Solid inhomogeneity

Gernez was the first to suggest that crevices in solids kept in suspension by the Brownian motion may act as nucleation sites.54 jn 1944 Harvey et al suggested that small amounts of gas can be trapped in conical crevices in solid inhomogeneities present in liquids.55 In view of its general appearance, this model has received considerable attention. Solvents such as water contain numerous small... 

Figure 34.6 Left) Surface SEM of polished Lao.sSro.sCoOs-g support prepared by colloidal filtration of untreated commercial powder followed by sintering at 1020°C. This cross section clearly demonstrates the presence of solid inhomogeneity and a hollow sphere that was formed in spray roasting of the powder. Right) Defect in 10-p.m-thick Lao.5Sro.5Co03 8 membrane prepared by pulsed laser deposition on support as shown right. A surface defect has caused a large, nonselective pinhole.

However, before extrapolating the arguments from the gross patterns through the reactor for homogeneous reactions to solid-catalyzed reactions, it must be recognized that in catalytic reactions the fluid in the interior of catalyst pellets may diSer from the main body of fluid. The local inhomogeneities caused by lowered reactant concentration within the catalyst pellets result in a product distribution different from that which would otherwise be observed. 

The development of tunable, narrow-bandwidtli dye laser sources in tire early 1970s gave spectroscopists a new tool for selectively exciting small subsets of molecules witliin inhomogeneously broadened ensembles in tire solid state. The teclmique of fluorescence line-narrowing [1, 2 and 3] takes advantage of tire fact tliat relatively rigid chromophoric... 

Direct sampling of solids may be carried out using laser ablation. In this technique a high-power laser, usually a pulsed Nd-YAG laser, is used to vaporize the solid, which is then swept into the plasma for ionization. Besides not requiring dissolution or other chemistry to be performed on the sample, laser ablation ICPMS (LA-ICPMS) allows spatial resolution of 20-50 pm. Depth resolution is 1-10 pm per pulse. This aspect gives LA-ICPMS unique dit nostic capabilities for geologic samples, surface features, and other inhomogeneous samples. In addition minimal, or no, sample preparation is required. 

There are advantages to direct solid sampling. Sample preparation is less time consuming and less prone to contamination, and the analysis of microsamples is more straightforward. However, calibration may be more difficult than with solution samples, requiring standards that are matched more closely to the sample. Precision is typically 5% to 10% because of sample inhomogeneity and variations in the sample vaporization step. 

Equations (2.9) and (2.10) are representative of all isotropic, homogeneous solids, regardless of the stress-strain relations of a solid. What is strongly materials specific and uncertain is the appropriate value for shear stress, particularly if materials are in an inelastic condition or anisotropic, inhomogeneous properties are involved. The limiting shear stress controlled by strength is termed r. ... 

Nevertheless, as response data have accumulated and the nature of the porous deformation problems has crystallized, it has become apparent that the study of such solids has forced overt attention to issues such as lack of thermodynamic equilibrium, heterogeneous deformation, anisotrophic deformation, and inhomogeneous composition—all processes that are present in micromechanical effects in solid density samples but are submerged due to continuum approaches to mechanical deformation models. 

Of course, the above discussion apphes only to systems exhibiting domain wall structure, i.e., to weakly inhomogeneous phases formed on surfaces with low corrugation of the gas-solid potential and characterized by the presence of more then one type of equivalent sublattices. When this is not the case, i.e., when the dense incommensurate phase can be considered to be... 

The concentrations of reactants are of little significance in the theoretical treatment of the kinetics of solid phase reactions, since this parameter does not usually vary in a manner which is readily related to changes in the quantity of undecomposed reactant remaining. The inhomogeneity inherent in solid state rate processes makes it necessary to consider always both numbers and local spatial distributions of the participants in a chemical change, rather than the total numbers present in the volume of reactant studied. This is in sharp contrast with methods used to analyse rate data for homogeneous reactions in the liquid or gas phases. 

M) were typically used for such a comparison to eliminate the influence of possible differences in the inner-layer capacities. However, C of different solid metals, as well as of liquid Ga, In(Ga), and Tl(Ga) alloys have shown such a large variation that this approach can hardly be considered as appropriate. It should be noted that the error in C, which for solid electrodes is much higher than for liquid electrodes, increases with the decrease ofcei further, as shown later (Section II.2 (iv)), the effects of surface crystallographic inhomogeneity also prove especially appreciable.24 67 74... 

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