Basicity acid-base behavior

Acid-Base Behavior. The relative acidity-basicity of the filler, generally determined by measuring the pH value of a slurry of a specific mass of filler in 100 mL of deionized water, can influence the behavior of a filler in some systems. For example, the curing behavior of some elastomers is sensitive to the pH value of carbon black. 

A further important concept related to electronegativity and polarity is that of acidity and basicity. We ll see, in fact, that much of the chemistry of organic molecules can be explained by their acid-base behavior. You may recall from a course in general chemistry that there are two frequently used definitions of acidity the Brtfnsted-Lowry definition and the Lewis definition. We ll look at the... 

Both our original prediction about the effect of ionization energy on acid-base behavior and the trend which we have observed in the first three elements lead us to expect that the hydroxide or oxide of silicon should not be basic, but perhaps should be weakly acidic. This is in fact observed. Silicon dioxide, Si02, can exist as a hydrated solid containing variable amounts of water,... 

The pattern of oxidation states correlates with the pattern of acid-base behavior of d-metal oxides. Although most d-metal oxides are basic, the oxides of a given element show a shift toward acidic character with increasing oxidation number, just as the oxoacids do (recall Section 10.10). The family of chromium oxides is a good... 

The two protonation steps of the M02(CN)4 3 complexes (M=Tc(V), Re(V) equilibria (4) and (6) in Scheme 1) occur in acidic medium while the two protonation steps for the [M02(CN)4]4 (M = Mo(IV), W(IV)) occur in basic aqueous solutions. The pKa values which demonstrate the acid/base behavior of the complexes are given in Table II. Other aspects of these complexes are also presented therein but are discussed in later sections. 

Organic solvents can also be classified according to their ability to accept or transfer protons (i.e., their acid-base behavior) [20,21]. Amphiprotic solvents possess donor as well as acceptor capabilities and can undergo autoprotolysis. They can be subdivided into neutral solvents that possess approximately equal donor and acceptor capabilities (water and alcohols), acidic solvents with predominantly proton donor properties (acetic acid, formic acid), and basic solvents with primarily proton acceptor characteristics (formamide, N-methylformamide, and N,N-dimethylformamide). Aprotic solvents are not capable of autoprotolysis but may be able to accept protons (ACN, DMSO, propylene carbonate). Inert solvents (hexane) neither accept nor donate protons nor are they capable of autoprotolysis. 

This latter reaction is very slow as written and is of more importance in the reverse, dehydration reaction.) The characterization of these metal and nonmetal oxides as acids and bases is of help in rationalizing the workings, for example, of a basic Bessemer converter in steetmatcing. The identification of these acidic and basic species will also prove useful in develop r a general definition of acid-base behavior. 

The pattern of oxidation states accounts for the pattern of acid-base behavior of d-metal oxides. Although most d-metal oxides are basic, the... 

Association constant — Solvents having a low dielectric constant (e.g., benzene er = 2.29) cannot split protons from acids. The acid/base behavior in these solvents is based on association reactions between acidic and basic components in the solution according to ... 

Just as the cation produced by dissociation of water (H30+) is the acidic species in aqueous solutions, the NH4+ ion is the acidic species in liquid ammonia. Similarly, the amide ion, NH2, is the base in liquid ammonia just as OH- is the basic species in water. Generalization to other nonaqueous solvents leads to the solvent concept of acid-base behavior. It can be stated simply as follows A substance that increases the concentration of the cation characteristic of the solvent is an acid, and a substance that increases the concentration of the anion characteristic of the solvent is a base. Consequently, NH4C1 is an acid in liquid ammonia, and NaNH2 is a base in that solvent. Neutralization becomes the reaction of the cation and anion characteristic of the particular solvent to produce unionized solvent. For example, in liquid ammonia the following is a neutralization ... 

Some liquid covalent halides can act as nonaqueous solvents " based on Lewis acid-base behavior, according to the donor-acceptor definition. The self-dissociated ions consist of a cation formed by subtraction of a hahde ion from the neutral compound, while the anion is formed by its addition (equation 24). Salts derived from such covalent halides can be considered as titration products of the parent acidic and basic compounds (equations 25 and 26). In such cases, both the cation and the anion usually possess a stable coordination number with a high geometrical symmetry. 

Some amino acids, such as aspartic acid and lysine, have acidic or basic side chains. These additional ionizable groups complicate somewhat the acid—base behavior of these amino acids. Table 28.1 lists the pAT values for these acidic and basic side chains as well. 

Inert solvents, with neither acidic nor basic properties, allow a wider range of acid-base behavior. For example, hydrocarbon solvents do not limit acid or base strength because they do not form solvent acid or base species. In such solvents, the acid or base strengths of the solutes determine the reactivity and there is no leveling effect. Balancing the possible acid-base effects of a solvent with requirements for solubility, safety, and availability is one of the challenges for experimental chemists. 

The first point to be made concerning acids and bases is that so-called acid-base theories are in reality definitions of what an acid or base is they are not theories in the sense of valence bond theory or molecular orbital theory. In a very real sense, we can make an acid be anything we wish the differences between the various acid-base concepts are not concerned with which is right but which is most convenient to use in a particular situation. All of the current definitions of acid-base behavior are compatible with each other. In fact, one of the objects in the following presentation of many different definitions is to emphasize their basic parallelism and hence to direct the students toward a cosmopolitan attitude toward acids and bases which will stand them in good stead in dealing with various chemical situations, whether they be in aqueous solutions of ions, organic reactions, nonaqueotis titrations, or other situations. 

Casamassima, M. et al., Acid-base behavior of aluminum and silicon oxides—a combination of two approaches XPS and Lewis acido-basicity rest potential and Brpnsted acido-basicity, Appl. Surf. Sci., 52, 205, 1991. 

Figure 8.17 The trend in acid-base behavior of eiement oxides. The trend in acid-base behavior for some common oxides of Group 5A(15) and Period 3 elements is shown as a gradation in color (red = acidic blue = basic). Note that the metals form basic oxides and the non-metals form acidic oxides. Aluminum forms an oxide (purple) that can act as an acid or as a base. Thus, as atomic size increases, ionization energy decreases, and oxide basicity increases.

Transition metal hydrides, which are weakly basic as isolated molecules, are expected to display acidic properties in solution. With an appropriate choice of solvent we are thus able to induce Umpolung of the acid-base behavior of certain transition metal hydrides. The break-even point of a TMH in water would be reached with 3.7. This relatively low value indicates that most transition metal hydrides will dissociate protons in water. 

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