Coadsorption measurements

Indeed, procedures (b) open various interesting possibilities to measure binary coadsorption equilibria and to design respective instruments for fully automated measurements, cp. for example Chap. 4, Fig. 4.11b. To get an overview, the various possibilities of coadsorption measurements by combining single component methods are sketched in Table 0.2. The numbers in the upper right portion of this matrix scheme indicate the number of components in the gas mixture which can be determined by the respective method. The numbers in the lower left portion of the matrix give the Chapter and Section where more information on this method can be found. Empty fields indicate that we did not do respective measurements and also are not aware of any institution where such measurements might have been realized. 

No coadsorption measurements at high temperatures using the volumetric / manometric method seem to have been performed yet. Some experiments with humid nitrogen, i. e. N2 / H2O mixtures are presently (2003) under way at the author s institute. Data will be reported in the homepage of IFT, cp. [4.15]. 

Data have been correlated by using a generabzed AI of Langmuir type, eq. (3.38). As can be seen from the figure, due to presorption of water of about 50 % of the limiting molar amount of CO2, the capacity for C02-adsorption is reduced by ca. 40 %. We expect that part of the CO2 adsorbed on zeolite with presorbed water will be dissolved in the surface-water . In view of experimental difficulties we have not been able to do truly binary coadsorption measurements for C02/H20-mixtures at near ambient temperatures. Consequently we do not know the composition of the adsorbed phase for sure but leave this question open to the interested experimenter. 

An instrument for gravimetric measurements of multicomponent gas adsorption equilibria has been designed and operated during 1993-2003 at the IFT, University of Siegen. It was part of a multipurpose instrument for different types of gas coadsorption measurements. A photo of it is included in Chap. 4, cp. Fig. 4.2. 

In this chapter we will present experimental information (Sect. 2.1), the theory of measurement (Sect 2.2), and uncertainties (Sect 2.3), and several examples (Sect. 2.4) of this method. Two modified versions of the measurement procedure which may be called densimetric-gravimetric and densimetric-volumetric / manometric methods (which especially seems to be suited for online industrial coadsorption measurements) are also outlined (Sect. 3). These methods also may be used to measure adsorption of gases and / or vapors on surfaces of arbitrary sohd materials as for example the inner walls of vessels, tubes, valves etc. of the experimental device(s) used (Sect.3.6). Advantages and disadvantages of the methods proposed are discussed in Sect. 4. A list of symbols used is given in Sect. 5, followed by references to journal articles and books cited. 

Figure 4.1. Experimental setup of a multipurpose instrument for coadsorption measurements of multicomponent gas mixtures on porous solids. The instrument allows volumetrie-chromatographic, gravimetric-chromatographic and also combined volumetric-gravimetric measurements for binary coadsorption equUihria.

Coadsorption measurements of sorptive gases including inert components are presently done at the author s institution. Results will be published in a forthcoming paper [4.7]. 

In practice an instrument for volumetric-gravimetric coadsorption measurement requires a considerable amount of equipment and expertise to operate it properly. Hence the instrument will be quite expensive, especially if it is designed and equipped for automatic measurements. 

Comparison of Densimetric-Gravimetric and Densimetric-Volumetric Binary Coadsorption Measurements... 

Figure 4. Schematic diagram of a gravimetric-chromatographic installation with a magnetic suspension balance for coadsorption measurements.

Figures 7.9 and 7.10 are simply simulations based on assumed interaction energies. The lateral interactions for specific cases can only be derived from measurement in favorable cases, such as the following example on the coadsorption of CO and N atoms.

Formation of CH3O, following CH3OH and 0 coadsorption and annealing the sample to 1/5 K, was verified with EELS measurements the spectra... 

The non situ experiment pioneered by Sass uses a preparation of an electrode in an ultrahigh vacuum through cryogenic coadsorption of known quantities of electrolyte species (i.e., solvent, ions, and neutral molecules) on a metal surface. " Such experiments serve as a simulation, or better, as a synthetic model of electrodes. The use of surface spectroscopic techniques makes it possible to determine the coverage and structure of a synthesized electrolyte. The interfacial potential (i.e., the electrode work function) is measured using the voltaic cell technique. Of course, there are reasonable objections to the UHV technique, such as too little water, too low a temperature, too small interfacial potentials, and lack of control of ionic activities. ... 

All electrochemical techniques measure charge transferred across an interface. Since charge is the measurable quantity, it is not surprising that electrochemical theory has been founded on an electrostatic basis, with chemical effects added as a perturbation. In the electrostatic limit ions are treated as fully charged species with some level of solvation. If we are to use UHV models to test theories of the double layer, we must be able to study in UHV the weakly-adsorbing systems where these ideal "electrostatic" ions could be present and where we would expect the effects of water to be most dominant. To this end, and to allow application of UHV spectroscopic methods to the pH effects which control so much of aqueous interfacial chemistry, we have studied the coadsorption of water and anhydrous HF on Pt(lll) in UHV (3). Surface spectroscopies have allowed us to follow the ionization of the acid and to determine the extent of solvation both in the layer adjacent to the metal and in subsequent layers. 

It was demonstrated that the radiotracer method, using labeled anions, is an adequate tool to follow anion adsorption in the course of voltammetric measurements and to gain simultaneous information on hydrogen and anion adsorption [163]. Coupling voltammetric and radiometric measurements in the study of platinized platinum electrodes gave insight in the anion-hydrogen atom coadsorption process. 

Early stages of copper electrodeposition and coadsorption of chloride on the Au(lll) electrode surface have been studied by Wu et al. [390] applying electrochemical methods and in situ X-ray absorption measurements. The results indicate a large degree of static disorder and exclude the presence of high-symmetry structures. Krznaric and Goricnik [391]... 

Fewer nonsteady-state measurements have been carried out on iridium than on platinum and palladium. Figure 50 shows the results of a 02—CO coadsorption experiment on Ir(lll) (203). Initially 02 was adsorbed, followed by CO adsorption, after which the crystal was heated with a linear temperature rise. It is seen that the peak temperature for COz desorption is shifted to lower values with increasing CO coverage. This may be due to a second-order desorption effect (203) or a reduced activation energy for the reaction owing to interactions in the adlayer, as was found on Pd(lll) (176). 

In this review, we will consider the adsorption of a single species coadsorption phenomena will not be considered, since it is generally impossible to divide the flow of charge among several species. We will present the thermodynamics on which the concept of the electrosorption valency is based, discuss methods by which it can be measured, and explain its relation to the dipole moment and to partial charge transfer. The latter can be explained within an extension of the Anderson-Newns model for adsorption, which is useful for a semi-quantitative treatment of electrochemical adsorption. Our review of concepts and methods will be concluded by a survey of experimental data on thiol monolayers, which nowadays are adsorbates of particular interest. 

C.5.2. Hydrogen Adsorption Followed by CO Adsorption. When the gas dosing sequence was reversed, the coadsorption behavior became more complex and depended on the temperature and the palladium surface structure. We start with measurements at 100 K. On hydrogen-precovered Pd(l 1 1), no CO adsorption was... 

Fig. 44. TD spectra characterizing H2 (mass 2), C2H4 (monitored by mass 27), and C2H6 (monitored by mass 29) on Pd/AfiOs (mean particle diameter, 6 mn). The spectra were measured after adsorption of H2 (a), C2H4 (b), and after C2H4-hydrogen coadsorption (c). Exposures were 50 L of H2 at 120 K (a), 1.5 L of C2H4 at 120 K (b) and 50 L of H2 followed by 1.5 L of C2H4 at 120 K (c) adapted from (68) with permission from Elsevier.

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