Thermal desorption, adsorption

SPME has been utilized for deterrnination of pollutants in aqueous solution by the adsorption of analyte onto stationary-phase coated fused-siUca fibers, followed by thermal desorption in the injection system of a capillary gas chromatograph (34). EuU automation can be achieved using an autosampler. Eiber coated with 7- and 100-p.m film thickness and a nitrogen—phosphoms flame thermionic detector were used to evaluate the adsorption and desorption of four j -triazines. The gc peaks resulting from desorption of fibers were shown to be comparable to those obtained using manual injection. 

Thermal Desorption. Thermal desorption is an innovative treatment that has been appHed primarily to soils. Wastes are heated to temperatures of 200 to 600°C to increase the volatilization of organic contaminants. Volatilized organics in the gas stream are removed by a variety of methods including incineration, carbon adsorption, and chemical reduction. 

Lab method using porous polymer adsorption tube and thermal desorption with gas chromatography Lab method using porous polymer diffusive samplers with thermal desorption and gas chromatography Lab method using pumped acid-coated filters, desorption and liquid chromatography... 

Lab method using pumped porous polymer adsorption tubes, thermal desorption and gas chromatography 40... 

Analysis of Thermal Desorption Data for Adsorption Studies... 

The specific rate of adsorption (in the thermal desorption method, the equivalent term readsorption is used frequently) for the considered model of a homogeneous surface is given by... 

Figure 4.43. Thermal desorption spectra after gaseous oxygen adsorption on a Pt film deposited on YSZ at 673 K and an 02 pressure of 4x 10"6 Torr for 1800 s (7.2 kL) followed by electrochemical O2 supply (I=+15 pA) for various time periods.29-30 Reprinted from ref. 30 with permission from Academic Press.

Figure 4.45. Thermal desorption spectra (bottom) and corresponding catalyst potential variation (top) after electrochemical O2 supply to Ag/YSZ at 260-320°C at various initial potentials Uwr Each curve corresponds to different adsorption temperature and current, thus different values of Uwr, in order to achieve nearly constant initial oxygen coverage.31 Reprinted with permission from Academic Press.

MDHS 1 Acrylonitrile in air Laboratory method using charcoal adsorption tubes and gas chromatography MDHS 2 Acrylonitrile in air Laboratory method using porous polymer adsorption tubes, and thermal desorption with gas chromatographic analysis... 

Measuring the uptake of a gas by a surface as a function of the dose to which the surface is exposed is the most straightforward way to determine a sticking coefficient. In such experiments, great care should be taken to ensure that gas and surface are in thermal equilibrium. In addition, we need to determine the coverage, either by surface sensitive methods (XPS, AES, IR) or by thermal desorption and ensure that adsorption is not accompanied by desorption. 

Desorption is important both because it represents the last step in a catalytic cycle and because it is also the basis of temperature-programmed desorption (TPD), a powerful tool used to investigate the adsorption, decomposition and reaction of species on surfaces. This method is also called thermal desorption spectroscopy (TDS), or sometimes temperature programmed reaction spectroscopy, TPRS (although strictly speaking the method has nothing to do with spectroscopy). 

We have undertaken a series of experiments Involving thin film models of such powdered transition metal catalysts (13,14). In this paper we present a brief review of the results we have obtained to date Involving platinum and rhodium deposited on thin films of tltanla, the latter prepared by oxidation of a tltanliua single crystal. These systems are prepared and characterized under well-controlled conditions. We have used thermal desorption spectroscopy (TDS), Auger electron spectroscopy (AES) and static secondary Ion mass spectrometry (SSIMS). Our results Illustrate the power of SSIMS In understanding the processes that take place during thermal treatment of these thin films. Thermal desorption spectroscopy Is used to characterize the adsorption and desorption of small molecules, In particular, carbon monoxide. AES confirms the SSIMS results and was used to verify the surface cleanliness of the films as they were prepared. 

It can be expected that the electronic structure changes would be reflected by the heats of adsorption of suitable chosen molecules. Indeed, Shek et al (17) report that one maximum in the thermal desorption profile of CO shifts to lower temperatures when the Cu content of alloys increases. If the variations in the entropy changes upon adsorption can be neglected (probably - they can) this would indicate a lower heat of adsorption of CO on alloys than on Pt from abt. 33 Kcal/mol on pure Pt,to 26 Kcal/mol for an alloy with abt. 20% Cu. 

Bertel, E. and Netzer, F.P. (1980) Adsorption of bromine on the reconstructed Au(lOO) surface LEED, thermal desorption and work function measurements. Surface Science, 97, 409-424. 

Solid-phase microextraction (SPME) consists of dipping a fiber into an aqueous sample to adsorb the analytes followed by thermal desorption into the carrier stream for GC, or, if the analytes are thermally labile, they can be desorbed into the mobile phase for LC. Examples of commercially available fibers include 100-qm PDMS, 65-qm Carbowax-divinylbenzene (CW-DVB), 75-qm Carboxen-polydimethylsiloxane (CX-PDMS), and 85-qm polyacrylate, the last being more suitable for the determination of triazines. The LCDs can be as low as 0.1 qgL Since the quantity of analyte adsorbed on the fiber is based on equilibrium rather than extraction, procedural recovery cannot be assessed on the basis of percentage extraction. The robustness and sensitivity of the technique were demonstrated in an inter-laboratory validation study for several parent triazines and DEA and DIA. A 65-qm CW-DVB fiber was employed for analyte adsorption followed by desorption into the injection port (split/splitless) of a gas chromatograph. The sample was adjusted to neutral pH, and sodium chloride was added to obtain a concentration of 0.3 g During continuous... 

The existence of various temperature intervals characterized by predominant manifestation of one of above interactions can be detected from thermal desorption spectra. For instance, the thermal desorption spectrum obtained in [71] for a cleaved ZnO (1010) monocrystal following its interaction with oxygen (Fig. 1.4) indicates the availability of such typical temperature intervals as interval of physical adsorption (a), chemisorption (b), interval of formation of surface defects (c) and, finally, the domain of formation of volume defects (d). 

Acid-base, hydrolysis, hydration, neutralization, oxidation-reduction, polymerization, thermal degradation Adsorption-desorption, precipitation-dissolution, immiscible-phase separation, biodegradation, complexation Acid-base, neutralization, oxidation-reduction (most inorganic and some biologically mediated), adsorption-desorption, precipitation-dissolution, complexation Hydrolysis, oxidation-reduction (biodegradation of anthropogenic inorganics), immiscible-phase separation... 

Fig. 2.3. Thermal desorption spectra after adsorption from the gas phase (a) adsorbed CO on Pt (b) H2 on Pt.

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