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1.
The non-isothermal reductive decomposition reaction of crystalline CaSO3·0.5H2O and anhydrous CaSO3 under CO, CO2 and CO-CO2 gas mixtures at the two heating rates of 25°C min−1 and 6°C min−1 up to 900°C, respectively, was investigated employing thermogravimetric analysis, X-ray powder diffraction, IR spectroscopy and continuous SO2 measurement by on-line fluorescence spectroscopy. During the heating process the reaction involved a multistage weight loss, in both cases, with a corresponding multistage SO2 release. The multistage weight loss and the corresponding SO2 release were presumed to be the consequence of different sequential reactions taking place along with the direct reduction of CaSO3 to CaS, including the formation and decomposition of CaCO3 and CaSO4, respectively. The corresponding SO2 evolution was found to be considerably lower at slow heating rates. In the presence of additional CO2, the SO2 release was increased and the highest SO2 concentration was found for a feed-gas mixture of 70% CO2 and 30% CO, and also in pure CO2. The CaCO3 product also increased with increasing CO2 concentration. The possible reaction pathway is discussed.  相似文献   

2.
He D  Bao L  Long Y  Wei W  Yao S 《Talanta》2000,50(6):525-1273
A new bulk acoustic wave (BAW) cellulase sensing technique, which is based on the enzymatic hydrolysis process of sodium carboxymethylcellulose (CMC) by cellulase, was established. The frequency shift curves of BAW sensor indicated that the viscosity of the tested solutions decreased during the hydrolysis process. The hydrolysis rate of CMC by cellulase was calculated from the frequency shift curves. The hydrolysis rate of CMC under different pH conditions at 30°C showed that cellulase had high hydrolysis ability approximately at pH 5.0. Kinetic parameters (the Michaelis constant Km and the maximum rate Vmax) of the process were estimated by using a linear method of Lineweaver–Burk plot. Km is 1.95±0.25 mg ml−1 and Vmax is −(4.25±0.58)×10−3 g1/2 cm−3/2 cP1/2 min−1. Also the activation energy (Ea) of the enzymatic hydrolysis, with a value of 51.99±1.26 kJ mol−1, was estimated in this work.  相似文献   

3.
K. Kinoshita   《Thermochimica Acta》1977,20(3):297-308
The reactions between Pt oxides and carbon black in helium and air were examined by DTA. The thermograms were dependent on the mode of sample preparation. 20 wt.% PtO2 supported on carbon catalyst heated in He at 10°C min−1 produced an exotherm at approximately 400°C. Physical mixtures of PtO2 and carbon only reacted at a higher temperature (approximately 550°C) in He where PtO2 is thermally decomposed to Pt and O2. In air, Pt catalyzed the oxidation of cabon in the 20 wt.%Pt supported on carbon sample. On the other hand, PtO2 in the physical mixture did not appear to catalyze the oxidation of carbon in air. This difference in behavior is explained by assuming that atomic oxygen is produced in the supported catalyst sample which reacts at low temperature with carbon. In the physical mixture, thermal decomposition of PtO2 yields molecular oxygen which reacts with carbon at a higher temperature than does atomic oxygen.  相似文献   

4.
The hydrogen permeation and stability of tubular palladium alloy (Pd–23%Ag) composite membranes have been investigated at elevated temperatures and pressures. In our analysis we differentiate between dilution of hydrogen by other gas components, hydrogen depletion along the membrane length, concentration polarization adjacent to the membrane surface, and effects due to surface adsorption, on the hydrogen flux. A maximum H2 flux of 1223 mL cm−2 min−1 or 8.4 mol m−2 s−1 was obtained at 400 °C and 26 bar hydrogen feed pressure, corresponding to a permeance of 6.4 × 10−3 mol m−2 s−1 Pa−0.5. A good linear relationship was found between hydrogen flux and pressure as predicted for rate controlling bulk diffusion. In a mixture of 50% H2 + 50% N2 a maximum H2 flux of 230 mL cm−2 min−1 and separation factor of 1400 were achieved at 26 bar. The large reduction in hydrogen flux is mainly caused by the build-up of a hydrogen-depleted concentration polarization layer adjacent to the membrane due to insufficient mass transport in the gas phase. Substituting N2 with CO2 results in further reduction of flux, but not as large as for CO where adsorption prevail as the dominating flow controlling factor. In WGS conditions (57.5% H2, 18.7% CO2, 3.8% CO, 1.2% CH4 and 18.7% steam), a H2 permeance of 1.1 × 10−3 mol m−2 s−1 Pa−0.5 was found at 400 °C and 26 bar feed pressure. Operating the membrane for 500 h under various conditions (WGS and H2 + N2 mixtures) at 26 bars indicated no membrane failure, but a small decrease in flux. A peculiar flux inhibiting effect of long term exposure to high concentration of N2 was observed. The membrane surface was deformed and expanded after operation, mainly following the topography of the macroporous support.  相似文献   

5.
A configuration of dense mixed ionic and electronic conducting (MIEC) membrane with layered morphological structure for oxygen separation, which combines the benefits of high oxygen permeation flux of cobalt-based membrane, high chemical stability of iron-based perovskite and high mechanical strength of thick membrane, was studied. The membrane is normally composed of two layers; each layer is a dense MIEC oxide. The substrate layer is a thick dense membrane with high oxygen permeability but relatively lower chemical stability. The feasibility of dense thick Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF5582) membrane as the substrate layer and Ba0.5Sr0.5Co0.2Fe0.8O3−δ (BSCF5528) as the thin-film layer was mainly experimentally investigated. Both the BSCF5582 and the BSCF5528 show the same cubic perovskite structure and the similar lattice constant with no detrimental reaction products formed. By optimizing fabrication parameters of a simple dry pressing process, dual-layered membrane, free of cracks, was successfully fabricated. The oxygen permeation flux of a dual-layered membrane with the thin-film BSCF5528 layer facing to the sweep gas reached 2.1 mL cm−2 min−1 [STP] (1.56 × 10−6 mol cm−2 s−1) at 900 °C, which is about 3.5 times higher than that of the BSCF5528 membrane (0.6 mL cm−2 min−1, [STP] (4.46 × 10−7 mol cm−2 s−1) under the same conditions.  相似文献   

6.
UV spectra and kinetics for the reactions of alkyl and alkylperoxy radicals from methyl tert-butyl ether (MTBE) were studied in 1 atm of SF6 by the pulse radiolysis-UV absorption technique. UV spectra for the radical mixtures were quantified from 215 to 340 nm. At 240 nm. σR = (2.6 ± 0.4) × 10−18 cm2 molecule−1 and σRO2 = (4.1 ± 0.6) × 10−18 cm2 molecule−1 (base e). The rate constant for the self-reaction of the alkyl radicals is (2.5 ± 1.1) × 10−11 cm3 molecule−1 s−1. The rate constants for reaction of the alkyl radicals with molecular oxygen and the alkylperoxy radicals with NO and NO2 are (9.1 ± 1.5) × 10−13, (4.3 ± 1.6) × 10−12 and (1.2 ± 0.3) × 10−11 cm3 molecule−1 s−1, respectively. The rate constants given above refer to reaction at the tert-butyl side of the molecule.  相似文献   

7.
The far-UV (193 nm) laser flash photolysis of nitrogen-saturated isooctane solutions of 1,1-dimethylsiletane allows the direct detection of 1,1-dimethylsilene as a transient species, which (at low laser intensities) decays with pseudo-first-order kinetics (τ 10 μs) and exhibits a UV absorption spectrum with λmax 255 nm. Characteristic rapid quenching is observed for the silene with methanol (kMcOH = (4.9 ± 0.2) × 109 M−1 s−1), tert-butanol (kBuOH = (1.8 ± 0.1) × 109 M−1 s−1) and oxygen (kO2 = (2.0 ± 0.5) × 108 M−1 s−1). The Arrhenius activation parameters for the reaction with methanol have been determined to be Ea = −2.6 ± 0.6 kcal mol−1 and log A = 7.7 ± 0.3.  相似文献   

8.
A flow injection on-line sorption preconcentration electrothermal atomic absorption spectrometric system for fully automatic determination of lead in water was investigated. The discrete non-flow-through nature of ETAAS, the limited capacity of the graphite tube and the relatively large volume of the knotted reactor (KR) are obstacles to overcome for the on-line coupling of the KR sorption preconcentration system with ETAAS. A new FI manifold has been developed with the aim of reducing the eluate volume and minimizing dispersion. The lead diethyldithiocarbamate complex was adsorbed on the inner walls of a knotted reactor made of PTFE tubing (100 cm long, 0.5 mm i.d.). After that, an air flow was introduced to remove the residual solution from the KR and the eluate delivery tube, then the adsorbed analyte chelate was quantitatively eluted into a delivery tube with 50 μl of ethanol. An air flow was used to propel the eluent from the eluent loop through the reactor and to introduce all the ethanolic eluate onto the platform of the transversely heated graphite tube atomizer, which was preheated to 80°C. With the use of the new FI manifold, the consumption of eluent was greatly reduced and dispersion was minimized. The adsorption efficiency was 58%, and the enhancement factor was 142 in the concentration range 0.01–0.05 μg l−1 Pb at a sample loading rate of 6.8 ml min−1 with 60 s preconcentration time. For the range 0.1–2.0 μg l−1 of Pb a loading rate of 3.0 ml min−1 and 30 s preconcentration time were chosen, resulting in an adsorption efficiency of 42% and an enhancement factor of 21, respectively. A detection limit (3σ) of 2.2 ng l−1 of lead was obtained using a sample loading rate of 6.8 ml min−1 and 60 s preconcentration. The relative standard deviation of the entire procedure was 4.9% at the 0.01 μg l−1 Pb level with a loading rate of 6.8 ml min−1 and 60 s preconcentration, and 2.9% at the 0.5 μg l−1 Pb level with a 3.0 ml min−1 loading rate and 30 s preconcentration. Efficient washing of the matrix from the reactor was critical, requiring the use of the standard addition method for seawater samples. The analytical results obtained for seawater and river water standard reference materials were in good agreement with the certified values.  相似文献   

9.
Saran L  Cavalheiro E  Neves EA 《Talanta》1995,42(12):2027-2032
The highly neutralized ethylenediaminetetraacetate (EDTA) titrant (95–99% as Y4− anion) precipitates with Ag+ cations to form the Ag4Y species, in aqueous medium, which is well characterized from conductometric titration, thermal analysis and potentiometric titration of the silver content of the solid. The precipitate dissolves in excess Y4− to form a complex, AgY3−. Equilibrium studies at 25°C and ionic strength 0.50 M (NaNO3) have shown from solubility and potentiometric measurements that the formation constant (95% confidence level) β1 = (1.93 ± 0.07) × 105 M−1 and the solubility products are KS0 = [Ag +]4[Y4−] = (9.0 ± 0.4) × 10−18 M5 and KS1 = [Ag +]3[AgY3−] = (1.74 ± 0.08) × 10−12 M4. The presence of Na+, rather than ionic strength, markedly affects the equilibrium; the data at ionic strength 0.10 M are: β1 = (1.19 ± 0.03) × 106 M−1, KS0 = (1.6 ± 0.4) × 10−19 M5 and KS1 = (1.9 ± 0.5) × 10−13 M4; at ionic strength tending to zero; β1 = (1.82 ± 0.05) × 107 M−1, KS0 = (2.6 ± 0.8) × 10−22 M5 and KS1 = (5 ± 1) × 10−15 M4. The intrinsic solubility is 2.03 mM silver (I) in 0.50 M NaNO3. Well-defined potentiometric titration curves can be taken in the range 1–2 mM with the Ag indicator electrode. Thermal analysis revealed from differential scanning calorimetry a sharp exothermic peak at 142°C; thermal gravimetry/differential thermal gravimetry has shown mass loss due to silver formation and a brown residue, a water-soluble polymeric acid (decomposition range 135–157°C), tending to pure silver at 600°C, consistent with the original Ag4Y salt.  相似文献   

10.
Stabilised polypropylene fibres of 28 μm diameter have been exposed at 80 °C under 5 MPa oxygen pressure, in dry conditions, in pure water and in alkaline medium. Their residual stability is determined from the temperature Tox of the onset of the oxidation exotherm, measured by differential scanning calorimetry at 10 K min−1 scanning rate. The time tex to reach the characteristics of unstabilised samples (Tox=175 °C) is of the order of 220 (dry conditions), 160 h (water) and 80 h (alkaline medium), whereas it is of the order of 750 h at 110 °C in classical tests made at atmospheric pressure. This increase of ageing rate is discussed in terms of kinetic effect of O2 pressure and efficiency of the liquid medium to extract stabilisers.  相似文献   

11.
The collisional quenching of electronically excited germanium atoms, Ge[4p2(1S0)], 2.029 eV above the 4p2(3P0) ground state, has been investigated by time-resolved atomic resonance absorption spectroscopy in the ultraviolet at λ = 274.04 nm [4d(1P10) ← 4p2(1S0)]. In contrast to previous investigations using the ‘single-shot mode’ at high energy, Ge(1S0) has been generated by the repetitive pulsed irradiation of Ge(CH3)4 in the presence of excess helium gas and added gases in a slow flow system, kinetically equivalent to a static system. This technique was originally developed for the study of Ge[4p2(1D2)] which had eluded direct quantitative kinetic study until recently. Absolute second-order rate constants obtained using signal averaging techniques from data capture of total digitised atomic decay profiles are reported for the removal of Ge(1S0) with the following gases (kR in cm3 molecule−1 s−1, 300 K): Xe, 7.1 ± 0.4 × 10−13; N2, 4.7 ± 0.6 × 10−12; O2, 3.6 ± 0.9 × 10−11; NO, 1.5 ± 0.3 × 10−11; CO, 3.4 ± 0.5 × 10−12; N2O, 4.5 ± 0.5 × 10−12; CO2, 1.1 ± 0.3 × 10−11; CH4, 1.7 ± 0.2 × 10−11; CF4, 4.8 ± 0.3 × 10−12; SF6, 9.5 ± 1.0 × 10−13; C2H4, 3.3 ± 0.1 × 10−10; C2H2, 2.9 ± 0.2 × 10−10; Ge(CH3)4, 5.4 ± 0.2 × 10−11. The results are compared with previous data for Ge(1S0) derived in the single-shot mode where there is general agreement though with some exceptions which are discussed. The present data are also compared with analogous quenching rate data for the collisional removal of the lower lying Ge[4p2(1D2)] state (0.883 eV), also characterized by signal averaging methods similar to that described here.  相似文献   

12.
The reaction: F + HCl→ HF (v 3) + Cl (1), has been initiated by photolysing F2 using the fourth-harmonic output at 266 nm from a repetitively pulsed Nd: YAG laser By analysing the time-dependence of the HF(3,0) vibrational chemiluminescence, rate constants have been determined at (296 ± 5) K for reaction (1), k1 = (7.0 ± 0.5) × 10−12 cm3 molecule−1 s−1, and for the relaxation of HF(v = 3) by HCl, CO2, N2O, CO, N2 and O2: kHCl = (1.18 ±0.14) × 10−11 kCO2 = (1.04 ± 0. 13) × 10−12, kN2O = (1.41 ± 0.13) × 10−11 kCO = (2.9 ± 0.3) × (10−12, kN2 = (7.1 ± 0.6) × 10−14 and kO2 = (1.9 ± 0.6) × 10−14 cm3molecule−1s−1.  相似文献   

13.
This article gives the degradation rate constants of meso-tetrakis(3,5-disulfonatomesityl)porphinatomanganese(III) X (where X=H2O and/or OH depending on pH) (MnTMSP) and its β-brominated analogue (MnTMSPBr8) toward the oxidants NaOCl, H2O2, and (CH3)3COOH at various pHs, I=0.2 M and 30°C. In addition, the degradation rate constants of MnTMSP was determined when it was bound to cationic supports — namely, CTAB, a poly(vinylbenzyltrimethylammonium chloride) latex, 2,6-ionene and 2,10-ionene. MnTMSP showed high structural stability toward the peroxides in strong acidic medium and the degradation rate constants were found as low as 10−4 min−1 at pH<1.50. When NaOCl was employed as the oxidant, the pH dependence of the stability of MnTMSP was vice versa and its degradation rate constant was determined as 1.43×10−4 min−1 at pH 14.10. In strong acidic solution, the supports CTAB and latex made the stability of MnTMSP toward the peroxides improve significantly. In strong basic solution, only latex-bound MnTMSP showed higher stability toward NaOCl than the homogeneous MnTMSP. Because MnTMSPBr8 was not stable in solutions having pH higher than 9 and containing no oxidant, its stability was investigated at pH<9 and it showed slightly lower stability toward the peroxides than the non-brominated analogue.  相似文献   

14.
The calorimetric glass transition behaviour in the amorphous forms of water is reviewed: for a heating rate of 30 K min−1 the onset temperature, or Tg, of the glass transition is 136±1 K for hyperquenched glassy water and annealed vapour-deposited amorphous solid water, and 129±1 K for the low-density form of pressure-amorphized hexagonal ice. The increase in heat capacity in the glass transition region is between 1.6–2 J K mol for the three amorphous forms. Annealing of the samples a few degrees below Tg or heating several degrees above the glass transition region has no influence on the onset temperatures at 136 K and 129 K respectively, which is contrary to ‘normal’ behaviour. The results are discussed with respect to the ‘structure’ of the three amorphous forms of water below the glass transition region and a “gel-like” state of water above Tg.  相似文献   

15.
The second-order rate constants of gas-phase Lu(2D3/2) with O2, N2O and CO2 from 348 to 573 K are reported. In all cases, the reactions are relatively fast with small barriers. The disappearance rates are independent of total pressure indicating bimolecular abstraction processes. The bimolecular rate constants (in molecule−1 cm3 s−1) are described in Arrhenius form by k(O2)=(2.3±0.4)×10−10exp(−3.1±0.7 kJmol−1/RT), k(N2O)=(2.2±0.4)×10−10exp(−7.1±0.8 kJmol−1/RT), k(CO2)=(2.0±0.6)×10−10exp(−7.6±1.3 kJmol−1/RT), where the uncertainties are ±2σ.  相似文献   

16.
Quantitative IR solution data in carbon tetrachloride and chloroform are recorded for the CO and OH regions of 31 chromones. In the 1580–1700 cm−1 region, 5-hydroxychromones show three main maxima, the two of highest frequency, at 1663 ± 3 cm−1 and 1630 ± 5 cm−1 in CCl4 (1661 ± 2 cm−1 and 1627 ± 5 cm−1 in CHCl3), being sufficiently intense as to possess high CO character. Typically, 5-alkoxychromones exhibit two intense maxima in this region, 1663 ± 3 cm−1 and 1613 ± 7 cm−1 in CCl4 (1657 ± 2 cm−1 and 1608 ± 12 cm−1 in CHCl3). Diagnostically useful changes in contour and principal peak positions can be seen for substituted and annellated 5-hydroxychromones. In the 2500–3650 cm−1 region, the stretching frequencies of OH groups at the most commonly encountered positions (C-5, C-7, and 2-CH2OH) in natural chromones, are identified.  相似文献   

17.
The compound [Zn(H2O)4]2[H2As6V15O42(H2O)]·2H2O (1) has been synthesized and characterized by elemental analysis, IR, ESR, magnetic measurement, third-order nonlinear property study and single crystal X-ray diffraction analysis. The compound 1 crystallizes in trigonal space group R3, a=b=12.0601(17) Å, c=33.970(7) Å, γ=120°, V=4278.8(12) Å3, Z=3 and R1(wR2)=0.0512 (0.1171). The crystal structure is constructed from [H2As6V15O42(H2O)]4− anions and [Zn(H2O)4]2+ cations linked through hydrogen bonds into a network. The [H2As6V15O42(H2O)]6− cluster consists of 15 VO5 square pyramids linked by three As2O5 handle-like units.  相似文献   

18.
Mercuric 5-nitrotetrazole is a possible replacement for lead azide. The thermal decomposition peak maximum ranged from 185 to 270°C as the heating rate increased from 0.1 to 100°C min−1. The activation energy and frequency factor for thermal decomposition were determined from dynamic and isothermal DSC and isothermal TG data; the average values were 38.8 kcal mol−1 and 3.56×1014 s−1. A half-life experiment confirmed the kinetic constants and indicated that the decomposition reaction was first order. The heat of explosion was determined by a pressure DSC test and found to be 2587 J g−1. The linear coefficient of expansion was 37±2×10−6°C−1 from −60 to 160°C and indicated secondary transitions near −10 and 90°C. The specific heat was 0.0003154T+0.1339 in the region −40–90°C. The critical temperature for a slab with a half-thickness of 0.035 cm was calculated to be 232 °C.  相似文献   

19.
The optimisation of ICPMS collision/reaction cell conditions for the simultaneous analysis of arsenic and selenium is described. A mixture of 3.8 mL min−1 of H2 and 0.5 mL min−1 of He was found to be suitable for the removal of both ArAr+ and ArCl+ interferences. Detection limits down to 30 ng (element) L−1 in total analysis, and between 81 and 230 ng (element) L−1 in speciation analysis were achieved in chloride matrix (1 g L−1 NaCl). After validation, the method was applied to commercially available mineral waters.  相似文献   

20.
用丁烷代替苯为原料生产马来酸酐 ,是低碳烷烃选择氧化成功实现工业化的极少数例子之一 [1] ,其中 VPO复氧化物是唯一能高活性且高选择性地催化这一过程的催化剂 .因而 ,这一领域的研究备受关注 [2 ,3] .以 VPO铵盐单晶结构的研究为例 ,迄今已对α- NH4 V ( HPO4 ) [4 ] ,β- NH4 V ( HPO4 ) [5] ,NH4 VOPO4 [6 ] ,NH4 VOPO4 · H2 O[7] 和 α- NH4 VO2 HPO4 [8] 等进行了结构研究 .作为催化剂活性物质( VO) 2 P2 O7的前驱体 ,β- NH4 ( VO2 ) ( HPO4 )也曾被 Pulvin等 [9,10 ] 由粉末衍射数据推测分子组成为NH4 ( VO…  相似文献   

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