Oxidation isotherms

Fig. 27. Oxidation isotherms of single crystal copper surfaces 78-323°K O run No. 1 run No. 2. Samples No. 1 to No. 24 of crystal faces (100), (110), and (111). Isotherms curves are calculated. [After Rhodin, J. Am. Chem. Soc. 73, 3143 (1951).]...

Family Differences in textural classes, mineralogy, acidity, and temperature. Clayey oxidic isothermic Typic Kandihumult Plants generally react in a similar manner to the same soil family. 

There are complexities. The wetting of carbon blacks is very dependent on the degree of surface oxidation Healey et al. [19] found that q mm in water varied with the fraction of hydrophilic sites as determined by water adsorption isotherms. In the case of oxides such as Ti02 and Si02, can vary considerably with pretreatment and with the specific surface area [17, 20, 21]. Morimoto and co-workers report a considerable variation in q mm of ZnO with the degree of heat treatment (see Ref. 22). 

Molecular area, a ,(Ar), of argon at 77 K on nonporous oxides (Argon BET plots constructed withp (liquid) BET surface areas calculated from nitrogen isotherms, with a (Na) = 16-2 A )... 

As already mentioned, the choice of the supercooled liquid as reference state has been questioned by some workers who use the saturation vapour pressure of the solid, which is measured at the working temperature in the course of the isotherm determination. The effect of this alternative choice of p° on the value of a for argon adsorbed on a number of oxide samples, covering a wide range of surface areas, is clear from Table 2.11 the average value of is seen to be somewhat higher, i.e. 18 OA. ... 

Type IV isotherms are often found with inorganic oxide xerogels and other porous solids. With certain qualifications, which will be discussed in this chapter, it is possible to analyse Type IV isotherms (notably those of nitrogen at 77 K) so as to obtain a reasonable estimate of the specific surface and an approximate assessment of the pore size distribution. 

Further evidence pointing in the same direction was provided by Pierce, Wiley and Smith, who found that on steam activation of a particular char at 900°C the saturation uptake increased three-fold, yet the isotherm was still of Type I. They argued that even if the width of the pores was only two molecular diameters before activation, it would increase, by removal of oxides, during the activation so that the second Type I isotherm would correspond to pores more than two molecular diameters wide. (The alternative explanation, that activation produced new pores of the same width as the old, seems unlikely.)... 

Fig. 4.25 Adsorption isotherms showing low-pressure hysteresis, (a) Carbon tetrachloride at 20°C on unactivated polyacrylonitrile carbon Curves A and B are the desorption branches of the isotherms of the sample after heat treatment at 900°C and 2700°C respectively Curve C is the common adsorption branch (b) water at 22°C on stannic oxide gel heated to SOO C (c) krypton at 77-4 K on exfoliated graphite (d) ethyl chloride at 6°C on porous glass. (Redrawn from the diagrams in the original papers, with omission of experimental points.)...

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... 

Prior to determination of an isotherm, all physisorbed material has to be removed from the surface of the adsorbent. This is best achieved by exposure of the surface to high vacuum, the exact conditions required (temperature and residual pressure) being dependent on the particular gas-solid system. In routine determinations of surface area it is generally advisable not to remove any chemisorbed species which may be present thus, the hydroxylated oxides are usually outgassed at 1S0°C. Microporous adsorbents such as zeolites or active carbons however require higher temperatures (350-400 C, say) for complete removal of physisorbed material from their narrowest pores. An outgassing period of 6-10 hours (e.g. overnight) is usually sufficient to reduce the residual pressure to 10 Torr. 

Ferritic stainless steels depend on chromium for high temperature corrosion resistance. A Cr202 scale may form on an alloy above 600°C when the chromium content is ca 13 wt % (36,37). This scale has excellent protective properties and occurs iu the form of a very thin layer containing up to 2 wt % iron. At chromium contents above 19 wt % the metal loss owiag to oxidation at 950°C is quite small. Such alloys also are quite resistant to attack by water vapor at 600°C (38). Isothermal oxidation resistance for some ferritic stainless steels has been reported after 10,000 h at 815°C (39). Grades 410 and 430, with 11.5—13.5 wt % Cr and 14—18 wt % Cr, respectively, behaved significandy better than type 409 which has a chromium content of 11 wt %. 

Fig. 15. Compaiison of MoSi and othei intermetaUics and supeiaUoys (a), isothermal and (b), cyclic oxidation (1200°C) behavior (80).

Ozone can be analyzed by titrimetry, direct and colorimetric spectrometry, amperometry, oxidation—reduction potential (ORP), chemiluminescence, calorimetry, thermal conductivity, and isothermal pressure change on decomposition. The last three methods ate not frequently employed. Proper measurement of ozone in water requites an awareness of its reactivity, instabiUty, volatility, and the potential effect of interfering substances. To eliminate interferences, ozone sometimes is sparged out of solution by using an inert gas for analysis in the gas phase or on reabsorption in a clean solution. Historically, the most common analytical procedure has been the iodometric method in which gaseous ozone is absorbed by aqueous KI. 

Oxide-supported metals constitute one of the most important classes of heterogeneous catalysts, and for this reason they have been investigated by many techniques adsorption isotherms, IR of chemisorbed molecules, electron microscopy, EXAFS, etc. Flowever, the fact that they have been studied by so many methods proves that no one technique is totally satisfactory. 

These equations hold if an Ignition Curve test consists of measuring conversion (X) as the unique function of temperature (T). This is done by a series of short, steady-state experiments at various temperature levels. Since this is done in a tubular, isothermal reactor at very low concentration of pollutant, the first order kinetic applies. In this case, results should be listed as pairs of corresponding X and T values. (The first order approximation was not needed in the previous ethylene oxide example, because reaction rates were measured directly as the total function of temperature, whereas all other concentrations changed with the temperature.) The example is from Appendix A, in Berty (1997). In the Ignition Curve measurement a graph is made to plot the temperature needed for the conversion achieved. 

Vapor-phase decomposition and collection (Figs 4.16 to 4.18) is a standardized method of silicon wafer surface analysis [4.11]. The native oxide on wafer surfaces readily reacts with isothermally distilled HF vapor and forms small droplets on the hydrophobic wafer surface at room temperature [4.66]. These small droplets can be collected with a scanning droplet. The scanned, accumulated droplets finally contain all dissolved contamination in the scanning droplet. It must be dried on a concentrated spot (diameter approximately 150 pm) and measured against the blank droplet residue of the scanning solution [4.67-4.69]. VPD-TXRF has been carefully evaluated against standardized surface analytical methods. The user is advised to use reliable reference materials [4.70-4.72]. 

CORCON initially assumes that the molten core debris is stratified as a dense oxidic layer on the bottom and a less dense metallic layer on the top. Later, when molten concrete slag dilutes the heavy oxide layer, the lighter oxide layer than the metal layer rises to the top. Each layci is assumed to be isothermal and heat is exchanged between (1) the melt and the concrete, (2) layers of the melt, and (3) the top surface of the melt and the atmosphere above it. When the concrete heats up to about 2500 F, CORCON predicts the release of steam and COj from concrete decomposition. Tile lieat of reaction of the gases reacting with the materials of the melt are calculated. 

In practice, thermal cycling rather than isothermal conditions more frequently occurs, leading to a deviation from steady state thermodynamic conditions and introducing kinetic modifications. Lattice expansion and contraction, the development of stresses and the production of voids at the alloy-oxide interface, as well as temperature-induced compositional changes, can all give rise to further complications. The resulting loss of scale adhesion and spalling may lead to breakaway oxidation " in which linear oxidation replaces parabolic oxidation (see Section 1.10). 

Ward et a/."" have shown that, under cyclical loading, the oxidation rate of steels is similar to that under unstressed isothermal conditions, provided the fatigue stress is below the stress required to exceed the scale failure strain. If, however, the failure strain is exceeded, the oxidation rate is accelerated due to repetitive scale failure, and linear kinetics are observed. 

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