Sphere factor

If F is unknown, the sphere factor has to be determined as described for the Hoppler viscosimeter via calibration measurements. An exact evaluation of the state of flow is not possible. When a doubling of the traction does not lead to half the measuring time, it is very likely that the sample shows a non-Newtonian flow behavior, since the product of force and time should be constant for a Newtonian fluid. Advantages of the viscobalance are the great measuring range and the possibility to examine nontransparent and high viscous fluids of unknown density. 

Force, sphere factor of the visco-balance Figure... 

Reference 115 gives the diffusion coefficient of DTAB (dodecyltrimethylammo-nium bromide) as 1.07 x 10" cm /sec. Estimate the micelle radius (use the Einstein equation relating diffusion coefficient and friction factor and the Stokes equation for the friction factor of a sphere) and compare with the value given in the reference. Estimate also the number of monomer units in the micelle. Assume 25°C. 

The solution was first obtained independently by Wertheim [32] and Thiele [33] using Laplace transfonns. Subsequently, Baxter [34] obtained the same solutions by a Wiener-Hopf factorization teclmique. This method has been generalized to charged hard spheres. 

This treatment may be extended to spheres core-shell structure. If the core density is p 0 to fp the shell density is p2 in the range o density of the surrounding medium is Pq, th of the structure factor becomes... 

For many practically relevant material/environment combinations, thennodynamic stability is not provided, since E > E. Hence, a key consideration is how fast the corrosion reaction proceeds. As for other electrochemical reactions, a variety of factors can influence the rate detennining step. In the most straightforward case the reaction is activation energy controlled i.e. the ion transfer tlrrough the surface Helmholtz double layer involving migration and the adjustment of the hydration sphere to electron uptake or donation is rate detennining. The transition state is... 

The simplest approach to computing the pre-exponential factor is to assume that molecules are hard spheres. It is also necessary to assume that a reaction will occur when two such spheres collide in order to obtain a rate constant k for the reactants B and C as follows ... 

The discrepancy between the pore area or the core area on the one hand and the BET area on the other is proportionately larger with silica than with alumina, particularly at the higher degrees of compaction. The fact that silica is a softer material than alumina, and the marked reduction In the BET area of the compact as compared with that of the loose material, indicates a considerable distortion of the particles, with consequent departure of the pore shape from the ideal of interstices between spheres. The factor R for cylinders (p. 171), used in the conversion to pore area in the absence of a better alternative, is therefore at best a crude approximation. 

Unless extremely high potentials are to be used, the intense electric fields must be formed by making the radius of curvature of the needle tip as small as possible. Field strength (F) is given by Equation 5.1 in which r is the radius of curvature and k is a geometrical factor for a sphere, k = 1, but for other shapes, k < 1. Thus, if V = 5000 V and r = 10 m, then, for a sphere, F = 5 x 10 V/m with a larger curvature of, say, Iff m (0.1 mm), a potential of 500,000 V would have to be applied to generate the same field. In practice, it is easier to produce and apply 5000 V rather than 500,000 V. 

The spherical geometry assumed in the Stokes and Einstein derivations gives the highly symmetrical boundary conditions favored by theoreticians. For ellipsoids of revolution having an axial ratio a/b, friction factors have been derived by F. Perrin, and the coefficient of the first-order term in Eq. (9.9) has been derived by Simha. In both cases the calculated quantities increase as the axial ratio increases above unity. For spheres, a/b = 1. 

The first term reflects the fact that, in practice, volume fraction is not the concentration unit ordinarily used. Even for nonsolvated spheres, some factors will modify the Einstein 2.5 term merely as a result of reconciling practical concentration units with

[Pg.597]

We shall see in Sec. 9.10 that sedimentation and diffusion data yield experimental friction factors which may also be described-by the ratio of the experimental f to fQ, the friction factor of a sphere of the same mass-as contours in solvation-ellipticity plots. The two different kinds of contours differ in detailed shape, as illustrated in Fig. 9.4b, so the location at which they cross provides the desired characterization. For the hypothetical system shown in Fig. 9.4b, the axial ratio is about 2.5 and the protein is hydrated to the extent of about 1.0 g water (g polymer)". ... 

This concludes our discussion of the viscosity of polymer solutions per se, although various aspects of the viscous resistance to particle motion continue to appear in the remainder of the chapter. We began this chapter by discussing the intrinsic viscosity and the friction factor for rigid spheres. Now that we have developed the intrinsic viscosity well beyond that first introduction, we shall do the same (more or less) for the friction factor. We turn to this in the next section, considering the relationship between the friction factor and diffusion. 

Rigid particles other than unsolvated spheres. It is easy to conclude qualitatively that either solvation or ellipticity (or both) produces a friction factor which is larger than that obtained for a nonsolvated sphere of the same mass. This conclusion is illustrated in Fig. 9.10, which shows the swelling of a sphere due to solvation and also the spherical excluded volume that an ellipsoidal particle requires to rotate through all possible orientations. 

The particle can be assumed to be spherical, in which case M/N can be replaced by (4/3)ttR P2, and f by 671770R- In this case the radius can be evaluated from the sedimentation coefficient s = 2R (p2 - p)/9t7o. Then, working in reverse, we can evaluate M and f from R. These quantities are called, respectively, the mass, friction factor, and radius of an equivalent sphere, a hypothetical spherical particle which settles at the same rate as the actual molecule. 

Like e, t is the product of two contributions the concentration N/V of the centers responsible for the effect and the contribution per particle to the attenuation. It may help us to become oriented with the latter to think of the scattering centers as opaque spheres of radius R. These project opaque cross sections of area ttR in the light path. The actual cross section is then multiplied by the scattering efficiency factor optical cross... 

Sphericity. Sphericity, /, is a shape factor defined as the ratio of the surface area of a sphere the volume of which is equal to that of the particle, divided by the actual surface area of the particle. 

Shape. Metal powder particles are produced in a variety of shapes, as shown in Figure 4. The desked shape usually depends to a large extent on the method of fabrication. Shape can be expressed as a deviation from a sphere of identical volume, or as the ratio between length, width, and thickness of a particle, as weU as in terms of some shape factors. 

R = factor for electrical relaxation D = dielectric constant of medium F = factor for size of spheres and = zeta potential. 

Solid sphere form with correction factor E... 

TABLE 6-9 Wall Correction Factor for Rigid Spheres in Stokes Law Region... 

Particle shape factor = (surface of sphere)/ Dimensionless Dimensionless Dimensionless... 

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