Outgassing measurement

A detailed study of the physical and chemical adsorption of water on three xerogels, ferric oxide, alumina and titania, as well as on silica (cf. p. 272) has been carried out by Morimoto and his co-workers. Each sample was outgassed at 600°C for 4 hours, the water isotherm determined at or near 20°C, and a repeat isotherm measured after an outgassing at 30 C. The procedure was repeated on the same sample after it had been evacuated at a... 

Sample cells were fabricated from tungsten. Additional crucibles composed of a Pt-40 w/o Rh-8 w/o W alloy were also used in experiments on the PuPt phase. Each tungsten cell was vacuum outgassed at 1800 for 1 h before an experiment. The cell temperature was determined during the measurements by sighting with a pyrometer (Pyrometer Instrument Co.) onto a blackbody hole in each cell base. The pyrometer and sight glasses were calibrated with an NBS standard lamp. 

Figure 3 shows the amount of Bronsted sites, as measured by the surface of the characteristic IR peak at 1540 cm after outgassing at 523 K, as a function of the composition of the mechanical mixtures. The dashed lines represent the addition of the contribution of the pure phases, calculated as in Equation 3. An enhancement of the amount of Bronsted sites on the mixtures, when compared to the theoretical values, is observed. This effect is not very clear in SA6 series, but it is more evident in SA12 and SA60 series. The reproducibility of the experiments has been checked the variation between different wafers of the same sample was always inferior to 10%. 

The specific surface area of the fresh and used catalysts was measured by nitrogen adsorption method (Sorptometer 1900, Carlo Erba Instruments). The catalysts were outgassed at 473 K prior to the measurements and the Dubinin equation was used to calculate the specific surface area. The acidity of investigated samples was measured by infrared spectroscopy (ATI Mattson FTIR) by using pyridine (>99.5%, a.r.) as a probe molecule for qualitative and quantitative determination of both Bronstcd and Lewis acid sites (further denoted as BAS and LAS). The amounts of BAS and LAS were calculated from the intensities of corresponding spectral bands by using the molar extinction coefficients reported by Emeis (23). Full details of the acidity measurements are provided elsewhere (22). 

In one of the earliest reports of the use of clean evaporated alloy films in surface studies, Stephens described the preparation and characterization of Pd-Au films and presented some results for the adsorption of oxygen on them 46). Films of pure Pd and 60% Au were evaporated directly from wires, while films of 80% Au and pure Au were evaporated from a pre-outgassed tungsten support wire. The films were evaporated in a UHV system and the pressure was kept below PC8 Torr during evaporation. After evaporation, the films were stabilized by cycling between —195° and 30°C four times. They w ere characterized by X-ray diffraction and chemical analysis surface areas were measured by the BET method using krypton adsorption. 

The 4A and 5A zeolite samples come from the French Institute of Petroleum (IFP). These samples named in the text 5A 67, 5A 73.5 and 5A 86 are exchanged at 67%, 73.5% and 86% by calcium ions, respectively. Prior each microgravimetric measurement, 20 mg of zeolite sample are outgassed at 350°C under primary vacuum... 

The strength of the Bronsted (BAS) and Lewis (LAS) acid sites of the pure and synthesized materials was measured by Fourier transformed infrared spectroscopy (ATI Mattson FTIR) by using pyridine as a probe molecule. Spectral bands at 1545 cm 1 and 1450 cm 1 were used to indentify BAS and LAS, respectively. Quantitative determination of BAS and LAS was calculated with the coefficients reported by Emeis [5], The measurements were performed by pressing the catalyst into self supported wafers. Thereafter, the cell with the catalyst wafer was outgassed and heated to 450°C for lh. Background spectra were recorded at 100°C. Pyridine was then adsorbed onto the catalyst for 30 min followed by desorption at 250, 350 and 450°C. Spectra were recorded at 100°C in between every temperature ramp. 

The surface area of the catalysts was measured by nitrogen physisorption (Sorptometer 1900, Carlo Erba). The fresh and regenerated samples were outgassed at 150°C and the spent samples at 100°C for 3 hours. The specific surface area was calculated with the Dubinin equation. 

Nitrogen adsorption was performed at -196 °C in a Micromeritics ASAP 2010 volumetric instrument. The samples were outgassed at 80 °C prior to the adsorption measurement until a 3.10 3 Torr static vacuum was reached. The surface area was calculated by the Brunauer-Emmett-Teller (BET) method. Micropore volume and external surface area were evaluated by the alpha-S method using a standard isotherm measured on Aerosil 200 fumed silica [8]. Powder X-ray diffraction (XRD) patterns of samples dried at 80 °C were collected at room temperature on a Broker AXS D-8 diffractometer with Cu Ka radiation. Thermogravimetric analysis was carried out in air flow with heating rate 10 °C min"1 up to 900 °C in a Netzsch TG 209 C thermal balance. SEM micrographs were recorded on a Hitachi S4500 microscope. 

The ir measurements were carried out with a Perkin Elmer 580 spectrometer and fused silica cell with KBr windows allowing to outgass the zeolitic wafer at a desired temperature and to introduce and further outgass a probe molecule without contact with air. 

Differential heats of NH adsorption were measured for the samples outgassed at different temperatures ranging from 400 to 800°C. Ammonia was chosen as a basic probe because its size is small, which may limitate diffusion effects in small pore zeolite materials. The variations of the differential heats of adsorption are plotted in fig. 3 as a function of the successive pulses of... 

Figure 4 Variations with coverage of the differential heats of NHg adsorption measured at 143°C on H-ZSM-11 samples outgassed at 400°C. Samples 3 (0) 4 ( ), 5 ( ) and 6 (A).

One of the first applications of this chopped-beam irradiation technitriplet spectra was reported by Labhart From a knowledge of the intensity of the irradiation light, he determined the quantum yield of triplet generation to be 0.55 0.11 for outgassed solutions of 1,2-benzanthrazene in hexane at room temperature. Hunziker 32) has applied this method to the study of the gas-phase absorption spectrum of triplet naphthalene. A gas mixture of 500 torr Na, 0.3 mtorr Hg, and about 10 mtorr naphthalene was irradiated by a modulated low-pressure mercury lamp. The mercury vapor in the cell efficiently absorbed the line spectrum of the lamp and acted as a photosensitizer. The triplet state of naphthalene was formed directly through collisional deactivation of the excited mercury atoms. 

Wade and Hackerman (302) measured the heats of immersion in water of both anatase and rutile as a function of particle size and outgassing temperature. Apart from the distinct influence of the particle size, a maximum in the heat of immersion was observed after outgassing at 300 to 350°, indicating a rehydroxylation reaction. This is similar to the behavior of silica. Whereas, with silica, the decrease at higher evacuation temperatures is caused by the slowness of the reopening of siloxane bonds (see Section III,A,2), it is very probably caused by a decrease in surface area in the case of TiOj. The maximum in the heat of immersion curves was distinct only with samples of high surface area. Stbber et al. (225) observed a decrease in the surface area of fine particle size anatase already at 450°. 

All measurements have been made on homogeneous membranes of Eastman Kodak 398-3 cellulose acetate (6). The membranes were cast on glass plates and evaporated slowly to dryness from 2% w/v solution in pure acetone in a controlled atmosphere. The membranes were carefully outgassed under vacuum at 40°C before annealing in water for 30 minutes at 80°C during which they became detached from their casting plates. 

We have seen that ZTRID can be successfully observed and interpreted for cluster ions. It is of interest to look as well at covalent molecular ions for new thermochemical information. The parent ion of tetraethylsilane illustrates these possibilities. The ion is formed in adequate abundance directly in the FTICR cell by electron impact, and the more abundant triethylsilyl ion is readily removed by ion ejection. Temperatures substantially above room temperature are needed to give measurable ZTRID rates. Figure 10 shows the low-pressure dissociation chemistry at 403 K. At this temperature, some water vapor outgasses in the cell and reacts with the tetraethylsilane parent ion to give the EtjSi(H20) ion, but this competing bimolecular reaction is well behaved and easily allowed for in the kinetic fitting. The parent ion undergoes the ZTRID process. 

The BET method (Brunauer, Emmett and Teller, 1938) with N2 as the adsorbate, is by far the most common method of measuring the surface areas of Fe oxides. Various commerical instruments are available for these measurements. The method involves measuring the extent of adsorption of N2 (at the boiling temperature of liquid N2 - 77 K) on the outgassed solid as a function of the relative pressure, p/po. he. the adsorption isotherm p is the partial pressure of the adsorbate and po is its equilibrium vapour pressure. The following linear relationship exists between the amount adsorbed, v, (cm g ) and the relative vapour pressure, p/po, ... 

Clausen, L. I. Fabricius (2000) BET measurements Outgassing of minerals. J. Colloid Interface Sci. 227 7-15... 

In order to accurately determine the chemisorbed amount from the overall adsorption isotherm, the sample can be further outgassed at the same temperature to remove the physically adsorbed amount, after which a new adsorption procedure is carried out to obtain isotherm II. The difference between the first and second isotherm gives the extent of irreversible adsorption ( ) at a given temperature (Figure 13.5b), and can be considered as a measurement of the amount of strong sites in the catalyst. However, in the first approximation, the magnitude of the heat of adsorption can be considered as a simple criterion to distinguish between physical and chemical adsorption. 

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