Apparatus, isothermal surface

Recently an automatic apparatus for surface areas and pore size determination has been described [125]. The Isothermegraphe is a volumetric apparatus, with a calibrated tube, which draws complete adsorption-desorption isotherms using a piston of mercury which modifies the pressure slowly at a programmed speed. 

Physical adsorption of nitrogen was carried out on an ASAP 2400 Micromeritics apparatus. Before measurements, samples were evacuated overnight at 350 °C at vacuum of 2 Pa. For all samples the same adsorption data table was used. Collected adsorption data were treated by BET-isotherm in the range 0.05 < P/micropore volume and mesopore + external surface, t-plot method, with master isotherm of nonporous alumina (Harkins-Jura) was used, t-plot was linearized in the range of 0.35 < t < 0.6 nm. 

Chemical composition was determined by elemental analysis, by means of a Varian Liberty 200 ICP spectrometer. X-ray powder diffraction (XRD) patterns were collected on a Philips PW 1820 powder diffractometer, using the Ni-filtered C Ka radiation (A, = 1.5406 A). BET surface area and pore size distribution were determined from N2 adsorption isotherms at 77 K (Thermofinnigan Sorptomatic 1990 apparatus, sample out gassing at 573 K for 24 h). Surface acidity was analysed by microcalorimetry at 353 K, using NH3 as probe molecule. Calorimetric runs were performed in a Tian-Calvet heat flow calorimeter (Setaram). Main physico-chemical properties and the total acidity of the catalysts are reported in Table 1. 

Enantiomeric discrimination and its relation to film component reorganization upon compression can also be observed in dynamic surface tension hysteresis loops. Figure 26 shows the WjA isotherms generated upon five successive compression/expansion cycles (from II = 0 to lOdyncm-1) of racemic and enantiomeric films containing 17 mole percent palmitic acid. The hysteresis loops, obtained on the apparatus described in Section 2 (p. 63), show that the first compression/expansion cycle of the racemic system is repeated in each successive cycle. Upon expansion of the film from the maximum surface pressure back to Odyncm-1, the racemic film returns to its original state without detectable reorganization of the components. However, the... 

An unusually extensive battery of experimental techniques was brought to bear on these comparisons of enantiomers with their racemic mixtures and of diastereomers with each other. A very sensitive Langmuir trough was constructed for the project, with temperature control from 15 to 40°C. In addition to the familiar force/area isotherms, which were used to compare all systems, measurements of surface potentials, surface shear viscosities, and dynamic suface tensions (for hysteresis only) were made on several systems with specially designed apparatus. Several microscopic techniques, epi-fluorescence optical microscopy, scanning tunneling microscopy, and electron microscopy, were applied to films of stearoylserine methyl ester, the most extensively investigated surfactant. 

Figure 7-24 Adsorption equilibrium apparatus to determine adsorption isotherms and surface areas of catalysts. From the saturation of a sample of known weight, the surface area can be determined if the area occupied by a...

All equipment designed to measure surface area, adsorption-desorption isotherms or pore volume by adsorption actually determines the quantity of gas condensed on a solid surface at some equilibrium vapor pressure. The surface area or pore volumes and pore sizes are then calculated by means of an appropriate theory used to treat the adsorption and/or desorption data. Depending on the apparatus employed, the adsorbed quantity is measured as volume or weight. The accuracy of an adsorption apparatus is, therefore, dependent upon its ability to correctly measure either of these quantities. 

Once equilibrium has been reached, the height difference between the two liquid surfaces is all that remains to be measured. The primary factor to note here is that capillaries are used to minimize the dilution effects. This means that corrections for capillary rise must be taken into account unless the apparatus allows the difference between two carefully matched capillaries to be measured. We discuss capillary rise in Chapter 6, Sections 6.2 and 6.4. Finally, there is an extremely important practical reason, in addition to the theoretical requirement of isothermal conditions, for good thermostating in osmometry experiments. The apparatus consists of a large liquid volume attached to a capillary and therefore has the characteristics of a liquid thermometer The location of the meniscus is quite sensitive to temperature fluctuations. 

Apparatus and Procedure. Surface Isotherms. The technique for determining the n-A and AV-A curves of the lipid films has been described (6). Briefly, the Wilhelmy plate method was used to measure surface tension, from which the surface pressure was calculated (n = 7h2o—yfiim) The surface potential was measured by means of a radioactive (226Ra) air electrode and a saturated calomel electrode connected to a high impedance model 610 B Keithley electrometer (Keithley Instruments, Cleveland, Ohio). 

The bulk crystal structure of the samples was determined by XRD (Rigaku D-max B) using a filtered Cu Ka radiation. Surface structure and composition were monitored by XPS (Perkin-Elmer PHI 5400). The N2 BET surface area and CO chemisorption were measured in a constant-volume adsorption apparatus. For the latter, two successive isotherms separated by evacuation were obtained at RT for a sample and the difference extrapolated to zero pressure was taken as chemisorbed CO. 

The volumetric method is mainly used for the purpose of determining specific surface areas of solids from gas (particularly nitrogen) adsorption measurements (see page 134). The gas is contained in a gas burette, and its pressure is measured with a manometer (see Figure 5.4). All of the volumes in the apparatus are calibrated so that when the gas is admitted to the adsorbent sample the amount adsorbed can be calculated from the equilibrium pressure reading. The adsorption isotherm is obtained from a series of measurements at different pressures. 

The shape of the experimental isotherm (Fig. 3.38) is qualitatively similar to that found by van Vliet [226] with foam films from aqueous solutions of polyvinyl alcohol. It is also characteristic of the interaction energy as a function of the distance between two mica surfaces bearing grafted polymer brushes in good solvent as determined with Surface Force Apparatus (SFA) [e.g. 242],... 

Accurate information on the isotherm trends of various VOC groups (in relation to the individual boiling points of low, medium and high boilers) was essential in order to describe the entire process and to elaborate a suitable design for the plant. The isotherms of various VOCs were measured on a commercial microporous ACC using the equilibrium apparatus previously described. The specific surface of this activated carbon fibre cloth was 1000 mVg, pore diameter was between 1 and 2 nm and the specific pore volume for solvents was 0.45 cmVg. 

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