Desorbate

The mixture to be studied is injected by syringe into the head of the column and the molecules comprising the mixture are adsorbed in varying degrees by the stationary phase and desorbed by the liquid phase. At the end of this succession of equilibria, the components of the mixture, more or less separated from each other, leave the column with the solvent. 

The higher the eluting force of the solvent, the more easily the components are desorbed. This force is represented by the solvent s polarity which results in mainly three types of interaction between the solvent and the solute ... 

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

The cleaning process proceeds by one of three primary mechanisms solubilization, emulsification, and roll-up [229]. In solubilization the oily phase partitions into surfactant micelles that desorb from the solid surface and diffuse into the bulk. As mentioned above, there is a body of theoretical work on solubilization [146, 147] and numerous experimental studies by a variety of spectroscopic techniques [143-145,230]. Emulsification involves the formation and removal of an emulsion at the oil-water interface the removal step may involve hydrodynamic as well as surface chemical forces. Emulsion formation is covered in Chapter XIV. In roll-up the surfactant reduces the contact angle of the liquid soil or the surface free energy of a solid particle aiding its detachment and subsequent removal by hydrodynamic forces. Adam and Stevenson s beautiful photographs illustrate roll-up of lanoline on wood fibers [231]. In order to achieve roll-up, one requires the surface free energies for soil detachment illustrated in Fig. XIII-14 to obey... 

Alternatively, gas chromatography may be used Fig. XVII-5 shows a schematic readout of the thermal conductivity detector, the areas under the peaks giving the amount adsorbed or desorbed. 

We have seen various kinds of explanations of why may vary with 6. The subject may, in a sense, be bypassed and an energy distribution function obtained much as in Section XVII-14A. In doing this, Cerefolini and Re [149] used a rate law in which the amount desorbed is linear in the logarithm of time (the Elovich equation). 

Fig. XVIII-14. Schematic illustration of the movement of NO molecules on a Pt(lll) surface. Molecules diffuse around on terraces, get trapped at steps, escape, and repeat the process many times before eventually desorbing. [Reprinted with permission from M. Cardillo, Langmuir, 1, 4 (1985) (Ref. 140). Copyright 1985, American Chemical Society.]...

The Langmuir-Hinshelwood picture is essentially that of Fig. XVIII-14. If the process is unimolecular, the species meanders around on the surface until it receives the activation energy to go over to product(s), which then desorb. If the process is bimolecular, two species diffuse around until a reactive encounter occurs. The reaction will be diffusion controlled if it occurs on every encounter (see Ref. 211) the theory of surface diffusional encounters has been treated (see Ref. 212) the subject may also be approached by means of Monte Carlo/molecular dynamics techniques [213]. In the case of activated bimolecular reactions, however, there will in general be many encounters before the reactive one, and the rate law for the surface reaction is generally written by analogy to the mass action law for solutions. That is, for a bimolecular process, the rate is taken to be proportional to the product of the two surface concentrations. It is interesting, however, that essentially the same rate law is obtained if the adsorption is strictly localized and species react only if they happen to adsorb on adjacent sites (note Ref. 214). (The apparent rate law, that is, the rate law in terms of gas pressures, depends on the form of the adsorption isotherm, as discussed in the next section.)... 

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. 

Atom abstraction occurs when a dissociation reaction occurs on a surface in which one of the dissociation products sticks to the surface, while another is emitted. If the chemisorption reaction is particularly exothennic, the excess energy generated by chemical bond fomiation can be chaimelled into the kinetic energy of the desorbed dissociation fragment. An example of atom abstraction involves the reaction of molecular halogens with Si surfaces [27, 28]. In this case, one halogen atom chemisorbs while the other atom is ejected from the surface. 

It is the relationship between the bound potential energy surface of an adsorbate and the vibrational states of the molecule that detemiine whether an adsorbate remains on the surface, or whether it desorbs after a period of time. The lifetime of the adsorbed state, r, depends on the size of the well relative to the vibrational energy inlierent in the system, and can be written as... 

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. 

In corrosion, adsorbates react directly with the substrate atoms to fomi new chemical species. The products may desorb from the surface (volatilization reaction) or may remain adsorbed in fonning a corrosion layer. Corrosion reactions have many industrial applications, such as dry etching of semiconductor surfaces. An example of a volatilization reaction is the etching of Si by fluorine [43]. In this case, fluorine reacts with the Si surface to fonn SiF gas. Note that the crystallinity of the remaining surface is also severely disrupted by this reaction. An example of corrosion layer fonnation is the oxidation of Fe metal to fonn mst. In this case, none of the products are volatile, but the crystallinity of the surface is dismpted as the bulk oxide fonns. Corrosion and etching reactions are discussed in more detail in section A3.10 and section C2.9. 

For some materials, the most notable being silicon, heating alone sufiBces to clean the surface. Commercial Si wafers are produced with a thin layer of silicon dioxide covering the surface. This native oxide is inert to reaction with the atmosphere, and therefore keeps the underlying Si material clean. The native oxide layer is desorbed, i.e. removed into the gas phase, by heating the wafer in UHV to a temperature above approximately 1100 °C. This procedure directly fonus a clean, well ordered Si surface. 

A DIET process involves tliree steps (1) an initial electronic excitation, (2) an electronic rearrangement to fonn a repulsive state and (3) emission of a particle from the surface. The first step can be a direct excitation to an antibondmg state, but more frequently it is simply the removal of a bound electron. In the second step, the surface electronic structure rearranges itself to fonn a repulsive state. This rearrangement could be, for example, the decay of a valence band electron to fill a hole created in step (1). The repulsive state must have a sufficiently long lifetime that the products can desorb from the surface before the state decays. Finally, during the emission step, the particle can interact with the surface in ways that perturb its trajectory. 

The ESDIAD pattern does, however, provide very usefril infomiation on the nature and synnnetry of an adsorbate. As an example, figure A1.7.13(a) shows the ESDIAD pattern of desorbed collected from a 0.25 ML coverage of PF on Ru(OOOl) [89]. The pattern displays a ring of emission, which indicates that the molecule adsorbs intact and is bonded tlirough the P end. It freely rotates about the P-Ru bond so that tlie emission occurs at all azimuthal angles, regardless of the substrate structure. In figure A1.7.13(b), the... 

The first step consists of the molecular adsorption of CO. The second step is the dissociation of O2 to yield two adsorbed oxygen atoms. The third step is the reaction of an adsorbed CO molecule with an adsorbed oxygen atom to fonn a CO2 molecule that, at room temperature and higher, desorbs upon fomiation. To simplify matters, this desorption step is not included. This sequence of steps depicts a Langmuir-Hinshelwood mechanism, whereby reaction occurs between two adsorbed species (as opposed to an Eley-Rideal mechanism, whereby reaction occurs between one adsorbed species and one gas phase species). The role of surface science studies in fomuilating the CO oxidation mechanism was prominent. 

FigureBl.7.2. Schematic representations of alternative ionization methods to El and PI (a) fast-atom bombardment in which a beam of keV atoms desorbs solute from a matrix (b) matrix-assisted laser desorption ionization and (c) electrospray ionization.

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 value of a graded series of eluents is that if one member of the series succeeds in desorbing a portion of an adsorbate, then another more power ful eluent should remove a further portion of the adsorbate. By mixing the eluents in various proportions, a finer gradation may be obtained, e.g., petroleum ether benzene and petroleum ether benzene and ether ether and acetone, etc. 

Caffeine is extracted from beverages by a solid-phase microextraction using an uncoated fused silica fiber. The fiber is suspended in the sample for 5 min and the sample stirred to assist the mass transfer of analyte to the fiber. Immediately after removing the fiber from the sample it is transferred to the gas chromatograph s injection port where the analyte is thermally desorbed. Quantitation is accomplished by using a C3 caffeine solution as an internal standard. 

Occlusions, which are a second type of coprecipitated impurity, occur when physically adsorbed interfering ions become trapped within the growing precipitate. Occlusions form in two ways. The most common mechanism occurs when physically adsorbed ions are surrounded by additional precipitate before they can be desorbed or displaced (see Figure 8.4a). In this case the precipitate s mass is always greater than expected. Occlusions also form when rapid precipitation traps a pocket of solution within the growing precipitate (Figure 8.4b). Since the trapped solution contains dissolved solids, the precipitate s mass normally increases. The mass of the precipitate may be less than expected, however, if the occluded material consists primarily of the analyte in a lower-molecular-weight form from that of the precipitate. 

In a MALDl experiment, the sample is mixed or dissolved in a matrix material that has an absorption spectrum matching the laser wavelength of energy, The sample may not have a matching absorption peak (a), but this is not important because the matrix material absorbs the radiation, some of which is passed on to the dissolved sample. Neutral molecules and ions from both sample and matrix material are desorbed (b). 

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