Optochemical Sensor for Ammonia Based on a Lipophilized pH Indicator in a Hydrophobic Matrix

Abstract

An optical sensor for the determination of ammonia in water based on ion pairing has been investigated. A pH-sensitive dye is immobilized as an ion pair in a silicone matrix. The colour of the dye changes from yellow to blue depending on the concentration of ammonia in the sample solution. This change is reversible. The concentration of ammonia can be determined by measuring the transmittance at a given wavelength.

All measurements were performed with a dual-beam optical meter. The measurement range was from 5.9 × 10^?7 to 1 × 10^?3 M (0.01 to 17 mg/l) in 0.1 M phosphate buffer of pH 8. The detection limit was 10 μg/l. The response times at a flow rate of 2.5 ml/min were 4 min for t₉₀ and 10 min for t₁₀₀ at a change from 41.9 to 82.5 μM ammonia and 12 min for t₉₀ and 48 min for t₁₀₀ at a change from 160 to 0 μM ammonia. The operational lifetime of the ammonia sensor was limited to a period of a few days only. A continuous decrease in baseline signal and relative signal change was observed over the whole measurement. The storage stability was more than 10 months (dry). With respect to possible application of the ammonia sensor to environmental analysis, the influence of pH, typical interferences, such as amines and various detergents on the sensor response was investigated. No interference due to pH was observed in the range from pH 5 to pH 9. With methyl- and ethylamine the response was not completely reversible. The sensor was affected by cationic detergents, but not by anionic or neutral detergents.     

The gas phase oxidation of HCOOH by Cl and NH2 radicals. Proton coupled electron transfer versus hydrogen atom transfer*

ABSTRACT

The reaction of formic acid (HCOOH) with chlorine atom and amidogen radical (NH₂) have been investigated using high level theoretical methods such BH&HLYP, MP2, QCISD, and CCSD(T) with the 6–311?+?G(2df,2p), aug-cc-pVTZ, aug-cc-pVQZ and extrapolation to CBS basis sets. The abstraction of the acidic and formyl hydrogen atoms of the acid by the two radicals has been considered, and the different reactions proceed either by a proton coupled electron transfer (pcet) and hydrogen atom transfer (hat) mechanisms. Our calculated rate constant at 298?K for the reaction with Cl is 1.14?×?10^?13?cm³?molecule^?1?s^?1 in good agreement with the experimental value 1.8?±?0.12/2.0?×?10^?13?cm³?molecule^?1?s^?1 and the reaction proceeds exclusively by abstraction of the formyl hydrogen atom, via hat mechanism, producing HOCO+ClH. The calculated rate constant, at 298?K, for the reaction with NH₂ is 1.71?×?10^?15?cm³?molecule^?1?s^?1, and the reaction goes through the abstraction of the acidic hydrogen atom, via a pcet mechanism, leading to the formation of HCOO+NH₃.     

An optimized method for the determination of volatile and semi-volatile aldehydes and ketones in ambient particulate matter

A method has been developed to measure aldehydes and ketones associated with atmospheric particles. Carbonyl compounds from particulate material collected on Teflon-coated glass-fiber filters were simultaneously extracted and derivatized with an appropriate 2,4-dinitrophenylhydrazine (2,4-DNPH) solution. The efficiency of this procedure utilizing various 2,4-DNPH concentrations and solvent compositions was studied for 13 carbonyl compounds of atmospheric importance. These include formaldehyde, acetaldehyde, acetone, dicarbonyls such as glyoxal and methylglyoxal, and biogenic carbonyls such as pinonaldehyde and nopinone. An extraction solution containing 3 × 10^?2 M 2,4-DNPH, in 60% acetonitrile/40% water, and pH 3 was most efficient in extracting and derivatizing these aldehydes and ketones (83-100% recovery). Improved sample enrichment and 2,4-DNPH purification methods were developed that afforded detection limits of 0.009-5.6 ng m^?3. The relative standard deviation for replicate analyses were 1.9-10.1%. Carbonyl compounds in ambient particulate samples were quantified during a recent field study. Median values for nine carbonyl species ranged from 0.01-33.9 ng m^?3 during the study.     

An improved Sampling Strategy for the Measurement of VOCs in Air,Based on Cooled Sampling and Analysis by Thermodesorption-GC-MS/FID

Abstract

Reliable and comprehensive sampling methods are required to obtain accurate data for VOC concentrations in air samples. The major drawback of the adsorption tube sampling method, widely employed in environmental studies, is the fact that C₂ compounds are usually not trapped quantitatively.

The focus of this work was thus to improve sampling based on adsorption tubes packed with Molsieve and Carbosieve. To improve the sampling efficiency for the C₂ compounds, a cooling device, based on Peltier cooling was constructed, which could be operated at a temperature down to ?30°C.

Experiments under laboratory and field conditions were carried out to study the influence of the sampling temperatuie on the recovery of ethane and ethene as the most volatile VOCs. The results clearly demonstrate the need for a cooled sampling device for the analysis of C₂ compounds in air. Under the investigated conditions, the recoveries with ambient temperature sampling were only in the range of 38–46% for ethane and 33–59% for ethene respectively, in comparison to the cooled sampling device. These findings are only valid for the described conditions and can change significantly with temperature and concentration. A generalisation of the recovery is thus very difficult to give.

The use of the sampling device for a field study is reported, where samples were collected simultaneously at three different altitudes in a diurnal profile on the slope of the Schulterberg mountain in Tyrol (Austria).     

The lifetime of CFC substitutes studied by a network trained with chaotic mapping modified genetic algorithm and DFT calculations

The hydrohaloalkanes have attracted much attention as potential substitutes of chlorofluorocarbons (CFCs) that deplete the ozone layer and lead to great high global warming. Having a short atmospheric lifetime is very important for the potential substitutes that may also induce ozone depletion and yield high global warming gases to be put in use. Quantitative structure–activity relationship (QSAR) studies were presented for their lifetimes aided by the quantum chemistry parameters including net charges, Mulliken overlaps, E _HOMO and E _LUMO based on the density functional theory (DFT) at B3PW91 level, and the C-H bond dissociation energy based on AM1 calculations. Outstanding features of the logistic mapping, a simple chaotic system, especially the inherent ability to search the space of interest exhaustively have been utilized. The chaotic mapping aided genetic algorithm artificial neural network training scheme (CGANN) showed better performance than the conventional genetic algorithm ANN training when the structure of the data set was not favorable. The lifetimes of HFCs and HCs appeared to be greatly dependent on their energies of the highest occupied molecular orbitals. The perference of the RMSRE comparing to RMSE as objective function of ANN training was better for the samples of interest with relatively short lifetimes. C₂H₆ and C₃H₈ as potential green substitutes of CFCs present relatively short lifetimes.     

Side-lobeless far-field spectrum of a short pulse from a circular aperture with Gaussian form of transmittance

The spectrum change of a Gaussian pulse in the far field is studied with the Fresnel diffraction integral when it is incident on an aperture with Gaussian form transmittance. It is found that the side-lobes of the diffracted spectral intensity, which exist in a normal circular aperture with unit transmittance, can be eliminated completely under such a condition. Also, the red shift and blue shift of the spectral intensity maximum of the incident pulse are presented.     

The effect of terminal chain modifications on the mesomorphic properties of 4,4′-disubstituted diphenyldiacetylenes

The typical sidewalls produced in the fabrication of protrusion electrodes are proposed to create a low voltage (4.5 V_rms) and high transmittance (93%) blue-phase liquid crystal display (BP-LCD). The tilted electrodes produce a strong horizontal electrical field that reduces the operating voltage considerably. The common problem of the ‘dead zones’ is solved by reflecting the light onto the electrodes. In order to estimate the phase retardation of the reflected light, a ray tracing simulation program for anisotropic mediums has been developed. The proposed device is more competitive than vertical field switching based BP-LCD and also, has the advantages of protruded in-plane-switching structures. These facts make this technology a potential candidate for the next generation of BP-LCDs.     

Application of the Combustion Method in a Closed Flask to the Lead Determination in Atmospheric Aerosols

Abstract

The destruction of the filter for metal determination in atmospheric aerosols is an important step in the analysis. Nowadays the decomposition of this kind of sample has not been completely solved, so it is interesting to study new methods for filter sample attack. In the present work the application of the combustion method in a closed flask for mixed cellulose esters filter decomposition for lead determination is proposed. For this purpose optimum operating conditions as stopper flask design, sample size, flask volume, shaking time and volume and concentration of absorbing solution are established, and accuracy and precision of the proposed method using AAS for the measurements is given. The results obtained by the closed flask combustion are compared with those found by wet attack with HNO₃. The method proposed is rapid, has low reagent contamination and no loss of lead by volatilization or by amalgamation occurs. This method shows an accuracy and a precision in good agreement with the standard method.     

Fitting formula for the injection volume of a gas chromatograph for radio‐xenon sampling in the lower troposphere

GC is usually used for xenon concentration and radon removal in the International Monitoring System of the Comprehensive Nuclear‐Test‐Ban Treaty. In a gas chromatograph, the injection volume is defined to calculate the column capacity. In this paper, the injection volume was investigated and a fitting formula for the injection volume was derived and discussed subsequently. As a consequence, the xenon injection volume exponentially decreased with the column temperature increased, but exponentially increased as the flow rate increased.     

Glow Discharge Characteristics of Hollow Needle-Plate Electrode in Atmospheric Pressure ArgonSCIEI北大核心CSCD

Atmosphere pressure uniform plasma has the broad application prospect in the industrial field. Using hollow needle cathode - plate anode device excited by direct-current voltage, a uniform and stable glow discharge is generated at atmospheric pressure in ambient air with argon used as working gas. The influence of the experimental parameters (including gas flow rate and the gas gap width) on discharge has been investigated by optical method. It can be found that a glow-discharge plasma column can bridge the two electrodes. The plasma column is uniform, and no filaments can be discerned. Near the plate electrode, the diameter of the plasma column is largest of all positions. The maximal diameter of the plasma column increases with increasing the discharge current or the gas flow rate. Through electrical method, the voltage-current characteristic has been investigated. It has been found that the discharge voltage decreases with increasing the current which is similar with the characteristic of glow discharge in low pressure. It increases with increasing the gas gap width or the gas flow rate. By analyzing the optical emission spectrum scanning from 330 to 450 nm emitted from the direct-current glow discharge, the molecular vibrational temperature and the intensity ratio of spectral lines I-391.4/I-337.1 have been investigated as functions of the gas flow rate and gas gap width. Results indicate that both the vibrational temperature and the intensity ratio of spectral lines I-391.4/I-337.1 decrease with increasing the gas flow rate or the gas gap width. In addition, the molecular vibrational temperature and the intensity ratio of spectral lines I-391.4/I-337.1 have been investigated in spatial resolution along the direction of gas flow(plasma column axial), and give a qualitative analysis as well. It is found that the vibrational temperature and the average electron energy increase with increasing the distance from the hollow needle cathode. These results are important to the industrial applications of glow discharge.