Physically Significant Parameters

We have now completed the parametrisation of the non-structurally dependent part of the energy-band problem. In the process, we found that for each i quantum number only four parameters D, 9 and were needed to pro- 

The three first parameters in the standard set may be found in terms of the original D, f , and by means of (3.45,46,17), while the fourth parameter gives the width of the energy window (3.53). We prefer to use these standard potential parameters because they depend little upon the choice of E, have physically simple interpretations, and vary in a systematic way from element to element across the periodic table. 

As an example of a set of standard parameters, Table 4.1 lists all the potential-dependent information needed to perform an energy-band calculation for (non-magnetic) chromium metal. In the following, chromium is used as an example when we discuss the physical significance of each of the four potential parameters (4.1). At the end of the chapter we derive free-electron potential parameters, give expressions for the volume derivatives of some se- 

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The idea of an effective Hamiltonian for diatomic molecules was first articulated by Tinkham and Strandberg (1955) and later developed by Miller (1969) and Brown, et al., (1979). The crucial idea is that a spectrum-fitting model (for example Eq. 18 of Brown, et al., 1979) be defined in terms of the minimum number of linearly independent fit parameters. These fit parameters have no physical significance. However, if they are defined in terms of sums of matrix elements of the exact Hamiltonian (see Tables I and II of Brown, et al., 1979) or sums of parameters appropriate to a special limiting case (such as the unique perturber approximation, see Table III of Brown, et al., 1979, or pure precession, Section 5.5), then physically significant parameters suitable for comparison with the results of ab initio calculations are usually derivable from fit parameters. 

Finally we must draw attention to an Interesting and physically significant approximate relation between the numerical magnitudes of the parameters P and 9 in Table 11.1. Their ratio Is given by... 

We shall presently examine the physical significance of the shift factors, since they quantitatively embody the time-temperature equivalence principle. For the present, however, we shall regard these as purely empirical parameters. The following Ust enumerates some pertinent properties of a ... 

As a device for describing the effect of temperature on solution nonideality, it is entirely suitable to think of Eq. (8.115) as offering an alternate notation which accomplishes the desired effect with p and as adjustable parameters. We note, however, that the left-hand side of Eq. (8.115) contains only one such parameter, x, while the right-hand side contains two p and . Does this additional parameter have any physical significance ... 

Although the Pitzer correlations are based on data for pure materials, they may also be used for the calculation of mixture properties. A set of recipes is required relating the parameters T, Pc, and (0 for a mixture to the pure-species values and to composition. One such set is given by Eqs. (2-80) through (2-82) in Sec. 2, which define pseudopa-rameters, so called because the defined values of T, Pc, and (0 have no physical significance for the mixture. 

When i = J, all equations reduce to the appropriate values for a pure species. When i j, these equations define a set of interaction parameters having no physical significance. For a mixture, values of By and dBjj/dT from Eqs. (4-212) and (4-213) are substituted into Eqs. (4-183) and (4-185) to provide values of the mixture second virial coefficient B and its temperature derivative. Values of and for the mixture are then given by Eqs. (4-193) and (4-194), and values of In i for the component fugacity coefficients are given by Eq. (4-196). 

Numerous attempts have been made to develop hybrid methodologies along these lines. An obvious advantage of the method is its handiness, while its disadvantage is an artifact introduced at the boundary between the solute and solvent. You may obtain agreement between experiments and theory as close as you desire by introducing many adjustable parameters associated with the boundary conditions. However, the more adjustable parameters are introduced, the more the physical significance of the parameter is obscured. 

The parameters Ci, t2 were postulated to be dependent only upon the substrate, and d, d2, upon the solvent. A large body of kinetic data, embodying many structural types and leaving groups, was subjected to a statistical analysis. In order to achieve a unique solution, these arbitrary conditions were imposed cj = 3.0 C2 for MeBr Cl = C2 = 1.0 for f-BuCl 3.0 Ci = C2 for PhsCF. Some remarkably successful correlations [calculated vs. experimental log (fc/fco)l were achieved, but the approach appeared to lack physical significance and was not much used. Many years later Peterson et al. - showed a correspondence between Eqs. (8-69) and (8-74) in particular, the very simple result di + d, = T was found. 

Eigure 3.5 presents the dependence of A.S ° on temperature for chymotryp-sinogen denaturation at pH 3. A positive A.S ° indicates that the protein solution has become more disordered as the protein unfolds. Comparison of the value of 1.62 kj/mol K with the values of A.S ° in Table 3.1 shows that the present value (for chymotrypsinogen at 54.5°C) is quite large. The physical significance of the thermodynamic parameters for the unfolding of chymotrypsinogen becomes clear in the next section. 

The physical significance of the parameter n entering into the definition of the Poisson process can be established by noting that, for 8 > ,... 

Innumerable experimental rate measurements of many kinds have been shown to obey the Arrhenius equation (18) or the modified form [k = A T exp (—E/RT)] and, irrespective of any physical significance of the parameters A and E, the approach is an important, established method of reporting and comparing kinetic data. There are, however, grounds for a critical reconsideration for both the methods of application and the theoretical interpretations of observed obedience of experimental data for the reactions of solids to eqn. (18). 

A detailed account of transport phenomena in crystals is outside the scope of the present review, though it is relevant to point out that factors which determine the rate at which reactants penetrate a barrier layer include the numbers, distributions and mobilities of vacancies. Oleinikov et al. [1173] conclude that Arrhenius parameters are devoid of any physical significance if due allowance is not made for imperfection concentration, which may vary with temperature (and a [77]). 

In Equation 1, t is a thermal vibration frequency, U and P are, respectively activation energy and volume whereas c is a local stress. The physical significance and values for these parameters are discussed in Reference 1. Processes (a)-(c) are performed with the help of a Monte-Carlo procedure which, at regular short time intervals, also relaxes the entanglement network to its minimum energy configuration (for more details, see Reference 1). 

But when considered over a wide range of frequencies, the properties of a real electrode do not match those of the equivalent circuits shown in Fig. 12.12 the actual frequency dependence of Z and a does not obey Eq. (12.21) or (12.22). In other words, the actual values of R and or R and are not constant but depend on frequency. In this sense the equivalent circuits described are simplified. In practice they are used only for recording the original experimental data. The values of R and Cj (or R and C ) found experimentally for each frequency are displayed as functions of frequency. In a subsequent analysis of these data, more complex equivalent circuits are explored which might describe the experimental frequency dependence and where the parameters of the individual elements remain constant. It is the task of theory to interpret the circuits obtained and find the physical significance of the individual elements. 

For non-Newtonian fluids, any model parameter with the dimensions or physical significance of viscosity (e.g., the power law consistency, m, or the Carreau parameters r,]co and j/0) will depend on temperature in a manner similar to the viscosity of a Newtonian fluid [e.g., Eq. (3-34)]. 

The good agreement obtained for all data using the modified Froude number signifies the physical significance of the parameter. In fact, the dependence of jet penetration on the two-phase Froude number can be derived theoretically from the buoyancy theory following that of Turner (1973). 

The physical significance of the parameters (or K ) and K is obviously of considerable interest. In the formulation of the model, these are simply arbitrary parameters which define, respectively, the extent of primary and multiple adsorption. For the particular case evaluated above (x=0.5 and xs=l 0) K is approximately constant while appears to decrease exponentially with chain length n. It is expected that, for a given chain length, the parameters and K will both depend on x and X Further comparisons, similar to that given here, will be required to establish the precise correspondence of the parameters used in the two approaches. 

To test the validity of the extended Pitzer equation, correlations of vapor-liquid equilibrium data were carried out for three systems. Since the extended Pitzer equation reduces to the Pitzer equation for aqueous strong electrolyte systems, and is consistent with the Setschenow equation for molecular non-electrolytes in aqueous electrolyte systems, the main interest here is aqueous systems with weak electrolytes or partially dissociated electrolytes. The three systems considered are the hydrochloric acid aqueous solution at 298.15°K and concentrations up to 18 molal the NH3-CO2 aqueous solution at 293.15°K and the K2CO3-CO2 aqueous solution of the Hot Carbonate Process. In each case, the chemical equilibrium between all species has been taken into account directly as liquid phase constraints. Significant parameters in the model for each system were identified by a preliminary order of magnitude analysis and adjusted in the vapor-liquid equilibrium data correlation. Detailed discusions and values of physical constants, such as Henry s constants and chemical equilibrium constants, are given in Chen et al. (11). 

The measurement units of each parameter give a preliminary indication of the nature of these parameters, but for a more precise idea of their chemical and physical significance the reader is referred to the literature7-9. In the present context it is sufficient to bear in mind that most of these empirical parameters can be subdivided into parameters which measure the Lewis acidity (hence, the electrophilic power) and Lewis basicity (hence, the nucleophilic power) of a solvent. 

The ion hopping rate is an apparently simple parameter with a clear physical significance. It is the number of hops per second that an ion makes, on average. As an example of the use of hopping rates, measurements on Na )3-alumina indicate that many, if not all the Na" ions can move and at rates that vary enormously with temperature, from, for example, 10 jumps per second at liquid nitrogen temperatures to 10 ° jumps per second at room temperature. Mobilities of ions may be calculated from Eqn (2.1) provided the number of carriers is known, but it is not possible to measure ion mobilities directly. 

The parameters of this expansion, as well as the number N of Lorentzian functions, are determined (from the experimental data) by a non-linear least squares fit along with statistical tests. It can be noticed that this expansion has no physical meaning but is merely a numerical device allowing for smoothing and interpolation of the experimental data. Nevertheless, this procedure proves to be statistically more significant than the Cole-Cole equation and thus to account much better for the representation of experimental data. The two physically meaningful parameters, i.e., C(0) and (Xo), can then be easily deduced from the quantities involved in (71)... 

Because of the disorder, the bond parameters have no physical significance as they represent only the average values of all the possibilities in the mixed crystal. Therefore it is impossible to deduce the nature of the bonds in the crystal from X-ray diffraction data. 

Until now we have tried to keep aU quantities in dimensional form so their physical significances can be readily appreciated. Here, however, we define groups of parameters that we define as new parameters J and so that the equations look simpler and will be easier to manipulate. 

However, even if there are three steady states, there is stiU the question of whether a steady state is stable even if it is in the physically significant range of parameters. We ask the question, starting the reactor at some initial situation, wiU the reactor eventually approach these solutions Or, starting the reactor near one of the steady states, wiU it remain there To answer this, we must examine the transient equations. 

Pa K and the unit of q is K/s. Clearly there is some arbitrariness in this definition, especially in the value of 10 Pa K, which does not correspond to any physically significant property. Hence, some authors have adjusted this parameter slightly to make the rheological definition to be the same as other definitions. 

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