TPD

TPD Temperature-programmed desorption [171, 172] The surface is heated and chemisorbed species desorb at characteristic temperatures Characterization of surface sites and desorption kinetics... 

TDS, FDS Thermal desorption spectroscopy. Flash desorption spectroscopy [173] Similar to TPD Similar to TPD... 

TPRS Temperature-programmed Same as TPD reaction spectroscopy [174] Spectroscopy of Emitted Neutrons Same as TPD... 

Temperature-programmed desorption (TPD) is amenable to simple kinetic analysis. The rate of desorption of a molecular species from a uniform surface is given by Eq. XVII-4, which may be put in the form... 

Fig. XVni-10. TPD spectra for H2 on Pd(llO) for varying exposures (in langmuirs). (From Ref. 86.)...

Studies to determine the nature of intermediate species have been made on a variety of transition metals, and especially on Pt, with emphasis on the Pt(lll) surface. Techniques such as TPD (temperature-programmed desorption), SIMS, NEXAFS (see Table VIII-1) and RAIRS (reflection absorption infrared spectroscopy) have been used, as well as all kinds of isotopic labeling (see Refs. 286 and 289). On Pt(III) the surface is covered with C2H3, ethylidyne, tightly bound to a three-fold hollow site, see Fig. XVIII-25, and Ref. 290. A current mechanism is that of the figure, in which ethylidyne acts as a kind of surface catalyst, allowing surface H atoms to add to a second, perhaps physically adsorbed layer of ethylene this is, in effect, a kind of Eley-Rideal mechanism. 

When a molecule adsorbs to a surface, it can remain intact or it may dissociate. Dissociative chemisorption is conmion for many types of molecules, particularly if all of the electrons in the molecule are tied up so that there are no electrons available for bonding to the surface without dissociation. Often, a molecule will dissociate upon adsorption, and then recombine and desorb intact when the sample is heated. In this case, dissociative chemisorption can be detected with TPD by employing isotopically labelled molecules. If mixing occurs during the adsorption/desorption sequence, it indicates that the mitial adsorption was dissociative. 

In this maimer, it can also be seen that molecules will desorb as the surface temperature is raised. This is the phenomenon employed for TPD spectroscopy (see section Al.7.5.4 and section BT25). Note tliat some adsorbates may adsorb and desorb reversibly, i.e. the heats of adsorption and desorption are equal. Other adsorbates, however, will adsorb and desorb via different pathways. 

A tremendous amount of work has been done to delineate the detailed reaction mechanisms for many catalytic reactions on well characterized surfaces [1, 45]. Many of tiiese studies involved impinging molecules onto surfaces at relatively low pressures, and then interrogating the surfaces in vacuum with surface science teclmiques. For example, a usefiil technique for catalytic studies is TPD, as the reactants can be adsorbed onto the sample in one step, and the products fonned in a second step when the sample is heated. Note that catalytic surface studies have also been perfonned by reacting samples in a high-pressure cell, and then returning them to vacuum for measurement. 

Temperature progranuned desorption (TPD), also called thenual desorption spectroscopy (TDS), provides infonuation about the surface chemistry such as surface coverage and the activation energy for desorption [49]. TPD is discussed in detail in section B 1.25. In TPD, a clean surface is first exposed to a gaseous... 

TPD Temperature programmed desorption After pre-adsorption of gases on a surface, the desorption and/or reaction products are measured while the temperature Increases linearly with time. Coverages, kinetic parameters, reaction mechanism... 

Thenual desorption spectroscopy (TDS) or temperature progranuned desorption (TPD), as it is also called, is a simple and very popular teclmique in surface science. A sample covered with one or more adsorbate(s) is heated at a constant rate and the desorbing gases are detected with a mass spectrometer. If a reaction takes place diirmg the temperature ramp, one speaks of temperature programmed reaction spectroscopy (TPRS). 

TPD is frequently used to detenuine (relative) surface coverages. The area below a TPD spectrum of a certain species is proportional to the total amount that desorbs. In this way one can detennine uptake curves that correlate gas exposure to surface coverage. If tire pumping rate of the UHV system is sufiBciently high, the mass spectrometer signal for a particular desorption product is linearly proportional to the desorption rate of the adsorbate [20, 21] ... 

The disadvantage of TPD is that, in order to derive the kinetie parameters, rather involved eomputations are neeessary [21, 24]. As an alternative to the eomplete desorption analysis, many authors rely on simplified methods. The analysis of speetra using simplified analysis should be made with eare, as simplified analysis methods may easily give erroneous results [21]. 

Pig. 8. Stmctures of (a) hole transporter molecule W,Ar-biphenyl-W,Ar-bis(3-methylphen5l)l-lTiphen5l-4,4 diamine (TPD) (b) an oxidiazole derivative ... 

At very high dopant concentrations, transport occurs direcdy between the dopant molecules. The polymer acts only as a binder in most cases. Taking TPD-doped PVK as an example, at low TPD concentrations the hole mobihty first decreases from 3 x 10 cm /Vs to 10 cm /Vs with increasing TPD concentration, because TPD molecules act as hole traps (48,49). At higher TPD concentrations, new direct transport channels between the TPD molecules open up and the hole mobihty increases to lO " cm /Vs for ca 60% TPD doping (Table 1, entries 9—11) (48,49). In this case, there is no evidence for unusual interaction between TPD and PVK that affects the hole transport process. 

TABLE 25-69 Solid Waste Price Index, WTE Incinerator Intake TPD-Tip Fee, September 1994... 

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