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1.
We measured at 296 K the rotational line strengths and pressure-broadening coefficients for the 1.27-mum, a (1)D(g)-X (3)?(g)(-), v = 0-0 band of O(2) with a Fourier transform infrared spectrometer using an optical path length of 84 m, a spectral resolution of 0.01 cm(-1), and sample pressures between 13 and 104 kPa. The integrated band strength is 7.79(17) x 10(-6) m(-2) Pa(-1) [7.89(17) x 10(-5) cm(-2) atm(-1)], and the Einstein Acoefficient for spontaneous emission is 2.237(51) x 10(-4) s(-1), which corresponds to an upper-state1/e lifetime of 1.24(3) h. The pressure-broadening coefficients decrease with increasing N and range from 19 to 38 MHz/kPa (FWHM). The mean value for the transitions studied is 30.3(21) MHz/kPa [0.1024(71) cm(-1)/atm] (FWHM). The Einstein A coefficient determined here is in good agreement with the widely accepted value of 2.58 x 10(-4) s(-1) initially obtained by Badgeret al. [J. Chem. Phys. 43, 4345 (1965)] more than 30 years ago. The standard uncertainties given above are one standard deviation.  相似文献   

2.
The use of ionic liquids (ILs) as a solvent for thermal lens measurements has been investigated. It was found that ILs provide a better medium for thermal lens measurements than water. Specifically, not only the ILs offer at least 20 times higher sensitivity than water but that the enhancement can be appropriately adjusted by changing either the cation or the anion of the ILs. For example, the sensitivity in [BMIm]+[Tf2N]- is approximately 26 times higher than in water. It can be increased up to 31 times by changing the anion to [PF6]- (i.e., [BMIm]+[PF6]-) or to 35 times by changing the cation to [OMIm]+ (i.e., [OMIm]+[Tf2N]-). In fact, the sensitivity of thermal lens measurements in ILs is comparable to those in volatile organic solvents such as benzene, carbon tetrachloride, and hexane. However, the ILs are more desirable as they have virtually no vapor pressure. Furthermore, additional sensitivity enhancement (up to 42 times higher than that in water) can be achieved by simply adding surfactants into the ILs. Based on the thermal conductivity (k) and dn/dT values, calculated from the measured thermal time constant tc and thermal lens strength theta, it is evident that the observed sensitivity enhancement by the ILs is due to their relatively better thermooptical properties. More specifically, the enhancement is due not to the relatively modest lowering of the thermal conductivity but rather to the substantial increase in their dn/dT values. Because of the relationship between dn/dT and drho/dT, it is expected that ILs can serve as an attractive and superior solvent not only for thermal lens measurements but also for other photothermal and photoacoustic techniques as well. Also equally important is the fact that the thermal lens technique in particular and photothermal techniques, in general, can offer a unique means to determine themooptical and thermal physical properties of the ILs (e.g., thermal conductivity, thermal diffusivity, and phase transition temperatures). This type of data is currently lacking but is of extreme importance for implementing ILs as a solvent in various industrial applications.  相似文献   

3.
Chemical warfare agent detection using MEMS-compatible microsensor arrays   总被引:1,自引:0,他引:1  
Microsensors have been fabricated consisting of TiO/sub 2/ and SnO/sub 2/ sensing films prepared by chemical vapor deposition (CVD) on microelectromechanical systems array platforms. Response measurements from these devices to the chemical warfare (CW) agents GA (tabun), GB (sarin), and HD (sulfur mustard) at concentrations between 5 nmol/mol (ppb) and 200 ppb in dry air, as well as to CW agent simulants CEES (chloroethyl ethyl sulfide) and DFP (diisopropyl fluorophosphate) between 250 and 3000 ppb, are reported. The microsensors exhibit excellent signal-to-noise and reproducibility. The temperature of each sensor element is independently controlled by embedded microheaters that drive both the CVD process (375/spl deg/C) and sensor operation at elevated temperatures (325/spl deg/C-475/spl deg/C). The concentration-dependent analyte response magnitude is sensitive to conditions under which the sensing films are grown. Sensor stability studies confirm little signal degradation during 14 h of operation. Use of pulsed (200 ms) temperature-programmed sensing over a broad temperature range (20/spl deg/C-480/spl deg/C) enhances analyte selectivity, since the resulting signal trace patterns contain primarily kinetic information that is unique for each agent tested.  相似文献   

4.
Bak J 《Applied optics》2002,41(15):2840-2846
Monitoring the amount of gaseous species in the atmosphere and exhaust gases by remote infrared spectroscopic methods calls for the use of a compilation of spectral data, which can be used to match spectra measured in a practical application. Model spectra are based on time-consuming line-by-line calculations of absorption cross sections in databases by use of temperature as input combined with path length and partial and total pressure. It is demonstrated that principal component analysis (PCA) can be used to compress the spectrum of absorption cross sections, which depend strongly on temperature, into a reduced representation of score values and loading vectors. The temperature range from 300 to 1000 K is studied. This range is divided into two subranges (300-650 K and 650-1000K), and separate PCA models are constructed for each. The relationship between the scores and the temperature values is highly nonlinear. It is shown, however, that because the score-temperature relationships are smooth and continuous, they can be modeled by polynomials of varying degrees. The accuracy of the data compression method is validated with line-by-line-calculated absorption data of carbon monoxide and water vapor. Relative deviations between the absorption cross sections reconstructed from the PCA model parameters and the line-by-line-calculated values are found to be smaller than 0.15% for cross sections exceeding 1.27 x 10(-21) cm(-1) atm(-1) (CO) and 0.20% for cross sections exceeding 4.03 x 10(-21) cm(-1) atm(-1) (H2O). The computing time is reduced by a factor of 10(4).  相似文献   

5.
A high-temperature technique was developed for vapor pressure determination of solid and liquid γ-La2S3 (we called it the boiling point technique). Melting temperatures and total vapor pressures were measured for incongruently vaporizing γ-La2S3 at 1853–2210 K and 0.3–3.0 atm pressures. Having compared the slopes of the log p(S2) versus 1/T plots measured by various techniques, we recommend the equation log p(S2) [atm] = (6.31 ± 0.15) ? (12720±310)T ?1 for T = 1021–2013 K as the most reliable for practical use.  相似文献   

6.
The need for the detection of chemical warfare agents (CWAs) is no longer confined to battlefield environments because of at least one confirmed terrorist attack, the Tokyo Subway [Emerg. Infect. Dis. 5, 513 (1999)] in 1995, and a suspected, i.e., a false-alarm of a CWA in the Russell Senate Office Building [Washington Post, 9 February 2006, p. B01]. Therefore, detection of CWAs with high sensitivity and low false-alarm rates is considered an important priority for ensuring public safety. We report a minimum detection level for a CWA simulant, dimethyl methyl phosphonate (DMMP), of <0.5 ppb (parts in 10(9)) by use of a widely tunable external grating cavity quantum cascade laser and photoacoustic spectroscopy. With interferents present in Santa Monica, California street air, we demonstrate a false-alarm rate of 1:10(6) at a detection threshold of 1.6 ppb.  相似文献   

7.
Vacuum-outlet GC with atmospheric-pressure air as the carrier gas is implemented at outlet pressures up to 0.8 atm using a low-dead-volume polymer-coated surface acoustic wave (SAW) detector. Increases in the system outlet pressure from 0.1 to 0.8 atm lead to proportional increases in detector sensitivity and significant increases in column efficiency. The latter effect arises from the fact that optimal carrier gas velocities are lower in air than in more conventional carrier gases such as helium or hydrogen due to the smaller binary diffusion coefficients of vapors in air. A 12-m-long, 0.25-mm-i.d. tandem column ensemble consisting of 4.5-m dimethyl polysiloxane and 7.5-m trifluoropropylmethyl polysiloxane operated at an outlet pressure of 0.5 atm provides up to 4 x 10(4) theoretical plates and a peak capacity of 65 (resolution, 1.5) for a 3-min isothermal analysis. At 30 degrees C, mixtures of vapors ranging in vapor pressure from 8.6 to 76 Torr are separated in this time frame. The SAW detector cell has an internal volume of < 2 microL, which allows the use of higher column outlet pressures with minimal dead time. The sensor response is linear with solute mass over at least 2-3 decades and provides detection limits of 20-50 ng for the vapors tested. The combination of atmospheric-pressure air as carrier gas, modest operating pressures, and SAW sensor detection is well-suited for field instrumentation since it eliminates the need for support gases, permits smaller, low-power pumps to be used, and provides sensitivity to a wide range of vapor analytes.  相似文献   

8.
T Ueda  N Kato  A Takemura  H Koishi  A Morinaga 《Applied optics》2012,51(20):4660-4666
A tunable multimode unidirectional traveling-wave Ti:sapphire laser was developed to measure in situ the atmospheric absorption spectra using intracavity absorption spectroscopy. The effective absorption path length was 2100 km. O2 and H2O vapor lines in atmosphere with absorption coefficients of 10(-6)-10(-8) cm(-1) were measured with uncertainties <5%, and the absorption coefficients were in agreement with those estimated from the HITRAN database. By tuning the wavelength, a weak absorption line with an absorption coefficient of 10(-9) cm(-1) was measured with a sensitivity of 2×10(-10) cm(-1). The sensitivity was limited by the residual parasitic variation that appeared in the spectrum.  相似文献   

9.
The Gas Metrology Group at the National Institute of Standards and Technology was tasked, by a congressional climate change act, to support the atmospheric measurement community through standards development of key greenhouse gases. This paper discusses the development of a methane (CH(4)) primary standard gas mixture (PSM) suite to support CH(4) measurement needs over a large amount-of-substance fraction range 0.3-20,000 μmol mol(-1), but with emphasis at the atmospheric level 300-4000 nmol mol(-1). Thirty-six CH(4) in dry air PSMs were prepared in 5.9 L high-pressure aluminum cylinders with use of a time-tested gravimetric technique. Ultimately 14 of these 36 PSMs define a CH(4) standard suite covering the nominal ambient atmospheric range of 300-4000 nmol mol(-1). Starting materials of pure CH(4) and cylinders of dry air were exhaustively analyzed to determine the purity and air composition. Gas chromatography with flame-ionization detection (GC-FID) was used to determine a CH(4) response for each of the 14 PSMs where the reproducibility of average measurement ratios as a standard error was typically (0.04-0.26) %. An ISO 6134-compliant generalized least-squares regression (GenLine) program was used to analyze the consistency of the CH(4) suite. All 14 PSMs passed the u-test with residuals between the gravimetric and the GenLine solution values being between -0.74 and 1.31 nmol mol(-1); (0.00-0.16)% relative absolute. One of the 14 PSMs, FF4288 at 1836.16 ± 0.75 nmol mol(-1) (k = 1) amount-of-substance fraction, was sent to the Korea Research Institute of Standards and Science (KRISS), the Republic of Korea's National Metrology Institute, for comparison. The same PSM was subsequently sent to the National Oceanic and Atmospheric Administration (NOAA) for analysis to their standards. Results show agreement between KRISS-NIST of +0.13% relative (+2.3 nmol mol(-1)) and NOAA-NIST of -0.14% relative (-2.54 nmol mol(-1)).  相似文献   

10.
Near-infrared (NIR) spectrometry was successfully used for the non-invasive and in situ determination of concentrations and structure of water absorbed by room-temperature ionic liquids (RTILs). It was found that RTILs based on 1-butyl-3-methylimidazolium, namely, [BuMIm]+ [BF4]-, [BuMIm]+ [bis((trifluoromethyl)sulfonyl)amide, or Tf2N]- and [BuMIm]+ [PF6]-, are hydroscopic and can quickly absorb water when they are exposed to air. Absorbed water interacts with the anions of the RTILs, and these interactions lead to changes in the structure of water. Among the RTILs studied, [BF4]- provides the strongest interactions and [PF6]- the weakest. In 24 hours, [Bu-MIm]+ [BF4]- can absorb up to 0.320 M of water, whereas [Bu-MIm]+ [PF6]- can only absorb 8.3 x 10(-2) M of water. It seems that higher amounts of water can be absorbed when the anion of the RTIL can strongly interact and hence stabilize absorbed water molecules by forming hydrogen bonds with them or inducing hydrogen bonds among water molecules. More importantly, the NIR technique can be sensitively used for the noninvasive, in situ determination of absorbed water in RTILs, without any pretreatment, and at limits of detection as low as 3.20 x 10(-3) M.  相似文献   

11.
Effect of air in the thermal decomposition of 50 mass% hydroxylamine/water   总被引:1,自引:0,他引:1  
This paper presents experimental measurements of 50 mass% hydroxylamine (HA)/water thermal decomposition in air and vacuum environments using an automatic pressure tracking adiabatic calorimeter (APTAC). Overall kinetics, onset temperatures, non-condensable pressures, times to maximum rate, heat and pressure rates versus temperature, and mixture vapor pressures for the experiments in vacuum were similar when compared to the corresponding data for HA decomposition in air. Determined was an overall activation energy of 119+/-8 kJ/mol (29+/-2 kcal/mol), which is low compared to 257 kJ/mol (61.3 kcal/mol) required to break the H(2)N-OH bond reported in the literature. The availability of oxygen from air did not affect detected runaway decomposition products, which were H(2), N(2), N(2)O, NO, and NH(3), for samples run in vacuum or with air above the sample. A delta H(rxn) of -117 kJ/mol (28 kcal/mol) was estimated for the HA decomposition reaction under runaway conditions.  相似文献   

12.
The first passive sampling device for the determination of airborne peroxyacetic acid (PAA) is presented. 2-([3-{2-[4-Amino-2-(methylsulfanyl)phenyl]-1-diazenyl}phenyl]sulfonyl)-1-ethanol (ADS) is used to impregnate glass fiber filters, and the reagent is oxidized by PAA to the corresponding sulfoxide ADSO. After elution of the filters, ADS and ADSO are separated by reversed-phase HPLC and detected by UV/visible absorbance. Limit of detection is 30 ppb, limit of quantification is 90 ppb (for 30 min sampling), and the linear range comprises 2 orders of magnitude. Thorough investigations were carried out with respect to the selectivity of the method toward hydrogen peroxide, and air samples were analyzed successfully after disinfection of a laboratory area.  相似文献   

13.
A narrow-linewidth pulsed alexandrite laser has been greatly modified for improved spectral stability in an aircraft environment, and its operation has been evaluated in the laboratory for making water-vapor differential absorption lidar measurements. An alignment technique is described to achieve the optimum free spectral range ratio for the two étalons inserted in the alexandrite laser cavity, and the sensitivity of this ratio is analyzed. This technique drastically decreases the occurrence of mode hopping, which is commonly observed in a tunable, two-intracavity-étalon laser system. High spectral purity (> 99.85%) at 730 nm is demonstrated by the use of a water-vapor absorption line as a notch filter. The effective cross sections of 760-nm oxygen and 730-nm water-vapor absorption lines are measured at different pressures by usingthis laser, which has a finite linewidth of 0.02 cm(-1) (FWHM). It is found that for water-vapor absorption linewidths greater than 0.04 cm(-1) (HWHM), or for altitudes below 10 km, the laser line can be considered monochromatic because the measured effective absorption cross section is within 1% of the calculated monochromatic cross section. An analysis of the environmental sensitivity of the two intracavity étalons is presented, and a closed-loop computer control for active stabilization of the two intracavity étalons in the alexandrite laser is described. Using a water-vapor absorption line as a wavelength reference, we measure a long-term frequency drift (≈ 1.5 h) of less than 0.7 pm in the laboratory.  相似文献   

14.
Water-vapor absorption features near 7117, 7185, and 7462 cm(-1) were probed at pressures to 65 atm (1 atm = 760 Torr) and temperatures to 1800 K in shock-heated mixtures of H(2)O in N(2) and Ar with a diode-laser source. Calculated absorbances based on Voigt line shapes and measured line parameters were in good agreement, within 10%, with measured absorbances at 7185.4 and 7117.4 cm(-1). We obtained temperature-dependent N(2) and Ar shift parameters for H(2)O absorption features by shifting the calculated spectra to match the recorded absorption scan. Absorbance simulations based on line parameters from HITRAN and HITEMP were found to be similar over the range of temperatures 600-1800 K and were within 25% of the measurements. The combined use of Toth's [Appl. Opt. 36, 4851 (1994)] line positions and strengths and HITRAN broadening parameters resulted in calculated absorption coefficients that were within 15% of the measurements at all three probed wavelengths.  相似文献   

15.
Experimental data, obtained with an oxygen optical sensor constituted by a polysulfone layer embedding ruthenium(II)(4,7-diphenyl-l,l0-phenanthroline)octylsulfate (Ru(dpp)OS), were rationalized by using the digital simulation technique and generalized for different sensors. The experimental, asymmetric, emission shape was used to define two sensible parameters, ASY (asymmetry factor) and DeltaI(%) (percent variation of emission intensity), to characterize the sensitivity of a generic oxygen optical sensor (represented by the Stern-Volmer constant, K'(sv)). Correlations between ASY and K'(sv) and between DeltaI(%) and K'(sv) were established, and a double working curve was proposed to evaluate with a single light emission measurement the K'(sv) value with the best precision. Sensitive membranes (-log K'(sv) = pK'(sv) < 0.5) had high precision only for low %O(2) values; poorly sensitive membrane (pK'(sv)> 2.5) had constant but scarce precisions in a large %O(2) interval. For %O(2) up to 21% (air) good values are pK'(sv)= 0.5-1.0. In order to monitor a wider %O(2) range, pK'(sv) = 1.5-2.0 are good choices. A simple mathematical model allowed one to estimate the oxygen diffusion coefficient inside the layer, D(O2), and its solubility in the polymer matrix, s(O2), from the simple measurement of the membrane thickness, response time, t(90), and luminescence lifetime. D(O2) = 2 x 10(-8) cm2 s(-1) and s(O2) = 2.2 x 10(-3) mol atm(-1) dm(-3) [corrected] were estimated for our membranes. The proposed working curves gave very good results even with literature data.  相似文献   

16.
The presence of trace water vapor in process gases such as phosphine, used for compound semiconductor epitaxial growth, can negatively affect the optical and electrical properties of the final device. Therefore, sensitive H2O measurement techniques are required to monitor precursor purity and detect unacceptable contamination levels. A commercial cavity ring-down spectrometer that monitors an H2O absorption line at a wavelength of 1392.53 nm was investigated for service in high purity PH3. Spectral parameters such as the line shape of water vapor in the presence of PH3 as well as background features due to PH3 were measured at different pressures and incorporated into the data analysis software for accurate moisture readings. Test concentrations generated with a diffusion vialbased H2O source and dilution manifold were used to verify instrument accuracy, sensitivity, linearity, and response time. H2O readings at 13.2 kPa corresponded well to added concentrations (slope=0.990+/-0.01) and were linear in the tested range (0-52.7 nmol mol-1). The analyzer was sensitive to changes in H2O concentration of 1.3 nmol mol-1 based on 3sigma of the calibration curve intercept for a weighted linear fit. Local PH3 absorption features that could not be distinguished from the H2O line were present in the purified PH3 spectra and resulted in an additional systematic uncertainty of 9.0 nmol mol-1. Equilibration to changing H2O levels at a flow rate of 80 std cm3 min-1 PH3 occurred in 10-30 minutes. The results indicate that cavity ring-down spectroscopy (CRDS) at 1392.53 nm may be useful for applications such as on-line monitoring (and dry-down) of phosphine gas delivery lines or the quality control of cylinder sources.  相似文献   

17.
18.
We demonstrate that silicone block polyimide polymers have an unusually high sensitivity to nonpolar organic vapors, including chlorinated organic solvent vapors. When 0.18-5.34-microm-thick films of silicone block polyimide polymers were deposited onto 10-MHz thickness shear mode (TSM) oscillators, these films were implemented to detect parts-per-billion concentrations of trichloroethylene (TCE) with a detection sensitivity of 0.5-23.5 Hz per 500 ppb of vapor. With a film thickness of 3.4 microm (91.5-kHz frequency shift upon film deposition), optimized for the minimal sensor noise of 0.04 Hz, the calculated detection limit of sensor response (S/N = 3) was 3 ppb of TCE. Detection limits for other chlorinated organic solvent vapors, such as perchloroethylene (PCE), cis-1,2-dichloroethylene (DCE), trans-1,2-DCE, 1,1-DCE, and vinyl chloride (VC) were 0.6, 6, 6, 11, and 13 ppb, respectively. Assuming only the mass-loading response when deposited onto the TSM devices, silicone block polyimide polymers have partition coefficients of over 200 000 to parts-per-billion concentrations of TCE that make them at least 100 times more sensitive than other known polymers for TCE detection. We observed that unlike conventional polyimides, water sensitivity of the new hybrid polyimides is suppressed because of the silicone soft block. Water sensitivity is comparable with the sensor response to nonpolar organic vapors. The high sensitivity and long-term stability of these sensor materials make them attractive for ultrasensitive practical sensors.  相似文献   

19.
Quantitative detection of small volatile organic compounds in ambient air is demonstrated using a combination of continuous wave cavity ring-down spectroscopy (cw-CRDS) and the preconcentration of air samples with an adsorbent trap. The trap consists of a zeolite molecular sieve, selected for efficient trapping of the test compounds ethene (ethylene) and ethyne (acetylene). Upon heating of the trap, these organic compounds desorb into a small-volume ring-down cavity, and absolute concentrations are measured by CRDS at 6150.30 cm(-1) (ethene) and 6512.99 cm(-1) (ethyne) without the need for calibration. The efficiency of the trapping and desorption was tested using commercial standard gas mixtures and shown to be 100% in the case of ethene, whereas some ethyne is retained under the current operating conditions. Samples of indoor and outdoor air were analyzed for ethene content, and measurements were made of mixing ratios as low as 6 ppbv. Removal of water vapor and CO(2) from the air samples prior to trapping was unnecessary, and the selectivity of the trapping, desorption, and spectroscopic detection steps eliminates the need for gas chromatographic separation prior to analysis. With anticipated improvements to the design, measurements of these and other trace atmospheric constituents should be possible on time scales of a few minutes.  相似文献   

20.
We demonstrate a new method for tailoring the selectivity of chemical sensors using semiconductor nanowires (NWs) decorated with metal and metal oxide multicomponent nanoclusters (NCs). Here we present the change of selectivity of titanium dioxide (TiO(2)) nanocluster-coated gallium nitride (GaN) nanowire sensor devices on the addition of platinum (Pt) nanoclusters. The hybrid sensor devices were developed by fabricating two-terminal devices using individual GaN NWs followed by the deposition of TiO(2) and/or Pt nanoclusters (NCs) using the sputtering technique. This paper present the sensing characteristics of GaN/(TiO(2)-Pt) nanowire-nanocluster (NWNC) hybrids and GaN/(Pt) NWNC hybrids, and compare their selectivity with that of the previously reported GaN/TiO(2) sensors. The GaN/TiO(2) NWNC hybrids showed remarkable selectivity to benzene and related aromatic compounds, with no measurable response for other analytes. Addition of Pt NCs to GaN/TiO(2) sensors dramatically altered their sensing behavior, making them sensitive only to methanol, ethanol and hydrogen, but not to any other chemicals we tested. The GaN/(TiO(2)-Pt) hybrids were able to detect ethanol and methanol concentrations as low as 100 nmol mol(-1) (ppb) in air in approximately 100 s, and hydrogen concentrations from 1 μmol mol(-1) (ppm) to 1% in nitrogen in less than 60 s. However, GaN/Pt NWNC hybrids showed limited sensitivity only towards hydrogen and not towards any alcohols. All these hybrid sensors worked at room temperature and are photomodulated, i.e. they responded to analytes only in the presence of ultraviolet (UV) light. We propose a qualitative explanation based on the heat of adsorption, ionization energy and solvent polarity to explain the observed selectivity of the different hybrids. These results are significant from the standpoint of applications requiring room-temperature hydrogen sensing and sensitive alcohol monitoring. These results demonstrate the tremendous potential for tailoring the selectivity of the hybrid nanosensors for a multitude of environmental and industrial sensing applications.  相似文献   

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