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Time distribution of adsorption entropy of gases on heterogeneous surfaces by reversed-flow gas chromatography.

The reversed-flow gas chromatography (RF-GC) technique has been applied to measure the adsorption entropy over time, when gaseous pentane is adsorbed on the surface of two solids (gamma-alumina and a silica supported rhodium catalyst) at 393.15 and 413.15K, respectively. Utilizing experimental chromatographic data, this novel methodology also permits the simultaneous measurement of the local adsorption energy, epsilon, local equilibrium adsorbed concentration, c(s)(*), and local adsorption isotherm, theta(p, T, epsilon) in a time resolved way. In contrast with other inverse gas chromatographic methods, which determine the standard entropy at zero surface coverage, the present method operates over a wide range of surface coverage taking into account not only the adsorbate-adsorbent interaction, but also the adsorbate-adsorbate interaction. One of the most interesting observations of the present work is the fact that the interaction of n-pentane is spontaneous on the Rh/SiO(2) catalyst for a very short time interval compared to that on gamma-Al(2)O(3). This can explain the different kinetic behavior of each particular gas-solid system, and it can be attributed to the fact that large amounts of n-C(5)H(12) are present on the active sites of the Rh/SiO(2) catalyst compared to those on gamma-Al(2)O(3), as the local equilibrium adsorbed concentration values, c(s)(*), indicate.

Adsorption↗

Monitoring and modelling of biosphere/atmosphere exchange of gases and aerosols in Europe.

Monitoring and modelling of deposition of air pollutants is essential to develop and evaluate policies to abate the effects related to air pollution and to determine the losses of pollutants from the atmosphere. Techniques for monitoring wet deposition fluxes are widely applied. A recent intercomparison experiment, however, showed that the uncertainty in wet deposition is relatively high, up to 40%, apart from the fact that most samplers are biased because of a dry deposition contribution. Wet deposition amounts to about 80% of the total deposition in Europe with a range of 10-90% and uncertainty should therefore be decreased. During recent years the monitoring of dry deposition has become possible. Three sites have been operational for 5 years. The data are useful for model development, but also for model evaluation and monitoring of progress in policy. Data show a decline in SO(2) dry deposition, whereas nitrogen deposition remained constant. Furthermore, surface affinities for pollutants changed leading to changes in deposition. Deposition models have been further developed and tested with dry deposition measurements and total deposition measurements on forests as derived from throughfall data. The comparison is reasonable given the measurement uncertainties. Progress in ozone surface exchange modelling and monitoring shows that stomatal uptake can be quantified with reasonable accuracy, but external surface uptake yields highest uncertainty.

Aerosols↗

Adsorption properties of gases on mesoporous chromium silicate.

The properties of nitrogen, carbon dioxide, and nitrogen dioxide adsorption onto mesoporous chromium silicates were studied by measurements of both the adsorption isotherms and the IR spectra. The pore sizes of two types of chromium silicates, Cr-FSM-16 (Si/Cr=170 (Cr-FSM-16 [170]) and 390 (Cr-FSM-16 [390])), which contain different amount of Cr, were 2.75 nm. BET surface areas of Cr-FSM-16 were 590 m2/g and they were smaller than that onto FSM-16. The initial heat of adsorption of nitrogen onto Cr-FSM-16 was higher than that onto FSM-16. But the initial heat of adsorption of carbon dioxide onto Cr-FSM-16 was smaller than that onto FSM-16. These results indicated that Cr in Cr-FSM-16 decreased adsorption interaction with carbon dioxide. When nitrogen dioxide was adsorbed on FSM-16 and Cr-FSM-16 at 303 K under no light, an absorption band of nitrogen monoxide adsorbed was measured by IR spectroscopy. This decomposition of nitrogen dioxide by FSM-16 and Cr-FSM-16 was caused by SiOH and Cr, respectively.

Adsorption↗

Effect of vessel size and shape on experimental flammability limits of gases.

The flammability limits of methane and propane have been measured using cylindrical vessels of various sizes and one spherical vessel. An ac discharge ignition method has been employed. For a cylindrical vessel of small diameter with a large height, the flammability limits are primarily determined by the quenching effect of the wall. For cylindrical vessels of smaller heights, the experimental flammability limits are affected by hot gas accumulation at the vessel ceiling, unburned gas heating, self heating of the incipient flame by the reflection both from walls and ceiling, and the quenching effect of the walls. If the vessel size is large enough so that all these effects become negligible, the experimental values of flammability limits may approach to the values that would be obtained in free space. In order to approach this condition for a cylindrical vessel, it is desirable to use a container at least 30 cm in diameter and 60 cm in height. For comparison purpose, the measurement has also been done using ASHRAE type 12l spherical flask.

Equipment Design↗

Kinetics of the removal of mono-chlorobenzene vapour from waste gases using a trickle bed air biofilter.

The performance of a trickle bed air biofilter (TBAB) in the removal of mono-chlorobenzene (MCB) was evaluated in concentrations varying from 0.133 to 7.187 g m(-3) and at empty bed residence time (EBRT) varying from 37.7 to 188.52 s. More than 90% removal efficiency in the trickle bed air biofilter was achieved for the inlet MCB concentration up to 1.069 g m(-3) and EBRT less than 94.26 s. The trickle bed air biofilter was constructed with coal packing material, inoculated with a mixed consortium of activated sludge obtained from sewage treatment plant. The continuous performance of the removal of MCB in the trickle bed air biofilter was monitored for various gas concentrations, gas flow rates, and empty bed residence time. The experiment was conducted for a period of 75 days. The trickle bed air biofilter degrading MCB with an average elimination capacity of 80 g m(-3) h(-1) was obtained. The effect of starvation was also studied. After starvation period of 8 days, the degradation was low but recovered within a short period of time. Using macrokinetic determination method, the Michaelis-Menten kinetic constant K(m) and maximum reaction rate, r(max) evaluated as 0.121 g m(-3) s(-1) and 7.45 g m(-3), respectively.

Air Pollution↗

Spatial and temporal visualization of gases and vapours in air using computed tomography. Numerical studies.

Numerical studies were performed to evaluate a new method for human exposure assessment and source monitoring, based upon optical remote sensing (ORS) and computed tomography (CT). With an ORS-CT system, two-dimensional maps of chemical concentrations in air, with good spatial and temporal resolution, can be created over a confined space such as a workplace room. The ORS-CT system was evaluated using 15 simulated test maps that model the generation and dispersion of contaminant plumes over time. A program simulated field measurements from these maps assuming different remote sensing scan times. Using these measurements, reconstructed maps were generated and compared with original maps. Qualitative and quantitative methods were used to evaluate the effect on reconstruction quality of sample time, number of iterations used by the maximum likelihood expectation maximization reconstruction algorithm and sample density. For this study, scanning an entire room in 10 min was adequate for exposure evaluation, source monitoring and leak detection.

Air Pollutants↗

Prevention of water vapour adsorption by carbon molecular sieves in sampling humid gases.

The water uptake by the solid sorbents Carbosieve S-III, Carboxen 569, 1000 and 1001, all of which are used for sampling of volatile organic compounds from the atmosphere. was examined using a direct experimental approach. The content of retained water is affected both by the trap temperature and the initial water vapour concentration in the sampled gas. Two different adsorption mechanism are operative. At low relative humidities (RH) only active polar centres are involved. This adsorption is so weak that negative water interferences can easily be managed. Another mechanism, the micropore volume filling, involves substantial amounts of water, becomes operative once the threshold value for relative humidity (RHth) is surpassed. RHth is 45+/-3% for Carboxen 1000 decreasing to 35+/-3% for the three other sorbents studied. A novel but simple strategy was tested for water management: moderate heating of the trap during the sampling (a warm trap method). The temperature elevation required depends on the RHth characteristic for the specific sorbent, and RH and the temperature of the sampled gas. Usually the 5-15 degrees C elevation is sufficient; only under extreme RH conditions is an elevation of 20 degrees C necessary. The diagrams are given to determine this elevation. Since the sample RH is significantly decreased at an elevated temperature the negative effect of water uptake on the safe sampling volume is alleviated. Consequently the sampled gas volume can be as large as desired which decreases detection limits.

Adsorption↗

Determination of the amount of wash amines and ammonium ion in desulfurization products of process gases and results of related studies.

This paper describes a method for the determination of the so-called wash amines and their degradation products, including ammonium ions, in process liquids and wastewater generated during the desulfurization of hydrogen sulfide gas in the process of crude oil refining and also reports the results of related studies. Ion-exchange liquid chromatography employing an inexpensive cation-exchange HPLC column and refractometric detection was used. The results obtained were compared with those obtained by potentiometric titration. Analytical characteristics and a description of the developed procedure are provided. Examples of the results of routine determinations of amines, their degradation products and ammonium ions in process liquids and wastewater are given.

Amines↗

Solubility properties in polymers and biological media. II. A new method for the characterisation of the adsorption of gases and vapours on solids.

Henry's constants at zero solute pressure have been determined by the gas chromatographic peak shape method for twenty-two solutes on four adsorbents (Rohm and Haas Ambersorb XE-348F carbonaceous adsorbent at 323 and 373 K, Sutcliffe Speakman 207A and 207C at 323 K, and Calgon Filtrasorb activated carbon at 323 K). The limiting values of log KH have been analysed in terms of solute dipolarity (pi 2*), solute hydrogen-bond acidity (alpha 2), and basicity (beta 2), and a new solute parameter (log L16), the solute Ostwald absorption coefficient on eta-hexadecane. The multiple linear regression equation, SP = SP0 + l.log L16 + s(pi 2* + d delta 2) + a alpha 2 + b beta 2 where in this instance SP = -log KH, can be used to identify the nature of the solute-adsorbent interactions, and to predict further values of log KH. For the solutes and solids we have studied, only the l.log L16 term is statistically significant, and hence--log KH is proportional to l.log L16. It is concluded that interactions between the gaseous solutes (that include alcohols and amines) and the four adsorbents involve just general dispersion forces.

Acetonitriles↗