首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 31 毫秒
1.
Nitrogen dioxide (NO2) concentrations were used to evaluate the air quality before and after the infrastructural change of an important traffic artery in Mortsel, Antwerp (Belgium). During the reconstruction works two pairs of traffic lanes were reduced to one in each direction. Two sampling campaigns were conducted: the first one before the works in 2003 and the second one in 2005, after the road works were finished. Sampling was performed on a weekly base with the use of passive diffusion tubes on the streets, and also indoors in nearby houses. The samples were analyzed by ion chromatography, from which data the NO2 concentrations in air could be calculated. These results were compared with NO2 values from the air monitoring station 42R801 of the Flemish Environment Agency in Borgerhout, Antwerp. On the base of different NO2 concentrations, correlated well with the traffic density, sampling locations were classified into three groups as follows: 1) ‘heavily polluted’ (heavy traffic); 2) ‘moderately polluted’ (medium traffic); or 3) ‘less polluted’ (low traffic density). Sampling sites located further from the road works, enclosed to the group ‘less polluted’, showed the lowest NO2 concentrations. The highest NO2 level was found for the locations close to reconstruction works, which belonged to the group ‘heavily polluted’. The contribution of NO2 was at the same level before and after the road works. During the first campaign it ranged from 30 ± 7 µg/m3 to 71 ± 11 µg/m3 and during the second sampling it was between 36 ± 17 µg/m3 and 73 ± 17 µg/m3. These modernization works had no impact on preventing the traffic-related pollutant as NO2 and as a consequence no significant effect on the air quality in the studied region. It has been proven that the impact of traffic on the air quality is unmistakably high and simply reduction of the number of the traffic lanes, intended to discourage the traffic flow, had apparently no environmentally advantageous effect.  相似文献   

2.
It is found that charge-transfer on NO2 with Cl2 is fast at thermal energy. The Cl2 ion reacts with NO2 to produce Cl and NO2Cl, and SH charge-transfers rapidly with both Cl2 and NO2. From the exothermicities implied it is deduced that EA (SH)<EA (NO2)< EA (Cl2) or EA (NO2) = 2.38 ± 0.06 eV and EA (Cl2 = 2.46 ± 0.14 eV.  相似文献   

3.
Two pure strontium borates SrB2O4·4H2O and SrB2O4 have been synthesized and characterized by means of chemical analysis and XRD, FT-IR, DTA-TG techniques. The molar enthalpies of solution of SrB2O4·4H2O and SrB2O4 in 1 mol dm−3 HCl(aq) were measured to be −(9.92 ± 0.20) kJ mol−1 and −(81.27 ± 0.30) kJ mol−1, respectively. The molar enthalpy of solution of Sr(OH)2·8H2O in (HCl + H3BO3)(aq) were determined to be −(51.69 ± 0.15) kJ mol−1. With the use of the enthalpy of solution of H3BO3 in 1 mol dm−3 HCl(aq), and the standard molar enthalpies of formation for Sr(OH)2·8H2O(s), H3BO3(s), and H2O(l), the standard molar enthalpies of formation of −(3253.1 ± 1.7) kJ mol−1 for SrB2O4·4H2O, and of −(2038.4 ± 1.7) kJ mol−1 for SrB2O4 were obtained.  相似文献   

4.
The kinetics of Mn2O3 digestion in various H2SO4 solutions (0.5-2.0 M) and at various temperatures (ambient to 80 °C) to form solid γ-MnO2 and soluble Mn(II) have been examined using X-ray diffraction. Using a modified first-order Avrami expression to describe digestion kinetics, rate constants in the range 0.02-0.98 h−1 were found for Mn2O3 disappearance, and 0.03-0.42 h−1 for γ-MnO2 formation, with higher H2SO4 concentrations and temperatures leading to faster conversion rates. Also, for a particular set of experimental conditions, the rate of γ-MnO2 formation was always slower than Mn2O3 disappearance. This was interpreted in terms of the solubility and stability of the soluble Mn(III) intermediated formed during the digestion. Activation energies for Mn2O3 dissolution and γ-MnO2 formation were also determined.  相似文献   

5.
Hydroboration reactions of 1-octene and 1-hexyne with H2BBr·SMe2 in CH2Cl2 were studied as a function of concentration and temperature, using 11B NMR spectroscopy. The reactions exhibited saturation kinetics. The rate of dissociation of dimethyl sulfide from boron at 25 °C was found to be (7.36 ± 0.59 and 7.32 ± 0.90) × 10−3 s−1 for 1-octene and 1-hexyne, respectively. The second order rate constants, k2, for hydroboration worked out to be 7.00 ± 0.81 M s−1 and 7.03 ± 0.70 M s−1, while the overall composite second order rate constants, k K, were (3.30 ± 0.43 and 3.10 ± 0.37) × 10−2 M s−1, respectively at 25 °C. The entropy and enthalpy values were found to be large and positive for k1, whilst for k2 these were large and negative, with small values for enthalpies. This is indicative of a limiting dissociative (D) for the dissociation of Me2S and associative mechanism (A) for the hydroboration process. The overall activation parameters, ΔH and ΔS, were found to be 98 ± 2 kJ mol−1 and +56 ± 7 J K−1 mol−1 for 1-octene whilst, in the case of 1-hexyne these were found out to be 117 ± 7 kJ mol−1 and +119 ± 24 J K−1 mol−1, respectively. When comparing the kinetic data between H2BBr·SMe2 and HBBr2·SMe2, the results showed that the rate of dissociation of Me2S from H2BBr·SMe2 is on average 34 times faster than it is in the case of HBBr2·SMe2. Similarly, the rate of hydroboration with H2BBr·SMe2 was found to be on average 11 times faster than it is with HBBr2·SMe2. It is also clear that by replacing a hydrogen substituent with a bromine atom in the case of H2BBr·SMe2 the mechanism for the overall process changes from limiting dissociative (D) to interchange associative (Ia).  相似文献   

6.
Reaction of trans-[PtClMe(SMe2)2] with the mono anionic ligands azide, bromide, cyanide, iodide and thiocyanate result in substitution of the chloro ligand as the first step. In contrast the neutral ligands pyridine, 4-Me-pyridine and thiourea substitute a SMe2 ligand in the first step as confirmed by 1H NMR spectroscopy and the kinetic data. Detailed kinetic studies were performed in methanol as solvent by use of conventional stopped-flow spectrophotometry. All processes follow the usual two-term rate law for square-planar substitutions, kobs = k1 + k2[Y] (where k1 = kMeOH[MeOH]), with k1 = 0.088 ± 0.004 s−1 and k2 = 1.18 ± 0.13, 3.8 ± 0.3, 17.8 ± 1.3, 34.9 ± 1.4, 75.3 ± 1.1 mol−1 dm3 s−1 for Y = N3, Br, CN, I and SCN respectively at 298 K. The reactions with the neutral ligands proceed without an appreciable intercept with k2 = 5.1 ± 0.3, 15.3 ± 1.8 and 195 ± 3 mol−1 dm3 s−1 for Y = pyridine, 4-Me-pyridine and thiourea, respectively, at 298 K. Activation parameters for MeOH, , Br, CN, I, SCN, and Tu are ΔH = 47.1 ± 1.6, 49.8 ± 0.6, 39 ± 3, 32 ± 8, 39 ± 5, 34 ± 4 and 31 ± 3 kJ mol−1 and ΔS = −107 ± 5, −77 ± 2, −104 ± 9,−113 ± 28, −85 ± 18, −94 ± 14 and −97 ± 10 J K−1 mol−1, respectively. Recalculation of k1 to second-order units gives the following sequence of nucleophilicity: (1:13:42:57:170:200:390:840:2170) at 298 K. Variation of the leaving group in the reaction between trans-[PtXMe(SMe2)2] and SCN follows the same rate law as stated above with k2 = 75.3 ± 1.1, 236 ± 4 and 442 ± 5 mol−1 dm3 s−1 for X = Cl, I and N3, respectively, at 298 K. The corresponding activation parameters were determined as ΔH = 34 ± 4, 32 ± 2 and 39.3 ± 1.7 kJ mol−1 and ΔS = −94 ± 14, −86 ± 8 and −68 ± 6 J K−1 mol−1. All the kinetic measurements indicate the usual associate mode of activation for square planar substitution reactions as supported by large negative entropies of activation, a significant dependence of the reaction rate on different entering nucleophiles and a linear free energy relationship.  相似文献   

7.
The areas of the fusion and crystallization peaks of K3TaF8 and K3TaOF6 have been measured using the DSC mode of the high-temperature calorimeter (SETARAM 1800 K). On the basis of these quantities and the temperature dependence of the used calorimetric method sensitivity, the values of the enthalpy of fusion of K3TaF8 at temperature of fusion 1039 K: ΔfusHm(K3TaF8; 1039 K) = (52 ± 2) kJ mol−1 and of K3TaOF6 at temperature of fusion 1055 K: ΔfusHm(K3TaOF6; 1055 K) = (62 ± 3) kJ mol−1 have been determined.  相似文献   

8.
Low-temperature heat capacities of the compound Na(C4H7O5)·H2O(s) have been measured with an automated adiabatic calorimeter. A solid-solid phase transition and dehydration occur at 290-318 K and 367-373 K, respectively. The enthalpy and entropy of the solid-solid transition are ΔtransHm = (5.75 ± 0.01) kJ mol−1 and ΔtransSm = (18.47 ± 0.02) J K−1 mol−1. The enthalpy and entropy of the dehydration are ΔdHm = (15.35 ± 0.03) kJ mol−1 and ΔdSm = (41.35 ± 0.08) J K−1 mol−1. Experimental values of heat capacities for the solids (I and II) and the solid-liquid mixture (III) have been fitted to polynomial equations.  相似文献   

9.
In the present study, the stability of gaseous barium silicates was confirmed by the high temperature mass spectrometry. On the basis of equilibrium constants measured for gas-phase reactions, the standard formation enthalpies were determined for gaseous barium silicates as (−510 ± 15) kJ · mol−1 and (−884 ± 18) kJ · mol−1 at 298 K; standard atomization enthalpies as (1637 ± 17) kJ · mol−1 and (2318 ± 20) kJ · mol−1 at 298 K for BaSiO2 and BaSiO3, respectively. Based on the results obtained the critical analysis of the literature data was carried out.  相似文献   

10.
The kinetics and mechanism of the hydroboration reactions of 1-octene with HBBr2 · SMe2 and HBCl2 · SMe2, in CH2Cl2 as a solvent, were studied. Rates of hydroboration were monitored using 11B NMR spectroscopy. The reactions exhibited simple second-order kinetics of the form . The HBCl2 · SMe2 was found to be 20 times more reactive than the HBBr2 · SMe2. The overall activation parameters (ΔH, ΔS) for the reaction of HBBr2 · SMe2 with 1-octene were found to be 82 ± 1 kJ mol−1, −18 ± 4 J K−1 mol−1 and with 1-hexyne were 78 ± 4 kJ mol−1 −34 ± 12 J K−1 mol−1. For the reaction of HBCl2 · SMe2 with 1-octene, ΔH and ΔS were 104 ± 5 kJ mol−1 and 43 ± 16 J K−1 mol−1, respectively. The activation parameters (ΔH, ΔS) for the dissociation of Me2S from HBBr2 · SMe2 were found to be 104 ± 2 kJ mol−1, +33 ± 8 J K−1 mol−1, respectively. Based on the activation parameters, it was concluded that the detaching of Me2S from the boron centre follows a dissociative mechanism, while the hydroboration process follows an associative pathway. It was also concluded that the dissociation of Me2S from the boron centre is the rate determining step.  相似文献   

11.
Tetragonal PbSnF4 was prepared by precipitation method with Pb(NO3)2 and SnF2 aqueous solutions. The product was characterized using X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XFS), and the other chemical analyses. Tetragonal PbSnF4 exhibited the highest electric conductivity of 3.2 Sm−1 at 473 K in air as a fluoride ion conductor. We have investigated the possibility of COF2 formation using CO2 and F2 in an electrochemical cell with PbSnF4 as a solid electrolyte. At same time, we tried to produce an electric power from an electrochemical cell. This CO2/F2 electrochemical cell was constructed with a tetragonal PbSnF4 disk having Au electrodes. The electromotive force was about 0.9 V at room temperature for 0.1 MPa CO2/(0.01 MPa F2 + 0.09 MPa Ar). However, the short circuit current density was 0.24 A m−2, which was quite small. This current density was so small that no fluorocarbon compound was detected after 3 h discharge using FT-IR.  相似文献   

12.
Air monitoring networks are necessary to assess air quality in order to reduce pollution to levels which minimise harmful effects on human health and the environment. This paper describes a method to design air quality monitoring networks for nitrogen dioxide and ozone and its application in Cordova, Andalusia, southern Spain. The city has a population of 325,453 inhabitants and traffic is its main source of air pollution. The first step of this method made it possible to determine from historical data that two control stations for NO2 and one control stations for O3 are necessary according to the legislation. Sampling campaigns with passive diffusion samplers at 81 sites were then carried out to obtain information on the pollution distribution in Cordova. The sampling campaigns in 2001–2002 revealed an average concentration of 19.5 μg/m3 for NO2 with maximum values up to 28.6 μg/m3 in Cordova city centre. The average ozone concentrations were recorded downwind from the emission source, reaching 91.8 μg/m3; the average ozone value in Cordova was 65.3 μg/m3. After spatial interpolation of the obtained values with Geographical Information Systems, a selection of the best locations for the monitoring stations was made, in line with the macro- and microscale siting requirements of the European Directive 2008/50/EC on ambient air quality and cleaner air for Europe. A second sampling campaign with diffusive samplers was carried out in 2007 to control if the locations of the air quality assessment stations were still representative for their zone.  相似文献   

13.
There has been speculations on the structures of TiF4 polymeric complexes {TiF4L}n (L = molecular donor) for several decades, however no structurally characterized examples have been reported. In this work the complex {TiF4(PhCN)}3 was isolated from a solution of TiF4 in PhCN (donor number DN = 11.9 kcal mol−1) as well as from the mixtures PhCN/CH2Cl2 and PhCN/toluene and characterized by X-ray, IR, NMR, EI-MS. The structure of the complex {TiF4(PhCN)}3 can be regarded as formed by combining three face-TiF3(PhCN)(μ-F) units, containing octahedrally coordinated titanium centers surrounded by three terminal fluorine atoms on the face of the octahedron and the bridging fluorine atoms in cis-positions with respect to each other. The structure of {TiF4(PhCN)}3 represents the first example of a trimeric pseudo pentahalide MX4L (M = Ti, Zr, X = halogen, D = ligand), a class of potentially interesting Lewis acids. The characterization of {TiF4(PhCN)}3 by 19F NMR revealed that in solution it dissociated to a mixture of [TiF3(PhCN)3]+, TiF4(PhCN)2 and oligomers including [Ti4F18]2− and {TiF4(PhCN)}n. The existence of oligomeric complexes containing face-{TiF3(PhCN)3−n(μ-F)n} (n = 1-3) fragments was established by one- and two-dimensional variable temperature 19F NMR. In contrast, TiF4 has a low solubility in SO2, because the donor strength of SO2 (DN = 6.5 ± 2.2 kcal mol−1) is too weak to fully convert polymeric TiF4 into soluble TiF4-SO2 donor-acceptor adducts. TiF4 and MeCN (DN = 14.1 kcal mol−1) formed only the molecular complex TiF4(MeCN)2, characterized by preliminary X-ray structure, IR and EI-MS. Thus mononuclear donor-acceptor complexes TiF4L2 can only be isolated from MeCN and stronger basic solvents.  相似文献   

14.
The present study describes the adsorption characteristic of Cd(II) onto Nb2O5/Al2O3 mixed oxide dispersed on silica matrix. The characterization of the adsorbent has been carried out by infrared spectroscopy (IR), scanning electronic microscopy (SEM), energy dispersive spectroscopy (EDS), energy dispersive X-ray fluorescence analysis (EDXRF) and specific surface area (SBET). From batch experiments, adsorption kinetic of Cd(II) was described by a pseudo-second-order kinetic model. The Langmuir linear isotherm fitted to the experimental adsorption isotherm very well, and the maximum adsorption capacity was found to be 17.88 mg g−1. Using the effective material, a method for Cd(II) preconcentration at trace level was developed. The method was based on on-line adsorption of Cd(II) onto SiO2/Al2O3/Nb2O5 at pH 8.64, in which the quantitative desorption occurs with 1.0 mol L−1 hydrochloric acid towards FAAS detector. The experimental parameters related to the system were studied by means of multivariate analysis, using 24 full factorial design and Doehlert matrix. The effect of SO42−, Cu2+, Zn2+ and Ni2+ foreign ions showed no interference at 1:100 analyte:interferent proportion. Under the most favorable experimental conditions, the preconcentration system provided a preconcentration factor of 18.4 times, consumption index of 1.08 mL, sample throughput of 14 h−1, concentration efficiency of 4.35 min−1, linear range from 5.0 up to 35.0 μg L−1 and limits of detection and quantification of 0.19 and 0.65 μg L−1 respectively. The feasibility of the proposed method for Cd(II) determination was assessed by analysis of water samples, cigarette sample and certified reference materials TORT-2 (Lobster hepatopancreas) and DOLT-4 (Dogfish liver).  相似文献   

15.
Thermal behavior, relative stability, and enthalpy of formation of α (pink phase), β (blue phase), and red NaCoPO4 are studied by differential scanning calorimetry, X-ray diffraction, and high-temperature oxide melt drop solution calorimetry. Red NaCoPO4 with cobalt in trigonal bipyramidal coordination is metastable, irreversibly changing to α NaCoPO4 at 827 K with an enthalpy of phase transition of −17.4±6.9 kJ mol−1. α NaCoPO4 with cobalt in octahedral coordination is the most stable phase at room temperature. It undergoes a reversible phase transition to the β phase (cobalt in tetrahedra) at 1006 K with an enthalpy of phase transition of 17.6±1.3 kJ mol−1. Enthalpy of formation from oxides of α, β, and red NaCoPO4 are −349.7±2.3, −332.1±2.5, and −332.3±7.2 kJ mol−1; standard enthalpy of formation of α, β, and red NaCoPO4 are −1547.5±2.7, −1529.9±2.8, and −1530.0±7.3 kJ mol−1, respectively. The more exothermic enthalpy of formation from oxides of β NaCoPO4 compared to a structurally related aluminosilicate, NaAlSiO4 nepheline, results from the stronger acid-base interaction of oxides in β NaCoPO4 (Na2O, CoO, P2O5) than in NaAlSiO4 nepheline (Na2O, Al2O3, SiO2).  相似文献   

16.
The vaporization of DyI3(s) was investigated in the temperature range between 833 and 1053 K by the use of Knudsen effusion mass spectrometry. The ions DyI2+, DyI3+, Dy2I4+, Dy2I5+, Dy3I7+, and Dy3I8+ were detected in the mass spectrum of the equilibrium vapor. The gaseous species DyI3, (DyI3)2, and (DyI3)3 were identified and their partial pressures determined. Enthalpies and entropies of sublimation resulted according to the second- and third-law methods. The following sublimation enthalpies at 298 K were determined for the gaseous species given in brackets: 274.8±8.2 kJ mol−1 [DyI3], 356.0±11.3 kJ mol−1 [(DyI3)2], and 436.6±14.6 kJ mol−1 [(DyI3)3]. The enthalpy changes of the dissociation reactions (DyI3)2=2 DyI3 and (DyI3)3=3 DyI3 were obtained as ΔdH°(298)=193.3±5.6 and 390.3±13.0 kJ mol−1, respectively.  相似文献   

17.
A simple method has been developed for the determination of arsenic and antimony in environmental samples by solid sampling electrothermal atomic absorption spectrometry, which was validated using certified reference materials of soils (S-VM — Soil Eutric Cambisol; S-MS — Soil Orthic Luvisols; S-SP — Soil Rendzina), sewage sludge (WT-L; WT-M) and sediments (NIES2; GBW07906). The analytical procedure combines solid sampling with utilization of a matrix modifier admixture containing 5 µg of W and 5 µg of Mg. The tungsten in the admixture serves to stabilize the solid matrix during atomisation, which results in dramatically reduced non-specific absorption compared with the conventional palladium modifier. Magnesium was efficient in reducing the accumulation of the matrix residue on the platform. An alternative resonance line of 197.2 nm for arsenic and 206.8 nm for Sb was used in order to eliminate the spectral interferences caused by aluminum compounds, and silicon and iron compounds, respectively. Under optimized experimental conditions, the effective in situ analyte/matrix separation was achieved so that the use of aqueous standards for calibration became possible. With the modifier, a 3 SD detection limit of 0.5 µg g1 As and 0.1 µg g1 Sb and 10 SD quantification limit of 1.7 µg g1As and 0.3 µg g1 Sb and a characteristic mass of 65 pg As and 53 pg Sb were obtained. For all the matrices under scrutiny, a good agreement with certified values was achieved with RSD values less than 10%.  相似文献   

18.
A pure hydrated potassium borate K2B5O8(OH)·2H2O has been synthesized under mild hydrothermal conditions and characterized by single-crystal X-ray diffraction, XRD, FT-IR, Raman spectra and DTA-TG. The crystal structure consists of two K-O polyhedra and [B5O8(OH)]2− polyborate anion. The enthalpy of formation was determined to be −4772.6 ± 4.0 kJ mol−1 by solution calorimetry.  相似文献   

19.
Serge Zhuiykov  Eugene Kats 《Talanta》2010,82(2):502-5442
A Cu2O-doped RuO2 sensing electrode (SE) for potentiometric detection of dissolved oxygen (DO) was prepared and its structure and electrochemical properties were analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron microscopy (XPS) and energy-dispersive spectroscopy (EDS) techniques. Cu2O-RuO2-SE displayed a linear DO response from 0.5 to 8.0 ppm (log[O2], −4.73 to −3.59) within a temperature range of 9-30 °C. The maximum sensitivity of −47.4 mV/decade at 7.27 pH was achieved at 10 mol% Cu2O. Experimental evaluation of the Cu2O-doped RuO2-SE demonstrated that the doping of RuO2 not only improves its structure but also enhances both sensor's selectivity and antifouling properties. Selectivity measurements revealed that 10 mol% Cu2O-doped RuO2-SE is insensitive to the presence of Na+, Mg2+, K+, Ca2+, NO3, PO42− and SO42− ions in the solution in the concentration range of 10−7-10−1 mol/l.  相似文献   

20.
The molar heat capacities of 1-(2-hydroxy-3-chloropropyl)-2-methyl-5-nitroimidazole (Ornidazole) (C7H10ClN3O3) with purity of 99.72 mol% were measured with an adiabatic calorimeter in the temperature range between 79 and 380 K. The melting-point temperature, molar enthalpy, ΔfusHm, and entropy, ΔfusSm, of fusion of this compound were determined to be 358.59±0.04 K, 21.38±0.02 kJ mol−1 and 59.61±0.05 J K−1 mol−1, respectively, from fractional melting experiments. The thermodynamic function data relative to the reference temperature (298.15 K) were calculated based on the heat capacities measurements in the temperature range from 80 to 380 K. The thermal stability of the compound was further investigated by DSC and TG. From the DSC curve an intensive exothermic peak assigned to the thermal decomposition of the compound was observed in the range of 445-590 K with the peak temperature of 505 K. Subsequently, a slow exothermic effect appears when the temperature is higher than 590 K, which is probably due to the further decomposition of the compound. The TG curve indicates the mass loss of the sample starts at about 440 K, which corresponds to the decomposition of the sample.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号