mole ratio, at neutral pH. The reaction was carried out at 180 °C for 3 days under autogenous pressure yielding phase pure crystals product. The crystal structure was studied using both powder and single crystal X-ray crystallography, revealing the structure to be of the ({UuDd}:T*)α′ type in the SP+T class and Z-T subclass. The presence of the organic cation was confirmed by FT-IR spectrum and chemical composition analysis. The structure was thermally stable up to over 400 °C, and showed ferromagnetic character at room temperature with the maximum molar susceptibility of 8.26 × 10−3 emu/mol−1 at zero applied field.  相似文献   

14.
The 1O2 quenching rate constants (k Q ) of α-tocopherol (α-Toc) and carotenoids such as β-carotene, astaxanthin, canthaxanthin, and lycopene in liposomes were determined in light of the localization of their active sites in membranes and the micropolarity of the membrane regions, and compared with those in ethanol solution. The activities of α-Toc and carotenoids in inhibiting 1O2-dependent lipid peroxidation (reciprocal of the concentration required for 50% inhibition of lipid peroxidation: [IC50]−1) were also measured in liposomes and ethanol solution and compared with their k Q values. The k Q and [IC50]−1 values were also compared in two photosensitizing systems containing Rose bengal (RB) and pyrenedodecanoic acid (PDA), respectively, which generate 1O2 at different sites in membranes. The k Q values of α-Toc were 2.9×108M−1s−1 in ethanol solution and 1.4×107 M−1s−1 (RB system) or 2.5×106 M−1s−1 (PDA system) in liposomes. The relative [IC50]−1 value of α-Toc in liposomes was also five times higher in the RB system than in the PDA-system. In consideration of the local concentration of the OH-group of α-Toc in membranes, the k Q value of α-Toc in liposomes was recalculated as 3.3×106 M−1s−1 in both the RB and PDA systems. The k Q values of all the carotenoids tested in two photosensitizing systems were almost the same. The k Q value of α-Toc in liposomes was 88 times less than in ethanol solution, but those of carotenoids in liposomes were 600–1200 times less than those in ethanol solution. The [IC50]−1 value of α-Toc in liposomes was 19 times less than that in ethanol solution, whereas those of carotenoids in liposomes were 60–170 times less those in ethanol solution. There were no great differences (less than twice) in the k q and [IC50]−1 values of any carotenoids. The k Q values of all carotenoids were 40–80 times higher than that of α-Toc in ethanol solution but only six times higher that of α-Toc in liposomes. The [IC50]−1 values of carotenoid were also higher than that of α-Toc in ethanol solution than in liposomes, and these correlated well with the k Q values.  相似文献   

15.
Prussian Blue-modified graphite electrodes (G/PB) with electrocatalytic activity toward H2O2 reduction were obtained by PB potentiostatic electrodeposition from a mixture containing 2.5 mm FeCl3 + 2.5 mm K3[Fe(CN)6] + 0.1 m KCl + 0.1 m HCl. From cyclic voltammetric measurements, performed in KCl aqueous solutions of different concentrations (5 × 10−2–1 m), the rate constant for the heterogeneous electron transfer (k s) was estimated by using the Laviron treatment. The highest ks value (10.7 s−1) was found for 1 m KCl solution. The differences between the electrochemical parameters of the voltammetric response, as well as the shift of the formal potential, observed in the presence of Cl and NO3 compared to those observed in the presence of SO42− ions, points to the involvement of anions in the redox reactions of PB. The G/PB electrodes showed a good electrochemical stability proved by a low deactivation rate constant (0.8 × 10−12 mol cm2 s−1). The electrocatalytic efficiency, estimated as the ratio , was found to be 3.6 (at an applied potential of 0 mV vs. SCE; Γ = 5 × 10−8 mol cm−2) for a H2O2 concentration of 5 mm, thus indicating G/PB electrodes as possible H2O2 sensors.  相似文献   

16.
The first stage of the alkaline dehydrohalogenation of sodium 9,10-dichlorooctadecanoate (DCO) has been studied in ethylene glycol-water mixtures and in pure water at 90 C. The rate of the reaction was found to decrease rapidly with increasing water concentration. The rate of removal of the first chlorine from sodium 9,10-dichlorooctadecanoate was determined as a function of the water concentration in various ethylene glycol-water mixtures. The rate coefficient (kOH) in pure water solution was 1.4·10−4 kg·mole−1·min−1 as compared to the maximum value of 2.7·10−2 kg·mole−1·min−1 in 19 wt % solution. The effects of temperature and base concentration on the reaction rate were also investigated.  相似文献   

17.
Kazuo Mukai  Yuji Okauchi 《Lipids》1989,24(11):936-939
A kinetic study of the reaction between a tocopheroxyl radical and unsaturated fatty acid esters has been undertaken. The rates of allylic hydrogen abstraction from various unsaturated fatty acid esters (ethyl oleate2, ethyl linoleate3, ethyl linolenate4, and ethyl arachidonate5) by the tocopheroxyl radical (5,7-diisopropyltocopheroxyl6) in benzene have been determined spectrophotometrically. The second-order rate constants, k3, obtained are 1.04×10−5 M−1s−1 for2, 1.82×10−2 M−1s−1 for3, 3.84×10−2 M−1s−1 for4, and 4.83×10−2 M−1s−1 for5 at 25.0°C. Thus, the rate constants, kabstr/H, given on an available hydrogen basis are k3/4=2.60×10−6 M−1s−1 for2, k3/2=9.10×10−3 M−1s−1 for3, k3/4=9.60×10−3 M−1s−1 for4, and k3/6=8.05×10−3 M−1s−1 for5. The kabstr/H values obtained for the polyunsaturated fatty acid esters3,4, and5 containing H-atoms activated by two π-electron systems are similar to each other, and are about three orders of magnitude higher than that for the ethyl oleate2 containing H-atoms activated by a single π-system. From these results, it is suggested that the prooxidant effect of α-tocopherol in edible oils and fats may be induced by the above hydrogen abstraction reaction.  相似文献   

18.
The kinetics of the autoxidation of polyunsaturated fatty acids   总被引:11,自引:0,他引:11  
The kinetics of the autoxidation of a series of polyunsaturated fatty acids (PUFA) with increasing degrees of unsaturation and the mono-, di-and triglycerides of linoleate have been studied in homogeneous chlorobenzene solution at 37 C under 760 torr of oxygen. The autoxidations were initiated by thermal decomposition of azo initiators and followed by measuring the rate of oxygen uptake. The rate of chain initiation was determined by the induction period method using α-tocopherol as the chainbreaking antioxidant. The measured oxidizabilities of the PUFA are linearly dependent on the number of doubly allylic positions present in the molecule. Thus, the oxidizability of linoleate is 2.03×10−2 M−1/2 sec−1/2, and the value for docosahexaenoate is five times greater, 10.15×10−2 M−1/2 sec−1/2. The rate of autoxidation for all PUFA studied and for the mono- and diglyceride is proportional to the substrate concentration and to the square root of the rate of chain initiation, implying that the autoxidation of these compounds follows the usual kinetic rate law. The autoxidation of the triglyceride is more complex and does not appear to follow the same rate law at all substrate concentrations. This deviation from the usual kinetic rate expression may be due to lipid aggregation at low concentrations of the triglyceride.  相似文献   

19.
Abstract  A new ion-pair complex [1-(4-bromobenzyl)-3-methylpyridinium][Ni(dmit)2] (1), in which dmit = 4,5-dimercapto-1,3-dithiole-2-thione, has been synthesized and structurally characterized. The anions of [Ni(dmit)2] stack into dimers, which further construct into a two-leg ladder through lateral S···S interactions. The weak H-bonding interactions of C–H···S and van de Waals interactions between anion and cations were observed. The magnetic susceptibilities measured from 2–300 K indicate an AFM exchange interaction domination and an AFM ordering below ~8 K. The best fit to magnetic susceptibility above 40 K, using a dimer model with s = ?, gives rise to Δ/kB = 29.8 K, zJ′ = −0.72 K, C = 3.40 × 10−3 emu K mol−1 and χ 0 = −5.8 × 10−6 emu mol−1 with a fixed g = 2.0. Cyclovoltammetry revealed two quasi-reversible one-electron steps, which are attributed to Ni(IV/III) and Ni(III/II) redox couples. Graphical Abstract  [A novel complex [1-(4-bromobenzyl)-3-methylpyridinium][Ni(dmit)2] has been synthesized and structurally characterized. The anions of [Ni(dmit)2] stack into dimers, which further construct into two-leg ladder through lateral S···S interactions. The weak H–bonding interactions of C–H···S and van de Waals interactions between anion and cations were observed. Moreover, its magnetic property and electrochemical property have been investigated] .  相似文献   

20.
We investigated the mechanical and electrochemical properties of aluminum alloys. Aluminum alloys do not corrode due to the formation of an anti-corrosive passive film, such as Al2O3 or Al2O3 · 3H2O, which resists corrosion in neutral solutions. In seawater, however, Cl ions destroy this passive film. The current density in the first passivity range during the application of anodic protection had a similar value as that for concentration polarization by dissolved oxygen during the application of cathodic protection. The current density in the first passivity range had the lowest value overall. The lowest current densities in the potentiostatic and galvanostatic tests occurred at potentials of −1.4 to −0.7 V and −0.9 to −0.7 V, respectively.  相似文献   

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