Interaction Acid-Base

Conventional or Brpnsted acids are donors of protons (hydrogen ions H+) and the bases are proton acceptors. The concept dates from 1923. In 1938, G.N. Lewis proposed a broader definition in that an acid is an electron acceptor and a base is an electron donor. 

Boron trifluoride is an example of a Lewis acid and ammonia is a Lewis base. Ammonia is also a Brpnsted base, but boron trifluoride is not a Brpnsted acid. 

Because of the low position of boron in the periodic table, BF3 is electron deficient, which means that it has an sp orbital containing no electrons. In ammonia, there is a non-bonded sp orbital but this now contains two electrons. The two molecules join together by the two electrons being shared as shown in Fig. 8 heat is liberated. 

Lewis acids and bases have attracted much attention in adhesion science in recent years. The strengths of Lewis acids and bases can be obtained from their heats of reaction (-A/f) in poorly solvating solvents (usually hexane, cyclohexane or tetrachloromethane). The heats are related to aiid Ca which are empirical param- 

F a aiid are considered to be the susceptibiUties of the acid and base to undergo electrostatic interactions, and Ca and Cg are their susceptibilities to form covalent bonds. The heats of reaction can be measured by direct calorimetry or from shifts in IR spectra. An example of the latter is the shift in the OH stretching frequency of phenols (Av), when they react with amines in tetrachloromethane or tetrachloroethene, which is given by Eq. (4) [2]. 

A concept that has become increasingly popular is that of acid-base interactions at interfaces. In this definition, acid-base is not confined to the older Bronsted acid-base concepts, but includes the broader concept of donor-acceptor interactions, as would be included in the Lewis acid-base concept. Thus phenomena ranging from Bronsted acid-base interactions to hydrogen bonding and to tt-donor-tt-acceptor interactions are included in the concept of acid-base interactions. 

The first discussion of acid-base interactions in adhesion science was due to Bolger and Micheals. These authors described Bronsted-Lowrey interactions at oxide/ organic interfaces by means of standard equilibrium 

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Until surface contact, the force between molecules is always one of attraction, although this attraction has different origins in different systems. London forces, dipole-dipole attractions, acid-base interactions, and hydrogen bonds are some of the types of attraction we have in mind. In the foregoing list, London forces are universal and also the weakest of the attractions listed. The interactions increase in strength and also in specificity in the order listed. 

A solubihty parameter of 24.5-24.7 MPa / [12.0-12.1 (cal/cm ) ] has been calculated for PVF using room temperature swelling data (69). The polymer lost solvent to evaporation more rapidly than free solvent alone when exposed to air. This was ascribed to reestabUshment of favorable dipole—dipole interactions within the polymer. Infrared spectral shifts for poly(methyl methacrylate) in PVF have been interpreted as evidence of favorable acid—base interactions involving the H from CHF units (70). This is consistent with the greater absorption of pyridine than methyl acetate despite a closer solubihty parameter match with methyl acetate. 

In choosing a SAM system for surface engineering, there are several options. Silane monolayers on hydroxylated surfaces are an option where transparent or nonconductive systems are needed. However, trichlorosilane compounds are moisture-sensitive and polymeri2e in solution. The resulting polymers contaminate the monolayer surface, which occasionally has to be cleaned mechanically. CarboxyUc acids adsorb on metal oxide, eg, AI2O2, AgO through acid—base interactions. These are not specific therefore, it would be impossible to adsorb a carboxyUc acid selectively in the presence of, for example, a terminal phosphonic acid group. In many studies SAMs of thiolates on Au(lll) are the system of choice. 

Fig. 9. Genesis of acid tain (13). From the oxidation of C, S, and N during the combustion of fossil fuels, there is a buildup in the atmosphere (gas phase, aerosol particles, raindrops, snowflakes, and fog) of CO2 and the oxides of S and N, which leads to acid—base interaction. The importance of absorption of gases into the various phases of gas, aerosol, and atmospheric water depends on a number of factors. The genesis of acid rain is shown on the upper right as an acid—base titration. The data given are representative of the environment in the vicinity of Zurich, Switzedand.

Cosolvents ana Surfactants Many nonvolatile polar substances cannot be dissolved at moderate temperatures in nonpolar fluids such as CO9. Cosolvents (also called entrainers, modifiers, moderators) such as alcohols and acetone have been added to fluids to raise the solvent strength. The addition of only 2 mol % of the complexing agent tri-/i-butyl phosphate (TBP) to CO9 increases the solubility ofnydro-quinone by a factor of 250 due to Lewis acid-base interactions. Veiy recently, surfac tants have been used to form reverse micelles, microemulsions, and polymeric latexes in SCFs including CO9. These organized molecular assemblies can dissolve hydrophilic solutes and ionic species such as amino acids and even proteins. Examples of surfactant tails which interact favorably with CO9 include fluoroethers, fluoroacrylates, fluoroalkanes, propylene oxides, and siloxanes. 

A requirement underlying the validity of Zisman plots is that there be no specific interactions, such as acid-base interactions, between the solid surface and the probe liquids. Such interactions, however, can, in principle, be taken into account by Young s equation, provided the contact angle remains finite. Their... 

Acid-base interactions in the most general Lewis sense occur whenever an electron pair from one of the participants is shared in the formation of a complex, or an adduct . They include hydrogen bonding as one type of such a bond. The bond may vary from an ionic interaction in one extreme to a covalent bond in the other. Acid-base interactions and their importance in interfacial phenomena have been reviewed extensively elsewhere [35,78] and will be described only briefly here. 

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 technique of IGC may be employed to obtain acid-base information, as suggested by Schultz and Lavielle [99], by using acid and base probe gases on a solid for which the alkane line has already been obtained. If acid-base interaction is involved in the adsorption, the retention volume should be greater than that corresponding to the dispersion force interaction alone, which should be the same as that of the equivalent alkane , i.e. the hypothetical alkane for which the value... 

Numerous reports of comparable levels of success in correlating adhesion performance with the Scatchard-Hildebrand solubility parameters can be found in the literature [116,120-127], but failures of this approach have also been documented [128-132J. Particularly revealing are cases in which failure was attributed to the inability of the Scatchard-Hildebrand solubility parameter to adequately account for donor-acceptor (acid-base) interactions [130,132]. Useful reviews of the use of solubility parameters for choosing block copolymer compatibilizers have been prepared by Ohm [133] and by Gaylord [134]. General reviews of the use of solubility parameters in polymer science have been given by Barton [135], Van Krevelen [114], and Hansen [136]. 

Vrbanac, M.D., Acid-Base Interactions in Adhesion and Wetting, Dissertation Thesis, University of Washington, 1989. 

Mittal, K.L. and Anderson, H.R. Jr. (Eds.), Acid-Base Interactions Relevance to Adhesion Sciertce and Technology. VSP, Utrecht, 1991. 

Acid-base interactions with model elastomers... 

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. 

For the sake of completeness, it is worthwhile to briefly discuss role of acid-base interactions in adhesion. In this context, the term acid refers to a Lewis acid (an electron acceptor) and a Lewis base (electron donor), rather than the more conventional acid and base definitions. The role of acid-base interactions in adhesion is discussed in detail by Lee [105]. 

It should be intuitively obvious that the contribution to the work of adhesion arising from acid-base interactions cannot be expressed in terms of the geometric mean of the surface energies. Therefore, the entire work of adhesion would be... 

Upon combining Eqs. 88 and 85, one finds that the total work of adhesion is related to the surface energies of the contacting materials as well as the enthalpy associated with acid-base interactions by... 

The acid/base interaction between the two polymers significantly increases the cohesive strength of the polymer blend at normal use temperatures but at elevated temperature the interaction can be interrupted and the polymer can still be melt processed. Other examples of basic polymers use for crosslinking include polyethylenimines, vinyl pyridine copolymers, and the like. 

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