Static chemisorption

Hydrogen chemisorption Static H2 chemisorption at 100°C on the reduced cobalt catalysts was used to determine the number of reduced surface cobalt metal atoms. This is related to the overall activity of the catalysts during CO hydrogenation. Gas volumetric chemisorption at 100°C was performed using the method described by Reuel and Bartholomew [6]. The experiment was performed in a Micromeritics ASAP 2010 using ASAP 2010C V3.00 software. 

Total specific surface area Gas physisorption Mercury porosimetry Active site surface area Selective chemisorption (static or dynamic)... 

The role of the support on hydrogen chemisorption on supported rhodium catalysts was studied using static and frequency response techniques. In all Instances, several klnetlcally distinct H2 cheml-sorptlve sites were observed. On the basis of the kinetics, at least one site appears to sorb H2 molecularly at temperatures below 150°C, regardless of the support. At higher temperatures, a dissociative mechanism may become dominant. Inducement of the SMSI state In Rh/T102 does not significantly alter Its equilibrium H2 chemisorption. 

Static Chemisorption. Measurements were made by two procedures. In the first, the catalyst was evacuated at ca. 250°C for at least 8 hrs and cooled to the measurement temperature under vacuum. Hydrogen was then admitted at progressively higher pressures and the amount of gas adsorbed after 15-30 min at each pressure recorded. The sample was then evacuated for 30 min and the dosing procedure repeated so as to obtain a measure of the reversibly adsorbed gas. In the second (saturation) procedure, after reduction and evacuation, the catalyst was cooled to the... 

It Is apparent from even the static chemisorption results that not all chemisorbing sites have the same energetics, since In all catalysts a sizeable portion of the sorbed gas could be removed by pumping for a few minutes. The exact fraction of the reversible portion depends on support and temperature. For the catalysts used In this study, the reversible portion ranged between 10-30% of the total chemisorption. 

A comparison of the qualitative features of the FRC spectra for the catalyst studied show a clear distinction between Rh/S102 and Rh/T102, In terms of their reversible H2-chemlsorptlon. Suprlslngly, little difference was observed between normal and SMSI-Rh/T102. "Normal" Rh/T102 behaved quite differently from Rh/S102, In spite of their similarities In total, l.e., static, chemisorption behavior. 

Studies of the static and frequency response chemisorption of hydrogen on Rh catalysts supported on SlOo and TIO7 have shown that ... 

Carbon monoxide chemisorption was used to estimate the surface area of metallic iron after reduction. The quantity of CO chemisorbed was determined [6J by taking the difference between the volumes adsorbed in two isotherms at 195 K where there had been an intervening evacuation for at least 30 min to remove the physical adsorption. Whilst aware of its arbitrariness, we have followed earlier workers [6,10,11] in assuming a stoichiometry of Fe CO = 2.1 to estimate and compare the surface areas of metallic iron in our catalysts. As a second index for this comparison we used reactive N2O adsorption, N20(g) N2(g) + O(ads), the method widely applied for supported copper [12]. However, in view of the greater reactivity of iron, measurements were made at ambient temperature and p = 20 Torr, using a static system. 

The Ru metal area was determined by volumetric H2 chemisorption in the quartz U-tube of an Autosorb 1-C set-up (Quantachrome) following the procedure described in ref. [16]. Prior to chemisorption, the catalysts were activated by passing 80 Nml/min high-purity synthesis gas (Pnj / Phj -1/3) from a connected feed system through the U-tube and heating to 673 K for alkali-promoted catalysts or to 773 K for alkali-free catalysts with a heating rate of 1 K/min. The BET area was measured by static N2 physisorption in the same set-up. 

For the chemisorption experiments a weighed catalyst sample (wet) was put in a cell and mounted on the Micromeritics 2010 (static) chemisorption instmment. The sample was heated under vacuum to 150°C where it was exposed to hydrogen (0.7 atm) for 0.5 hour. The sample was then evacuated at room temperature, reexposed to hydrogen for 0.5 hour, then evacuated, and cooled to 30°C under vacuum. 

In a similar approach Riihe et al. [279] reported the preparation ofpoly(2-oxazoline) brushes by the grafting onto as well as grafting from method. For LCSIP of 2-ethyl-2-oxazolines silane functionalized undecane tosylate was first prepared and then immobilized on the substrate surface. SIP resulted in PEOx layers with thickness close to 30 nm. PEOx brushes were prepared by chemisorption of PEOx disulfides onto gold substrates. Preliminary static and dynamic swelling experiments are reported for these brushes. However, later observations [243] contradicted these findings. 

The term chemisorption was coined in order to classify the interaction between a particle in the gas phase and a solid surface, i.e. the result of the adsorption process [1]. If the interaction leads to the formation of a chemical bond the adsorbate formed is called a chem-isorbate. Where chemical bond formation is not important the process is classified as physisorption. There are several conceptual problems with such a differentiation which we briefly address in the following, and which indicate that a more detailed look at the entire process of adsorbate formation is needed before a reliable classification may be carried out. In fact, as it turns out, for a conclusive classification one would need the full theoretical and experimental understanding of the system under investigation. Such an approach must include the static aspects, i.e. the energies involved, as well as the dynamic aspects, i.e. the processes involved in the formation of the adsorptive interactions. 

The problem with sulfide catalysts (hydrotreatment) is to determine the active centres, which represent only part of their total surface area. Chemisorption of O2, CO and NO is used, and some attempts concern NIL, pyridine and thiophene. Static volumetric methods or dynamic methods (pulse or frontal mode) may be used, but the techniques do not seem yet reliable, due to the possible modification (oxidation) of the surface or subsurface regions by O2 or NO probe molecules or the kinetics of adsorption. CO might be more promising. Infrared spectroscopy, especially FTIR seems necessary to characterise co-ordinativcly unsaturated sites, which are essential for catalytic activity. CO and NO can also be used to identify the chemical nature of sites (sulfided, partially reduced or reduced sites). For such... 

In order to assign and compare catalyst reactivity rates, measured conversions were "normalized" to 3000 GHSV by multiplying observed conversions by the factor actual GHSV/3000. The normalized conversions were used to specify rates to individual products and rates for overall CO conversion. The reaction has b n shown not to be mass or heat transfer limited (12). CO and irreversible H2 chemisorption were measured at room temperature, the former using a pulse injection system and a thermal conductivity detector, and the latter using a static system. Prior to measurements, catalysts were reduced under the same schedule as for reactor runs. 

The in sim characterization of catalysts was earned out in an apparatus which included a quadiupole mass-spectrometer and a gas chromatograph for TPO and H2 chemisorption measurements. In situ coking was performed by injecting a mixture of He and n-hexane vapor over the reduced catalysts at 500 C, In TPO experiments, ihe coked sample was heated at a rate of 8 C/min in a stream of 2 voL% O2 + 98% He. The amount of CO2 produced was recorded. The chemisorption of H2 was carried out in the same appanitus by a flow method after reduction or caking. The flow rate of carrier gas (Ar) was maintained at 25 ml/min and the volume of H2 injected was 0.062 ml/pulse. Since the partial piessiire of H2 was very low in this system, the hydrogenation of coke was never observed. Isobaric H2 chemisorption measurements with fresh catalysts were carried out in a static adsorption apparatus. Dehydrogenation of n-butane was carried out in a flow micro-rcactor in H2 atmosphere at LHSV = 3 h-l and H2/HC=1. Reaction products were... 

Static hydrogen chemisorptions were performed using a standard volumetric glass adsorption apparatus. 

To determine nickel surface areas of fresh catalysts, hydrogen chemisorption measurements were performed with the atmospheric TPH apparatus described above. Nickel surface areas of the catalysts were also measured by static volumetric hydrogen chemisorption (Coulter Omnisorp 100 cx). Before these measurements, samples were reduced in situ in a pure hydrogen atmosphere by raising the temperature up to 900°C (20°C/min). The samples were then cooled in a helium flow and the measurements were performed at 30°C. The catalyst materials and the analytical methods are described in [4,6,7]. 

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