Lewis correlation

Accuracy of an Analogy Between Heat and Mass Transfer and the Lewis Correlation for Conditioners and Cooling Towers... 

FIGURE 4.15. Icsl of the Lewis correlation [Eq. (4.14)] for sorption of hydrocarbons on silica gel and two activated carbons. 

This result (the Lewis correlation) has been found empirically to be of more general applicability than the Langmuir equations from which it is derived. Representative data, taken from the work of Lewis et al., showing the approximate conformity of experimental data for sorption of several binary hydrocarbon mixtures on silica gel are shown in Figure 4.15. Combining Eq. (4.14) with Eq. (3.57) and the definition of separation factor (a) [Eq. (1.1)] yields... 

Figure 3.9 Lewis correlation for sorption of hydrocarbons on silica-gel and activated carbons.

The effect of substituents on the rate of the reaction catalysed by different metal ions has also been studied Correlation with resulted in perfectly linear Hammett plots. Now the p-values for the four Lewis-acids are of comparable magnitude and do not follow the Irving-Williams order. Note tlrat the substituents have opposing effects on complexation, which is favoured by electron donating substituents, and reactivity, which is increased by electron withdrawirg substituents. The effect on the reactivity is clearly more pronounced than the effect on the complexation equilibrium. 

So far the four metal ions have been compared with respect to their effect on (1) the equilibrium constant for complexation to 2.4c, (2) the rate constant of the Diels-Alder reaction of the complexes with 2.5 and (3) the substituent effect on processes (1) and (2). We have tried to correlate these data with some physical parameters of the respective metal-ions. The second ionisation potential of the metal should, in principle, reflect its Lewis acidity. Furthermore the values for Iq i might be strongly influenced by the Lewis-acidity of the metal. A quantitative correlation between these two parameters... 

The chemistry of Lewis acid-base adducts (electron-pair donor-acceptor complexes) has stimulated the development of measures of the Lewis basicity of solvents. Jensen and Persson have reviewed these. Gutmann defined the donor number (DN) as the negative of the enthalpy change (in kcal moL ) for the interaction of an electron-pair donor with SbCls in a dilute solution in dichloroethane. DN has been widely used to correlate complexing data, but side reactions can lead to inaccurate DN values for some solvents. Maria and Gal measured the enthalpy change of this reaction... 

Drago and co-workers have correlated a large body of enthalpies of adduct formation in Lewis acid-base systems, including some solvents as reactants, with this four-parameter equation ... 

Nucleophilicity roughly parallels basicity when comparing nucleophiles that have the same reacting atom. For example, OH- is both more basic and more nucleophilic than acetate ion, CH3CO2-, which in turn is more basic and more nucleophilic than H20. Since "nucleophilicity" is usually taken as the affinity of a Lewis base for a carbon atom in the Sfj2 reaction and "basicity" is the affinity of a base for a proton, it s easy to see why there might be a correlation between the two kinds of behavior. 

The correlation of Chao and Seader has been computerized and has been used extensively in the petroleum industry. It provides a useful method for estimating high-pressure vapor-liquid equilibria in hydrocarbon systems over a wide range of temperature, pressure, and composition, and presents a significant improvement over the previously used A -charts first introduced by W. K. Lewis, B. F. Dodge, G. G. Brown, M. Souders, and others (see D6) almost forty years ago. However, the Chao-Seader correlation is unreliable at conditions approaching the critical. Various extensions have been proposed (G2), especially for application at extreme temperatures. 

A comparison of these p/CHB values at constant pK of the bases reveals that the most important factor which determines the correlation between the structure and the hydrogen bonding ability depends on the electronegativity of the acceptor atom in the Lewis bases employed. Thus, the strength of the basicities of the oxygen compounds described above is... 

A fundament of the quantum chemical standpoint is that structure and reactivity are correlated. When using quantum chemical reactivity parameters for quantifying relationships between structure and reactivity one has the advantage of being able to describe the nature of the structural influences in a direct manner, without empirical assumptions. This is especially valid for the so-called Salem-Klopman equation. It allows the differentiation between the charge and the orbital controlled portions of the interaction between reactants. This was shown by the investigation of the interaction between the Lewis acid with complex counterions 18> (see part 4.4). 

A systematic NMR spectroscopic study of these adducts suggests that the steric repulsion between the trimethyl aluminum Lewis acid and the phosphane Lewis base rather than the electronic factors account for the detected changes in the P-NMR spectroscopic chemical shifts (Table 1). The change in the chemical shift (A) of the phosphanes on coordination to AlMe3 has been correlated to the... 

In the Brpnsted picture, the acid is a proton donor, but in the Lewis picture the proton itself is the acid since it has a vacant orbital. A Brpnsted acid becomes, in the Lewis picture, the compound that gives up the actual acid. The advantage of Lewis theory is that it correlates the behavior of many more processes. For example, AICI3 and BF3 are Lewis acids because they have only 6 electrons in the outer shell and have room for 8. Both SnCU and SO3 have eight, but their central elements, not being in the first row of the periodic table, have room for 10 or 12. Other Lewis acids are simple cations, like Ag. The simple reaction A + B- A—B is not very common in organic chemistry, but the scope of the Lewis picture is much larger because reactions of the types... 

The ab initio calculations of various three-electron hemibonded systems [122, 123] indicated that the inclusion of electron correlation corrections is extremely important for the calculation of three-electron bond energies. The Hartree-Fock (HF) error is found to be nonsystematic and always large, sometimes of the same order of magnitude as the bond energy. According to valence bond (VB) and MO theories, the three-electron bond is attributed to a resonance between the two Lewis structures... 

The ionization of benzoic acids in water at 25° was used by Hammett as the standard reaction for the original qp treatment (2a). This reaction and several analogous reactions, e.g., ionization and ester saponification rates of benzoic acids, cinnamic acids, and phenylpropiolic acids, gives ap correlations of relatively high precision. Taft and Lewis classified such reactions in an A category (2f). Reexamination of these A reactions, as well as additional analogous data which have become available subsequently, provided eight reaction series of data of apparently comparable reliability. In the para position, each of these sets of data meets the necessary condition of a minimal basis set... 

Hayash C.I., Shipley N., and Lewis R., Hypotheses that correlate the sequence, structure, and mechanical properties of spider silk proteins, Int. J. Biol. Macromol., 24, 271, 1999. 

The first task is to decide whether the members of a given group are Lewis acids or bases. Then evaluate the relative softness and hardness based on polarizability, taking into account correlations with electronegativity, size, and charge. Refer to the periodic table in assessing the trends. 

Winship IR, Plaa N, Murphy TH (2007) Rapid astrocyte calcium signals correlate with neuronal activity and onset of the hemodynamic response in vivo. J Neurosci 27 6268-6272 Wu MM, Buchanan J, Luik RM, Lewis RS (2006) Ca store depletion causes STIMl to accumulate in ER regions closely associated with the plasma membrane. J Cell Biol 174 803-813 Wyss-Coray T (2006) Inflammation in Alzheimer disease driving force, bystander or beneficial response Nat Med 12 1005-1015... 

Even acetone shows appreciable shifts following contact with metal halides - the magnitude of which correlates with the expected strength of the Lewis acid-base interaction. 

Purcell and coworkers obtained good correlations between the IR and H NMR methods by the use of 1,1,1,3,3,3-hexafluoropropanol and phenol as acids . Taddei and colleagues have reported that with CHCI3 as the donor, a free energy relationship is established between the association constants and the H NMR chemical shift values of CHCI3 in the presence of Lewis bases. However, a non-linear relationship has been observed for several other Lewis bases and CHCI3 by other authors . 

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