Bulk composition

A general prerequisite for the existence of a stable interface between two phases is that the free energy of formation of the interface be positive were it negative or zero, fluctuations would lead to complete dispersion of one phase in another. As implied, thermodynamics constitutes an important discipline within the general subject. It is one in which surface area joins the usual extensive quantities of mass and volume and in which surface tension and surface composition join the usual intensive quantities of pressure, temperature, and bulk composition. The thermodynamic functions of free energy, enthalpy and entropy can be defined for an interface as well as for a bulk portion of matter. Chapters II and ni are based on a rich history of thermodynamic studies of the liquid interface. The phase behavior of liquid films enters in Chapter IV, and the electrical potential and charge are added as thermodynamic variables in Chapter V. 

Generally, Httle is known in advance concerning the degree of homogeneity of most sampled systems. Uniformity, rarely constant throughout bulk systems, is often nonrandom. During the production of thousands of tons of material, size and shape distribution, surface and bulk composition, density, moisture, etc, can vary. Thus, in any bulk container, the product may be stratified into zones of variable properties. In gas and Hquid systems, particulates segregate and concentrate in specific locations in the container as the result of sedimentation (qv) or flotation (qv) processes. 

This equation gives the relation between the bulk compositions of the gas and liquid streams at each level in the tower for conditions in which the operating curve can be approximated by a straight hne. 

Other effects. In addition to the compound formation and ionisation effects which have been considered, it is also necessary to take account of so-called matrix effects. These are predominantly physical factors which will influence the amount of sample reaching the flame, and are related in particular to factors such as the viscosity, the density, the surface tension and the volatility of the solvent used to prepare the test solution. If we wish to compare a series of solutions, e.g. a series of standards to be compared with a test solution, it is clearly essential that the same solvent be used for each, and the solutions should not differ too widely in their bulk composition. This procedure is commonly termed matrix matching. 

Ensure if possible that standard and sample solutions are of similar bulk composition to eliminate matrix effects (matrix matching). 

The penetration theory has been used to calculate the rate of mass transfer across an interface for conditions where the concentration CAi of solute A in the interfacial layers (y = 0) remained constant throughout the process. When there is no resistance to mass transfer in the other phase, for instance when this consists of pure solute A, there will be no concentration gradient in that phase and the composition at the interface will therefore at all Limes lie the same as the bulk composition. Since the composition of the interfacial layers of the penetration phase is determined by the phase equilibrium relationship, it, too. will remain constant anil the conditions necessary for the penetration theory to apply will hold. If, however, the other phase offers a significant resistance to transfer this condition will not, in general, be fulfilled. 

As an example, it may be supposed that in phase 1 there is a constant finite resistance to mass transfer which can in effect be represented as a resistance in a laminar film, and in phase 2 the penetration model is applicable. Immediately after surface renewal has taken place, the mass transfer resistance in phase 2 will be negligible and therefore the whole of the concentration driving force will lie across the film in phase 1. The interface compositions will therefore correspond to the bulk value in phase 2 (the penetration phase). As the time of exposure increases, the resistance to mass transfer in phase 2 will progressively increase and an increasing proportion of the total driving force will lie across this phase. Thus the interface composition, initially determined by the bulk composition in phase 2 (the penetration phase) will progressively approach the bulk composition in phase 1 as the time of exposure increases. 

Effects of condensation are also seen in the bulk compositions of the planets and their satellites. The outer planets, Uranus and Neptune, have overall densities consistent with their formation from icy and stony solids. The satellites of Uranus have typical densities of 1.3g/cm which would tend to indicate a large ice com-... 

A collision with a Mars-sized object may have resulted in the formation of the Earth s moon. Our moon is by no means the largest satellite in the solar system, but it is unusual in that it and the moon of Pluto are the largest moons relative the mass of the planets they orbit. Geochemical studies of returned lunar samples have shown that close similarities exist between the bulk composition of the moon and the Earth s mantle. In particular, the abimdances of sidero-... 

Figure 4. Selectivity in isomerization, dehydrocycllzation and hydrogenolysis (cracking) of Pt/Cu alloys (on Si02). Bulk composition of alloys (% Pt) indicated. (Reproduced with permission from Ref.30. Chem.Soc.London)...

Table III. Variation of the Surface and Bulk Composition of Nl Th Alloy as a Function of Oxidation Conditions...

In very dilute HCl solutions, specifically those with a pH above 5-48, the 4 1 5 phase was found to be insoluble. By contrast, addition of concentrated HCl to the 4 1 5 phase was shown to lead to formation of the 1 1 2 phase (Sorrell, 1977). Below 35wt% HCl, the 4 1 5 phase was found to dissolve congruently. Since the 1 1 2 phase was also found to dissolve congruently in hydrochloric acid solutions with concentrations above 23 wt %, it follows that there is a range of concentrations over which both phases are soluble in aqueous HCl. This behaviour explains why the zinc oxychlorides have proved to be unsatisfactory in attempts to use them as dental cements. The preparation of such cements from concentrated aqueous solutions of ZnClj results in the formation either of the 1 1 2 phase alone or of mixtures of the 4 1 5 and 1 1 2 phases, neither of which is stable in the presence of water. Preparing dental cements from less concentrated solutions also results in the formation of mixed phases, unless the bulk composition has excessive amounts of ZnO present. In these latter cases the cement stability is acceptable but it lacks both a workable consistency and a reasonable working time. 

Singer and Kouda (1988, 1992) confirmed based on the statistical analysis of the distribution of minerals and bulk compositions of altered rocks in the Hokuroku district... 

Bulk compositions of altered andesite. Bulk compositions of altered andesite were obtained by XRF analysis (X-ray fluorescence analysis) (Shikazono et al., 2002). 

Average bulk compositions of samples from seafloor sulfide deposits at seamounts and back-arcs (Scott, 1997)... 

Bulk compositions of midoceanic ridge deposits and back-arc deposits are summarized in Tables 2.16 and 2.17. It is clear that midoceanic ridge ores contain higher amounts of Fe, Mn, Zn, Co, Ni, Se and Pt but lower amounts of Au, Ag, Cu, Pb, Ba, As and Sb compared with back-arc deposits (Tables 2.18 and 2.19). 

For the a-Pt02 system, we find that above an electrode potential of 1.2 V, the (001) surface with bulk composition is most stable and shows only minor relaxation effects (denoted as (OOl)-O in Fig. 5.11a). This surface structure corresponds to experimental UHV measurements of surface oxides on Pt(llO), supported by DFT calculations [Li et al., 2004]. In the case of a very thin surface layer, the layer composition might even be PtO. Increasing the electrode potential above 2.0 V would cause stronger interactions with the surrounding water dipoles and lead to a o -PtO2(011) surface with an enrichment of oxygen (as 0 ) on the surface. 

To evaluate the catalytic activity or to investigate the reaction mechanism, planar electrodes with well-defined characteristics such as surface area, surface and bulk compositions, and crystalline structure have often been examined in acidic electrolyte solutions. An appreciable improvement in CO tolerance has been found at Pt with adatoms such as Ru, Sn, and As [Watanabe and Motoo, 1975a, 1976 Motoo and Watanabe, 1980 Motoo et al., 1980 Watanabe et al., 1985], Pt-based alloys Pt-M (M = Ru, Rh, Os, Sn, etc.) [Ross et al., 1975a, b Gasteiger et al., 1994, 1995 Grgur et al., 1997 Ley et al., 1997 Mukeijee et al., 2004], and Pt with oxides (RuO cHy) [Gonzalez and Ticianelli, 2005 Sughnoto et al., 2006]. 

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