Proportional models

If the pore-mechanism applies, the rate of permeation should be related to the probability at which pores of sufficient size and depth appear in the bilayer. The correlation is given by the semi-empirical model of Hamilton and Kaler [150], which predicts a much stronger dependence on the thickness d of the membrane than the solubility-diffusion model (proportional to exp(-d) instead of the 1 Id dependence given in equation (14)). This has been confirmed for potassium by experiments with bilayers composed of lipids with different hydrocarbon chain lengths [148], The sensitivity to the solute size, however, is in the model of Hamilton and Kaler much less pronounced than in the solubility-diffusion model. 

Another idealized model is the localized adsorption, a rationale for the Langmuir isotherm. Now the surface is supposed to consist solely of identical distinct adsorption sites with the number concentration Ca in cm-2 the latter has a definite value for each particular adsorbent-adsorbate system. Let the fractional surface coverage be 6 = ca/Ca. In such a model, proportional to cg is ca/Ca(l - 6), the surface concentration divided by the concentration of free adsorption sites. Hence, strictly speaking, the corresponding dimensional constant fc c, now in cm3, is ... 

Yet some of the drawbacks of age reduction models proportional to time or age (summarized above) are not tackled by this extended effective age model. This work aims to include in effective age models two important, intuitive concepts, which have been overlooked so far in modeling imperfect maintenance actions ... 

Returning to Eq. XI-4, wiA C2 replacing 02, at low concentrations 112 will be proportional to C2 with a slope n b. At sufficiently high concentrations /I2 approaches the limiting value n . Thus is a measure of the capacity of the adsorbent and b of the intensity of the adsorption. In terms of the ideal model, nf should not depend on temperature, while b should show an exponential... 

Al.6.101) are precisely equivalent to these derivatives the rate of change of a population is proportional to the instantaneous coherence, a relationship which can be observed already in the vector precession model of the two-level system ( section Al.6.2.3). 

The unimolecular rate law can be justified by a probabilistic argument. The number (A Vdc x dc) of particles which react in a time dt is proportional both to this same time interval dt and to the number of particles present (A Vc x c). However, this probabilistic argument need not always be valid, as illustrated in figure A3.4.2 for a sunple model [20] ... 

Carpick et al [M] used AFM, with a Pt-coated tip on a mica substrate in ultraliigh vacuum, to show that if the defonnation of the substrate and the tip-substrate adhesion are taken into account (the so-called JKR model [175] of elastic adliesive contact), then the frictional force is indeed proportional to the contact area between tip and sample. Flowever, under these smgle-asperity conditions, Amontons law does not hold, since the statistical effect of more asperities coming into play no longer occurs, and the contact area is not simply proportional to the applied load. 

Figure B2.3.13. Model 2-level system describing molecular optical excitation, with first-order excitation rate constant W 2 proportional to the laser power, and spontaneous (first-order rate constant 21) stimulated (first-order rate constant 1 2 proportional to the laser power) emission pathways.

Monte Carlo simulations generate a large number of confonnations of tire microscopic model under study that confonn to tire probability distribution dictated by macroscopic constrains imposed on tire systems. For example, a Monte Carlo simulation of a melt at a given temperature T produces an ensemble of confonnations in which confonnation with energy E. occurs witli a probability proportional to exp (- Ej / kT). An advantage of tire Monte Carlo metliod is tliat, by judicious choice of tire elementary moves, one can circumvent tire limitations of molecular dynamics techniques and effect rapid equilibration of multiple chain systems [65]. Flowever, Monte Carlo... 

Despite the fact Chat there are no analogs of void fraction or pore size in the model, by varying the proportion of dust particles dispersed among the gas molecules it is possible to move from a situation where most momentum transfer occurs in collisions between pairs of gas molecules, Co one where the principal momentum transfer is between gas molecules and the dust. Thus one might hope to obtain at least a physically reasonable form for the flux relations, over the whole range from bulk diffusion to Knudsen streaming. 

Since the void fraction distribution is independently measurable, the only remaining adjustable parameters are the A, so when surface diffusion is negligible equations (8.23) provide a completely predictive flux model. Unfortunately the assumption that (a) is independent of a is unlikely to be realistic, since the proportion of dead end pores will usually increase rapidly with decreasing pore radius. 

Hite s treatment is based on equations (5.18) and (5.19) which describe the dusty gas model at the limit of bulk diffusion control and high permeability. Since temperature Is assumed constant, partial pressures are proportional to concentrations, and it is convenient to replace p by cRT, when the flux equations become... 

When developing the dusty gas model flux relations in Chapter 3, the thermal diffusion contributions to the flux vectors, defined by equations (3.2), were omitted. The effect of retaining these terms is to augment the final flux relations (5.4) by terms proportional to the temperature gradient. Specifically, equations (5.4) are replaced by the following generalization... 

Li) he so-called distance-dependent dielectric models. The simplest implementation of a dis-i.iiice-dependent dielectric is to make the relative permittivity proportional to the distance. Tine interaction energy between two charges qi and qj then becomes ... 

One distmbing finding was thaf a significant proportion of the models contained errors, ev including amino acids with the wrong stereochemistry. In addition, significant dcviatio... 

Ire boundary element method of Kashin is similar in spirit to the polarisable continuum model, lut the surface of the cavity is taken to be the molecular surface of the solute [Kashin and lamboodiri 1987 Kashin 1990]. This cavity surface is divided into small boimdary elements, he solute is modelled as a set of atoms with point polarisabilities. The electric field induces 1 dipole proportional to its polarisability. The electric field at an atom has contributions from lipoles on other atoms in the molecule, from polarisation charges on the boundary, and where appropriate) from the charges of electrolytes in the solution. The charge density is issumed to be constant within each boundary element but is not reduced to a single )oint as in the PCM model. A set of linear equations can be set up to describe the electrostatic nteractions within the system. The solutions to these equations give the boundary element harge distribution and the induced dipoles, from which thermodynamic quantities can be letermined. 

Each of these tools has advantages and limitations. Ab initio methods involve intensive computation and therefore tend to be limited, for practical reasons of computer time, to smaller atoms, molecules, radicals, and ions. Their CPU time needs usually vary with basis set size (M) as at least M correlated methods require time proportional to at least M because they involve transformation of the atomic-orbital-based two-electron integrals to the molecular orbital basis. As computers continue to advance in power and memory size, and as theoretical methods and algorithms continue to improve, ab initio techniques will be applied to larger and more complex species. When dealing with systems in which qualitatively new electronic environments and/or new bonding types arise, or excited electronic states that are unusual, ab initio methods are essential. Semi-empirical or empirical methods would be of little use on systems whose electronic properties have not been included in the data base used to construct the parameters of such models. 

Of the various parameters introduced in the Eyring theory, only r—or j3, which is directly proportional to it-will be further considered. We shall see that the concept of relaxation time plays a central role in discussing all the deformation properties of bulk polymers and thus warrants further examination, even though we have introduced this quantity through a specific model. 

In connection with a discussion of the Eyring theory, we remarked that Newtonian viscosity is proportional to the relaxation time [Eqs. (2.29) and (2.31)]. What is needed, therefore, is an examination of the nature of the proportionality between the two. At least the molecular weight dependence of that proportionality must be examined to reach a conclusion as to the prediction of the reptation model of the molecular weight dependence of viscosity. 

---