Acid-base interactions measurement acidity

VV -values for bromoform and pyrrole, acidic liquids, against poly(vinyl chloride), an acidic polymer, and dimethyl sulfoxide, a predominantly basic liquid, against polyfmethyl methacrylate), a basic polymer, but large values for the acidic liquids against PMMA and the basic liquid against PVC. 2-Iodoethanol, a bifunctional liquid, showed appreciable -values with both polymers. Despite these results in line with expectations, other results based on wettability measurements are not so clear-cut. For example, Vrbanac [94] found significant apparent acid-base interactions of various aromatic liquids against poly(ethylene), presumably a neutral substrate. 

The study of acid-base interaction is an important branch of interfacial science. These interactions are widely exploited in several practical applications such as adhesion and adsorption processes. Most of the current studies in this area are based on calorimetric studies or wetting measurements or peel test measurements. While these studies have been instrumental in the understanding of these interfacial interactions, to a certain extent the interpretation of the results of these studies has been largely empirical. The recent advances in the theory and experiments of contact mechanics could be potentially employed to better understand and measure the molecular level acid-base interactions. One of the following two experimental procedures could be utilized (1) Polymers with different levels of acidic and basic chemical constitution can be coated on to elastomeric caps, as described in Section 4.2.1, and the adhesion between these layers can be measured using the JKR technique and Eqs. 11 or 30 as appropriate. For example, poly(p-amino styrene) and poly(p-hydroxy carbonyl styrene) can be coated on to PDMS-ox, and be used as acidic and basic surfaces, respectively, to study the acid-base interactions. (2) Another approach is to graft acidic or basic macromers onto a weakly crosslinked polyisoprene or polybutadiene elastomeric networks, and use these elastomeric networks in the JKR studies as described in Section 4.2.1. 

In the spectrophotometric determination of enthalpies of adduct formation, one usually measures the equilibrium concentration of [AB] or [A]. Following a treatment of competing equilibria reported by Tamres 25) consider the effect of base-solvent interaction on this experiment when one investigates the properties corresponding to the free and complexed acid. Now, [AB] can be determined even if the base interacts with the solvent, say CCI4. Again, describing the system by equation ... 

Measurement of Acid-Base Interactions in Group IIIA Containing... 

X ray photoelectron spectroscopy (XPS) is powerful in identifying species present at the surface/interface and atoms or functional groups involved in acid-base interactions [116]. Since XPS measures the kinetic energy of photoelectrons emitted from the core levels of surface atoms upon X ray irradiation of the uppermost atomic layers, it can be used to characterize surface acid sites, in combination with base probe molecules adsorption. 

MEASUREMENT OF ACID-BASE INTERACTIONS IN GROUP IMA CONTAINING SAMPLES... 

The measurements have indicated a linear relation between P (or dP) and pK. The following components were used C H COOH, CH JCOOH, OH,C1COOH, CHCljCOOH, CClgCOOH, N-methylpyperidine, diethylamine, ethylamine. The majority of systems contained benzene as solvent and in two cases dioxan solution was used in order to test the stability of complexes with hydrogen bond, and to confirm the absence of their additional association. The attention was paid to the role of the so-called polar hydrogen bond in acid-base interactions. 

Spectral data (Amax and AE, and e x 10 3) for the pyrimidine bases investigated in a few representative papers are collected in Table XXVIII. The absorption bands are denoted by the capital letters A, B, C, etc. In Table XXVIII we have listed the results of the vacuum ultraviolet measurements by Yamada and Fukutome428 (cf. also ref. 429), who measured the spectra of sublimed films of cytosine, thymine, uracil (and also of guanine and adenine) down to 120 nm at room temperature. Several remarkable absorption peaks were found below 190 nm in addition to the already known ones near 260 and 200 nm. A weak absorption at 230-240 nm in cytosine was not indicated in the sublimed films of the molecule,428 but was visible in the stretched polyvinyl alcohol film spectrum.432 Crewe et al.i3° studied the interactions of fast electrons with the five nucleic acid bases and measured the energy-loss spectra of 20 keV electrons transmitted through thin films of these bases. These last data are also listed in Table XXVIII for comparison with the other spectral findings. 

For decades such adsorption had been assumed to involve dipole interactions and interacting sites were termed "polar." It is quite clear in the above studies that dipoles in the polymers and in the solid surfaces do not contribute measurably to adsorption. Even from carbon tetrachloride, the solvent most favorable to adsorption, the amount of basic polymer (PMMA) that adsorbed onto basic calcium carbonate was only 2.5% of the amount that adsorbed on the same area of silica surface. Similarly, the amount of acidic polymer (CPVC) that adsorbed onto the acidic silica from any of the six solvents was less than 0.2% of the amount that adsorbed from carbon tetrachloride or dichloromethane onto the same area of basic calcium carbonate. It is concluded that adsorption of organic acids or bases from neutral organic solvents onto inorganic solids is governed entirely by acid-base interactions and is quite independent of dipole phenomena. It is therefore proposed that heats of adsorption are actually enthalpies of acid-base interaction and should therefore be subject to the Drago correlation ... 

A study of the interaction of Lewis acids and bases (or electron acceptors and donors) in surface dynamics has led to new insight into interactions with various solid surfaces [26,64,99,100,104,110,130-142], as well as interactions at interfaces between two different substances. It is noted that the acid-base interactions of Lewis, including the orientational properties of charge transfer forces of Mulliken [143], occur between specific (or polar) groups in substances. These interactions are quite dependent on the Stockmayer degree of polarity, <5, [126] as measured by dipole moment in Eq. (58). Furthermore, it can be found that a concept of acids attract bases may be substituted... 

Trivalent gadolinium with f7 configuration has isotropic distribution of electrons and hence cannot produce pseudo contact shift. However, when the Lewis acid-base interaction is partly covalent, the unpaired electron spin density influences the molecular framework of the base and causes an LIS known as contact shift. Gd(III) is used to ascertain the contributions of contact shift to the measured LIS. 

A study of some C—H acids in dimethyl sulfoxide solution led to an acidity order that almost paralleled that found in the gas phase, whereas in protic solvents the order was different [116, 124, 125]. This result highlights the importance of specific solute/solvent interactions such as hydrogen bonding in comparing acid/base equilibria measured in the gas phase and in solution. 

Because of the rather localized negative charge at the phenoHc oxygen atom , the standard dye (44) is capable of specific HBD/HBA and Lewis acid/base interactions. Therefore, in addition to the nonspecific dye/solvent interactions, the betaine dye (44) predominately measures the specific HBD and Lewis acidity of organic solvents. On the other hand, the positive charge of the pyridinium moiety of (44) is delocalized. Therefore, the solvent Lewis basicity will not be registered by the probe molecule (44). If this solvent property is relevant for the system under study, other empirical measures of Lewis basicity should be used cf. Section 7.7. 

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