AQUEOUS ACID-BASE REACTIONS

Automobile batteries contain 40% H2SO4 by mass. When the battery has run down, the concentration of H2SO4 is significandy lower than 40%. A technician checks an automobile battery by drawing some battery acid into a hydrometer, which indicates the density of the solution. This density is related to the concentration of H2SO4, which is more dense than water. 

There are many practical applications of acid-base chemistry in which we must know the concentration of a solution of an acid or a base. 

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S. A. Arrhenius defined an acid as any hydrogen-containing species able to release protons and a base as any species able to form hydroxide ions [71]. The aqueous acid-base reaction is the reaction between hydrogen ions and hydroxide ions with water formation. The ions accompanying the hydrogen and hydroxide ions form a salt, so the overall Arrhenius acid-base reaction can be written ... 

The dissociated species are the dominant species in the pH ranges given in Eqs. 4.7-4.9. At pH < 2.15, nonionic H3PO4 is dominant and therefore, this region is not useful in forming ceramics, because it will not contribute to the aqueous acid-base reaction. 

A neutralization reaction is a reaction between an acid and a base. Generally, aqueous acid-base reactions produce water and a salt, which is an ionic compound made up of a cation other than and an anion other than OH or CP ... 

Aqueous acid-base reactions involve water not only as solvent but also in the more active roles of reactant and product. These reactions occur in processes as diverse as the biochemical synthesis of proteins, the industrial production of fertilizer, and some of the methods for revitalizing lakes damaged by acid rain. 

Aqueous Acid-Base Reactions 11-1 Calculations Involving Molarity 11-2 Titrations... 

In the next sample problem, the calorimeter is used to study the change in heat during an aqueous acid-base reaction. Recall that, if a reaction takes place at constant pressure, the heat of the reaction is equal to its enthalpy change (A//). 

This is an acid-base reaction, in which the base is the oxide ion (p. 89) the acidic oxide SiOj displaces the weaker acidic oxide CO2 in the fused mixture. But in aqueous solution, where the 0 ion cannot function as a strong basefp. 89),carbon dioxide displaces silica, which, therefore, precipitates when the gas is passed through the aqueous silicate solution. In a fused mixture of silica and a nitrate or phosphate, the silica again displaces the weaker acidic oxides N2O5 and P4OJ0 ... 

Oxides and hydroxides react with HCl to form a salt and water as in a simple acid—base reaction. However, reactions with low solubiHty or insoluble oxides and hydroxides is complex and the rate is dependent on many factors similar to those for reactions with metals. Oxidizing agents such as H2O2, H2SeO, and V2O3 react with aqueous hydrochloric acid, forming water and chlorine. 

In addition to simple dissolution, ionic dissociation and solvolysis, two further classes of reaction are of pre-eminent importance in aqueous solution chemistry, namely acid-base reactions (p. 48) and oxidation-reduction reactions. In water, the oxygen atom is in its lowest oxidation state (—2). Standard reduction potentials (p. 435) of oxygen in acid and alkaline solution are listed in Table 14.10- and shown diagramatically in the scheme opposite. It is important to remember that if or OH appear in the electrode half-reaction, then the electrode potential will change markedly with the pH. Thus for the first reaction in Table 14.10 O2 -I-4H+ -I- 4e 2H2O, although E° = 1.229 V,... 

The acidic and basic properties of aqueous solutions are dependent on an equilibrium that involves the solvent, water. The reaction involved can be regarded as a Bransted-Lowry acid-base reaction in which the H20 molecule shows its amphiprotic nature ... 

Now by taking one more step we can view acid-base reaction in a broader sense. Suppose we mix aqueous solutions of ammonium chloride, NH4CI, and sodium acetate, CH3COONa. A sniff indicates ammonia has been formed. Reaction occurs,... 

When we mix two solutions the result is often simply a new solution that contains both solutes. However, in some cases the solutes can react with each other. For instance, when we mix a colorless aqueous solution of silver nitrate with a clear yellow aqueous solution of potassium chromate, a red solid forms, indicating that a chemical reaction has occurred (Fig. 1.1). This section and the next two introduce three of the main types of chemical reactions precipitation reactions, acid-base reactions, and redox reactions, all of which are discussed in more depth in later chapters. (The fourth type of reaction discussed in this text, Lewis acid-base reactions, is introduced in Section 10.2.) Because many chemical reactions take place in solution, particularly in water, in this section we begin by considering the nature of aqueous solutions. 

FIGURE 15.4 When aqueous ammonia is added to a copper(ll) sulfate solution, first a light-blue precipitate ot Cu(OH)2 forms (the cloudy region at the top, which appears dark because it is backlit). The precipitate disappears when more ammonia is added to form the dark blue complex ru(NH))4 T by a Lewis acid-base reaction. 

Many of the d-block elements form characteristically colored solutions in water. For example, although solid copper(II) chloride is brown and copper(II) bromide is black, their aqueous solutions are both light blue. The blue color is due to the hydrated copper(II) ions, [Cu(H20)fJ2+, that form when the solids dissolve. As the formula suggests, these hydrated ions have a specific composition they also have definite shapes and properties. They can be regarded as the outcome of a reaction in which the water molecules act as Lewis bases (electron pair donors, Section 10.2) and the Cu2+ ion acts as a Lewis acid (an electron pair acceptor). This type of Lewis acid-base reaction is characteristic of many cations of d-block elements. 

Using Environmental Examples to Teach About Acids. Acid-base reactions are usually presented to secondary students as examples of aqueous equilibrium (2). In their study of acids and bases, students are expected to master the characteristic properties and reactions. They are taught to test the acidity of solutions, identify familiar acids and label them as strong or weak. The ionic dissociation of water, the pH scale and some common reactions of acids are also included in high school chemistry. All of these topics may be illustrated with examples related to acid deposition (5). A lesson plan is presented in Table I. 

First, the simple thermodynamic description of pe (or Eh) and pH are both most directly applicable to the liquid aqueous phase. Redox reactions can and do occur in the gas phase, but the rates of such processes are described by chemical kinetics and not by equilibrium concepts of thermodynamics. For example, the acid-base reaction... 

In acid-base reactions, the heat of neutralization of aqueous acids and bases can be sufficient to cause spitting from containers when the concentrated reagents interact. This is also encountered when concentrated sulphuric acid is diluted (refer to Table 6.1) the acid should always be added cautiously to water and not vice versa. Eye protection is obligatory when using such reagents. 

The quantitative aspects of acid-base chemistry obey the principles Introduced earlier in this chapter. The common acid-base reactions that are important in general chemistry take place in aqueous solution, so acid-base stoichiometry uses molarities and volumes extensively. Example Illustrates the essential features of aqueous acid-base stoichiometry. 

Another way of analyzing these combinations is by type of substance. Parts a and c involve mixing of two aqueous solution, parts b and d involve adding a metal to an aqueous system, and part e is the interaction of a metal with O2 gas. When solutions mix, we look first for acid-base reactions (part c), then for formation of a precipitate (part b). When a metal contacts an aqueous system, the most likely reaction, if any, is oxidation of the metal. Any time molecular oxygen is present, we can expect oxidation to be one possibility. 

Equilibria that occur in aqueous solution are of particular interest, because water is the medium of life and a major influence on the geography of our planet. Many substances dissolve in water, and the solutes in an aqueous solution may participate in a number of different types of equilibria. Solubility itself is one important type of equilibrium, as we describe in Chapter 18. Acid-base reactions, considered in detail in Chapter 17, are another. To conclude this chapter, we describe how to determine which equilibria are most important in any particular aqueous solution. 

Thus, the relationship between acid and base is a reciprocal one and an acid-base reaction involves the transfer of a proton. This concept is not restricted to aqueous solutions and it discards Arrhenius prerequisite of ionization. 

This concept covers most situations in the theory of AB cements. Cements based on aqueous solutions of phosphoric acid and poly(acrylic acid), and non-aqueous cements based on eugenol, alike fall within this definition. However, the theory does not, unfortunately, recognize salt formation as a criterion of an acid-base reaction, and the matrices of AB cements are conveniently described as salts. It is also uncertain whether it covers the metal oxide/metal halide or sulphate cements. Bare cations are not recognized as acids in the Bronsted-Lowry theory, but hydrated... 

The phosphate bonded cements described in this chapter are the products of the simple acid-base reaction between an aqueous solution of orthophosphoric acid and a basic oxide or silicate. Such reactions take place at room temperature. Excluded from this chapter are the cementitious substances that are formed by the heat treatment of aqueous solutions of acid metal phosphates. 

Oxysalt bonded cements are formed by acid-base reactions between a metal oxide in powdered solid form and aqueous solutions of metal chloride or sulphate. These reactions typically give rise to non-homo-geneous materials containing a number of phases, some of which are crystalline and have been well-characterized by the technique of X-ray diffraction. The structures of the components of these cements and the phase relationships which exist between them are complex. However, as will be described in the succeeding parts of this chapter, in many cases there is enough knowledge about these cements to enable their properties and limitations to be generally understood. 

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