Properties of the solid

The properties of the solids most commonly encountered are tabulated. An important problem arises for petroleum fractions because data for the freezing point and enthalpy of fusion are very scarce. The MEK (methyl ethyl ketone) process utilizes the solvent s property that increases the partial fugacity of the paraffins in the liquid phase and thus favors their crystallization. The calculations for crystallization are sensitive and it is usually necessary to revert to experimental measurement. 

Some aspects of adsorption on oxides and other semiconductors can be treated in terms of the electrical properties of the solid, and these are reviewed briefly here. More details can be found in Refs. 84 and 182. 

Many of the Vargaftik values also appear in Ohse, R. W, Handbook of Thetmodynamic and Ttanspoti Ftopetiies of Alkali Metals, Blackwell Sci. Pubs., Oxford, 1985 (1020 pp.). This source contains superheat data. Saturation and superheat tables and a diagram to 30 bar, 1650 K are given by Reynolds, W. C., Thetmodynamic Fropetiies in S.I., Stanford Univ. publ., 1979 (173 pp.). For a Mollier diagram from 0.1 to 250 psia, 1300 to 2700°R, see Weatherford, W. D., J. C. Tyler, et al., WADD-TR-61-96, 1961. An extensive review of properties of the solid and the saturated liquid is given by Alcock, C. B., M. W. Chase, et al.,y. Fhys. Chem. Ref Data, 23, 3 (1994) 385-497. 

Mixing of sohds is an important unit operation in the production of solids with consistent properties. A number of properties of the solid particles influence the mixing process, the design, and selection of mixing equipment. The second subsection elaborates on the theoiy of mixing, types of mixing equipment, and their operation. 

Mixed liberated particles can be separated from each other by flotation if there are sufficient differences in their wettability. The flotation process operates by preparing a water suspension of a mixture of relatively fine-sized particles (smaller than 150 micrometers) and by contacting the suspension with a swarm of air bubbles of air in a suitably designed process vessel. Particles that are readily wetted by water (hydrcmhiric) tend to remain in suspension, and those particles not wetted by water (hydrophobic) tend to be attached to air bubbles, levitate (float) to the top of the process vessel, and collect in a froth layer. Thus, differences in the surface chemical properties of the solids are the basis for separation by flotation. 

The thermodynamic properties of the solid silicates show the expected entropy change of formation from the constituent oxides of nearly zero, which is typical of the reaction type... 

The structure of the cake formed and, consequently, its resistance to liquid flow depends on the properties of the solid particles and the liquid phase suspension, as well as on the conditions of filtration. Cake structure is first established by hydrodynamic factors (cake porosity, mean particle size, size distribution, and particle specific surface area and sphericity). It is also strongly influenced by some factors that can conditionally be denoted as physicochemical. These factors are ... 

The heat-sensitive properties of the solid or liquid 4. Corrosive nature of solids and liquids... 

In addition to these micromechanical considerations, low pressure shock compression of porous powder compacts has distinctive features not encountered in low pressure solid density samples. Basically, the sample is dominated by the pores, and the wavespeed at pressures less than those required to crush the sample to solid density is unusually low and is little dependent on the properties of the solid. 

All magnitudes depending on the properties of the solid have now vanished, and w will therefore not depend on the condition of the latter. 

V is the volume, and F is a factor of proportionality, which is calculable from the elastic properties of the solid. The connection with elasticity was in fact suspected by Sutherland in 1910 (Phil, May., 20, 657), who found that the infra-red frequency of a solid was of the same order as the frequency of an elastic transversal vibration with a wave length equal to the distance between two neighbouring atoms. To every degree of freedom Debye assigns an amount of energy ... 

The Debye temperature, can be calculated from the elastic properties of the solid. Required are the molecular weight, molar volume, compressibility, and Poisson s ratio.11 More commonly, do is obtained from a fit of experimental heat capacity results to the Debye equation as shown above. Representative values for 9o are as follows ... 

The concept of a characteristic reaction temperature must, therefore, be accepted with considerable reservation and as being of doubtful value since the reactivity of a crystalline material cannot readily be related to other properties of the solid. Such behaviour may at best point towards the possible occurrence of common controlling factors in the reaction, perhaps related to the onset of mobility, e.g. melting of one component or eutectic formation, onset of surface migration or commencement of bulk migration in a barrier phase. These possibilities should be investigated in detail before a mechanism can be formulated for any particular chemical change. 

When an industrial pipeline is to be designed, there will be no a priori way of knowing what the in-line concentration of solids or the slip velocity will be. In general, the rate at which solids are to be transported will be specified and it will be necessary to predict the pressure gradient as a function of the properties of the solid particles, the pipe dimensions and the flow velocity. The main considerations will be to select a pipeline diameter, such that the liquid velocity and concentrations of solids in the discharged mixture will give acceptable pressure drops and power requirements and will not lead to conditions where the pipeline is likely to block. 

Table 5.3. Physical properties of the solids used for pneumatic conveying(77j...

It is thus clear from the previous discussion that the absolute electrode potential is not a property of the electrode material (as it does not depend on electrode material) but is a property of the solid electrolyte and of the gas composition. To the extent that equilibrium is established at the metal-solid electrolyte interface the Fermi levels in the two materials are equal (Fig. 7.10) and thus eU 2 (abs) also expresses the energy of transfering an electron from the Fermi level of the YSZ solid electrolyte, in equilibrium with po2=l atm, to a point outside the electrolyte surface. It thus also expresses the energy of solvation of an electron from vacuum to the Fermi level of the solid electrolyte. 

Equation (7.32) underlines the pinning of the Fermi levels of metal electrodes with the solid electrolyte and reminds the fact that the absolute electrode potential is a property of the solid electrolyte and of the gaseous composition but not of the electrode material.21... 

The description derived above gives useful insight into the general characteristics of the band structure in solids. In reality, band structure is far more complex than suggested by Fig. 6.16, as a result of the inclusion of three dimensions, and due to the presence of many types of orbitals that form bands. The detailed electronic structure determines the physical and chemical properties of the solids, in particular whether a solid is a conductor, semiconductor, or insulator (Fig. 6.17). 

In the first chapter, we defined the nature of a solid in terms of its building blocks plus its structure and symmetry. In the second chapter, we defined how structures of solids are determined. In this chapter, we will examine how the solid actually occurs in Nature. Consider that a solid is made up of atoms or ions that are held together by covalent/ionic forces. It is axiomatic that atoms cannot be piled together and forced to form a periodic structure without mistakes being made. The 2nd Law of Thermodynamics demands this. Such mistakes seriously affect the overall properties of the solid. Thus, defeets in the lattice are probably the most important aspect of the solid state since it is impossible to avoid defects at the atomistic level. Two factors are involved ... 

What we mean by this is that the chemical properties of the solid are not deternfined solely by its structure but also by the nature of its chemical composition and in particular by any defects that may be present. We will find that both physical and chemical properties of a solid are largely determined by the type and nature of defects present. It is axiomatic in inorganic chemistry that ... 

Note that "b" in this diagram is the same as that in 3.1.8. Because edge and volume defects propagate throughout the lattice, they affect the physical properties of the solid, whereas it is the point defects that affect the chemical properties of the solid. These latter properties include electrical and resistive, optical and reactivity properties of solids. Thus, we can now classify directs in solids as ... 

It is the intrinsic defects that have the most interest for us, since they affect the chemical properties of the solid while extrinsic defects havelittle effect. Extrinsic defects are the proper study for those interested in the mechanics of solids, particularly metals. 

Before we proceed to analyze defect reactions by a mathematical approach, let us consider an applications of solid state chemistry. In this example, the effect of a defect on the properties of the solid is described. 

From the previous results, it has been proven that the nature of the support, although it has no significant influence on the Pd electronic properties, modifies the catalytic properties of the solids To permit a better understanding of these supports effects, the surface properties of the supports (in the presence of the metal) have been studied, in particular the acidic properties and the oxygen mobilities. The A1203 and Z1O2 supports have been mainly onsidered. 

Solid-Fluid Equilibria The solubility of the solid is very sensitive to pressure and temperature in compressible regions, where the solvent s density and solubility parameter are highly variable. In contrast, plots of the log of the solubility versus density at constant temperature often exhibit fairly simple linear behavior (Fig. 20-19). To understand the role of solute-solvent interactions on sofubilities and selectivities, it is instructive to define an enhancement factor E as the actual solubihty divided by the solubility in an ideal gas, so that E = ysP/Pf, where P is the vapor pressure. The solubilities in CO2 are governed primarily by vapor pressures, a property of the solid... 

Doyen [158] was one who theoretically examined the reflection of metastable atoms from a solid surface within the framework of a quantum- mechanical model based on the general properties of the solid body symmetry. From the author s viewpoint the probability of metastable atom reflection should be negligibly small, regardless of the chemical nature of the surface involved. However, presence of defects and inhomogeneities of a surface formed by adsorbed layers should lead to an abrupt increase in the reflection coefficient, so that its value can approach the relevant gaseous phase parameter on a very inhomogeneous surface. 

The progress of this category of reactions is expected to depend on the composition of the materials within the phase as well as the temperature and pressure of the system. The rate of homogeneous reaction should not be affected by the shape of the container, the surface properties of the solid materials in contact with the phase, and the diffusion characteristics of the fluid. Thus the rate of reaction of component i may be expressed as... 

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