Refractive index, interactions between

Coleman et al. 2471 reported the spectra of different proportions of poly(vinylidene fluoride) PVDF and atactic poly(methyl methacrylate) PMMA. At a level of 75/25 PVDF/PMMA the blend is incompatible and the spectra of the blend can be synthesized by addition of the spectra of the pure components in the appropriate amounts. On the other hand, a blend composition of 39 61 had an infrared spectrum which could not be approximated by absorbance addition of the two pure spectra. A carbonyl band at 1718cm-1 was observed and indicates a distinct interaction involving the carbonyl groups. The spectra of the PVDF shows that a conformational change has been induced in the compatible blend but only a fraction of the PVDF is involved in the conformational change. Allara M9 250 251) cautioned that some of these spectroscopic effects in polymer blends may arise from dispersion effects in the difference spectra rather than chemical effects. Refractive index differences between the pure component and the blend can alter the band shapes and lead to frequency shifts to lower frequencies and in general the frequency shifts are to lower frequencies. 

Dipolar and induced dipolar interactions cause this general and fundamental attractive interaction. The character of this interaction is comparatively weak and comparatively long-range in order. The interaction is, in principal, proportional to the refractive index difference between the phases. The difference between oil and water is large and only fairly high concentrations of dissolved material reduce the van der Waals interactions significantly. 

Solvents exert their influence on organic reactions through a complicated mixture of all possible types of noncovalent interactions. Chemists have tried to unravel this entanglement and, ideally, want to assess the relative importance of all interactions separately. In a typical approach, a property of a reaction (e.g. its rate or selectivity) is measured in a laige number of different solvents. All these solvents have unique characteristics, quantified by their physical properties (i.e. refractive index, dielectric constant) or empirical parameters (e.g. ET(30)-value, AN). Linear correlations between a reaction property and one or more of these solvent properties (Linear Free Energy Relationships - LFER) reveal which noncovalent interactions are of major importance. The major drawback of this approach lies in the fact that the solvent parameters are often not independent. Alternatively, theoretical models and computer simulations can provide valuable information. Both methods have been applied successfully in studies of the solvent effects on Diels-Alder reactions. 

Fundamental Limitations to Beers Law Beer s law is a limiting law that is valid only for low concentrations of analyte. There are two contributions to this fundamental limitation to Beer s law. At higher concentrations the individual particles of analyte no longer behave independently of one another. The resulting interaction between particles of analyte may change the value of 8. A second contribution is that the absorptivity, a, and molar absorptivity, 8, depend on the sample s refractive index. Since the refractive index varies with the analyte s concentration, the values of a and 8 will change. For sufficiently low concentrations of analyte, the refractive index remains essentially constant, and the calibration curve is linear. 

Equations (10.17) and (10.18) show that both the relative dielectric constant and the refractive index of a substance are measurable properties of matter that quantify the interaction between matter and electric fields of whatever origin. The polarizability is the molecular parameter which is pertinent to this interaction. We shall see in the next section that a also plays an important role in the theory of light scattering. The following example illustrates the use of Eq. (10.17) to evaluate a and considers one aspect of the applicability of this quantity to light scattering. 

The theory of counterion condensation is implicit in Oosawa (1957) but the term was coined later (Imai, 1961). The phenomenon was demonstrated by Ikegami (1964), using refractive index measurements of the interaction between sodium and polyacrylate ions. It has since been confirmed for many mono-, di- and trivalent counterions and polyionic species (Manning, 1979). 

It is important to know the influence of the physicochemical parameters of the mobile phase (dipole moment, dielectric constant, and refractive index) on solvent strength and selectivity. The main interactions in planar chromatography between the molecules of the mobile phases and those of solutes are caused by dispersion forces related to the refractive index, dipole-dipole forces related to the dipole moment, induction forces related to a permanent dipole and an induced one, hydrogen bonding, and dielectric interactions related to the dielectric constant. Solvent strength depends mainly on the dipole moment of the mobile phase, whereas the solvent selectivity depends on the dielectric constant of the mobile phase. 

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