Rigid spheres

Apart from chemical composition, an important variable in the description of emulsions is the volume fraction, outer phase. For spherical droplets, of radius a, the volume fraction is given by the number density, n, times the spherical volume, 0 = Ava nl2>. It is easy to show that the maximum packing fraction of spheres is 0 = 0.74 (see Problem XIV-2). Many physical properties of emulsions can be characterized by their volume fraction. The viscosity of a dilute suspension of rigid spheres is an example where the Einstein limiting law is [2]... 

Since emulsion droplets are not rigid spheres, the coefficient of 0 is around 3-6 for many emulsion systems [3-5], More concentrated emulsions are non-Newtonian depends on shear rate and are thixotropic (ri decreasing with... 

Show that the maximum possible value for is 0.74 in the case of an emulsion consisting of uniform, rigid spheres. 

Carnahan N F and Starling K E 1969 Equation of state for nonattracting rigid spheres J. Chem. Phys. 51 635... 

Stillinger F 1973 Structure in aqueous solutions from the standpoint of scaled particle theory J. Solution Chem. 2 141 Widom B 1967 Intermolecular forces and the nature of the liquid state Sc/e/ ce 375 157 Longuet-Higgins H C and Widom B 1964 A rigid sphere model for the melting of argon Mol. Phys. 8 549... 

We call the correlation time it is equal to 1/6 Dj, where Dj is the rotational diffusion coefficient. The correlation time increases with increasing molecular size and with increasing solvent viscosity, equation Bl.13.11 and equation B 1.13.12 describe the rotational Brownian motion of a rigid sphere in a continuous and isotropic medium. With the Lorentzian spectral densities of equation B 1.13.12. it is simple to calculate the relevant transition probabilities. In this way, we can use e.g. equation B 1.13.5 to obtain for a carbon-13... 

These values enable many structures to be correctly predicted discrepancies arising mainly from the false assumption that ions behave entirely as rigid spheres. Some examples are given in Table 2.7. 

The first of these problems involves relative motion between a rigid sphere and a liquid as analyzed by Stokes in 1850. The results apply equally to liquid flowing past a stationary sphere with a steady-state (subscript s) velocity v or to a sphere moving through a stationary liquid with a velocity -v the relative motion is the same in both cases. If the relative motion is in the vertical direction, we may visualize the slices of liquid described above as consisting of... 

A somewhat similar problem arises in describing the viscosity of a suspension of spherical particles. This problem was analyzed by Einstein in 1906, with some corrections appearing in 1911. As we did with Stokes law, we shall only present qualitative arguments which give plausibility to the final form. The fact that it took Einstein 5 years to work out the bugs in this theory is an indication of the complexity of the formal analysis. Derivations of both the Stokes and Einstein equations which do not require vector calculus have been presented by Lauffer [Ref. 3]. The latter derivations are at about the same level of difficulty as most of the mathematics in this book. We shall only hint at the direction of Lauffer s derivation, however, since our interest in rigid spheres is marginal, at best. 

One thing that is apparent at the outset is that polymer molecules in solution are very different species from the rigid spheres upon which the Einstein theory is based. On the other hand, we saw in the last chapter that the random coil contributes an excluded volume to the second virial coefficient that is at least... 

Equation (9.40) treats the nondraining coil as a rigid sphere and shows that in this limit [r ] (fg M-... 

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. 

FIG. 6-60 Drag coefficient for water drops in air and air hiihhles in water. Standard drag curve is for rigid spheres. (From Clift, Grace, and Weher, Biih-hles. Drops and Particles, Academic, New York, 1978. )... 

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

David W. Taylor Model Basin, Washington, September 1953 Jackson, loc. cit. Valentin, op. cit.. Chap. 2 Soo, op. cit.. Chap. 3 Calderbank, loc. cit., p. CE220 and Levich, op. cit.. Chap. 8). A comprehensive and apparently accurate predictive method has been publisned [Jami-alahamadi et al., Trans ICE, 72, part A, 119-122 (1994)]. Small bubbles (below 0.2 mm in diameter) are essentially rigid spheres and rise at terminal velocities that place them clearly in the laminar-flow region hence their rising velocity may be calculated from Stokes law. As bubble size increases to about 2 mm, the spherical shape is retained, and the Reynolds number is still sufficiently small (<10) that Stokes law should be nearly obeyed. 

Often, Hertz s work [27] is presented in a very simple form as the solution to the problem of a compliant spherical indentor against a rigid planar substrate. The assumption of the modeling make it clear that this solution is the same as the model of a rigid sphere pressed against a compliant planar substrate. In these cases, the contact radius a is related to the radius of the indentor R, the modulus E, and the Poisson s ratio v of the non-rigid material, and the compressive load P by... 

Sephadex G-lO-G-50 behave as rigid spheres and the maximum linear velocity may be calculated by Darcy s law where U = K i p/L) U is the linear velocity... 

Fig. 10. Numerical solutions of the forced-convection mass-transfer equation for the case of irreversible first-order chemical reaction [after Johnson et al. (J4)] (Solid lines— rigid spheres dashed lines—circulating gas bubbles).

Experimental data on nitrogen obtained from spin-lattice relaxation time (Ti) in [71] also show that tj is monotonically reduced with condensation. Furthermore, when a gas turns into a liquid or when a liquid changes to the solid state, no breaks occur (Fig. 1.17). The change in density within the temperature interval under analysis is also shown in Fig. 1.17 for comparison. It cannot be ruled out that condensation of the medium results in increase in rotational relaxation rate primarily due to decrease in free volume. In the rigid sphere model used in [72] for nitrogen, this phenomenon is taken into account by introducing the factor g(ri) into the angular momentum relaxation rate... 

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