Acid-base equilibria salt solutions

Griess (1864a) had already observed that the diazo compounds obtained from primary aromatic amines in acid solution are converted by alkalis into salts of alkalis. The reaction is reversible. The compounds which Hantzsch (1894) termed sjw-diazotates exhibit apparently the same reactions as the diazonium ions into which they are instantaneously transformed by excess of acid. Clearly the reaction depends on an acid-base equilibrium. 

The rest of this chapter is a variation on a theme introduced in Chapter 9 the use of equilibrium constants to calculate the equilibrium composition of solutions of acids, bases, and salts. We shall see how to predict the pH of solutions of weak acids and bases and how to calculate the extent of deprotonation of a weak acid and the extent of protonation of a weak base. We shall also see how to calculate the pH of a solution of a salt in which the cation or anion of the salt may itself be a weak acid or base. 

C17-0025. Write the acid-base equilibrium that determines the pH of aqueous solutions of each of the following salts, and state whether the resulting solution is acidic, basic, or neither (a) NH4 I (b) NaClOq and (c) NaCHg CO2. ... 

Since the acid-base (precipitation) reaction takes place in non-aque-ous solution (isopropanol), a glass pH electrode could not be used to follow the titration. However, PANI is known to be pH sensitive as a result of the acid-base equilibrium between the emeraldine base (EB) and emeraldine salt (ES) forms of PANI [1-3]. Interestingly, the GC/ PANI electrode was found to give a reproducible response during the titrations despite the presence of the precipitate (trimeprazine tartrate) in the stirred solution. The same GC/PANI electrodes were used repeatedly for more than 2 months without any significant changes in the... 

FIGURE 7.4 Of the 16 chemistry topics examined (1-16) on the final exam, overall the POGIL students had more correct responses to the same topics than their L-I counterparts. Some topics did not appear on all the POGIL exams. Asterisks indicate topics that were asked every semester and compared to the L-I group. The topics included a solution problem (1), Lewis structures (2), chiral center identification (3), salt dissociation (4), neutralization (5), acid-base equilibrium (6), radioactive half-life (7), isomerism (8), ionic compounds (9), biological condensation/hydrolysis (10), intermolecular forces (11), functional group identification (12), salt formation (13), biomolecule identification (14), LeChatelier s principle (15), and physical/chemical property (16). 

The ionic nature of acids, bases and salts are removed from flue gases by wet scrubbing because the ionic separation that occurs in water creates advantageous equilibrium conditions. Removal may often be enhanced by manipulation of the chemistry of the scrubbing solution. 

The mass action law formalism, through its equilibrium constants, takes into account the interactions of the solvent with the various acids, bases, and salts these certainly are the dominant effects, comparable to Kepler s law in the above analogy. However, the formalism of the mass action law does not explicitly consider the mutual interaction of the solute particles, nor the effect of these solutes on the concentration of the solvent. Activity coefficients /have therefore been introduced in order to incorporate such secondary effects they are individual correction factors that multiply... 

Salt formation involves proton transfer from an acid to a base. In theory, any compound that exhibits acidic or basic characteristics can form salts. The major consideration is the relative acidity and/or basicity of the chemical species involved. To form a salt, the pKa of the acidic partner must be less than the pKa of the conjugate acid of the basic partner. These pKa values need to be about two units apart for total proton transfer to occur, otherwise an equilibrium mixture of all components (acid, base, and salt) is likely to result. Even so, equilibrium mixtures of this type can often be used to prepare salts if a driving force is present, such as the crystallization of the salt from solution. 

The acidity or basicity of a solution is frequently an important factor in chemical reactions. The use of buffers of a given pH to maintain the solution pH at a desired level is very important. In addition, fundamental acid-base equihbria are important in understanding acid-base titrations and the effects of acids on chemical species and reactions, for example, the effects of complexation or precipitation. In Chapter 6, we described the fundamental concept of equilibrium constants. In this chapter, we consider in more detail various acid-base equilibrium calculations, including weak acids and bases, hydrolysis, of salts of weak acids and bases, buffers, polyprotic acids and their salts, and physiological buffers. Acid-base theories and the basic pH concept are reviewed first. 

The partial ionization of weak acids, bases, and salts in solution, most commonly in aqueous solution, can be considered to be a chemical equilibrium process. Examples include the ionization of acetic acid. 

Fig. 3. Concentrations of ion pairs in equilibrium with triethylamine and six isomeric dinitrophenols in benzene solution. A, B, and S represent acid, base, and salt respectively. [Reproduced by permission from M. M. Davis, J. Am, Chem. Soc., 84, 3623 (1962).]...

The principles of chemical equilibrium already presented are utilized in the next three chapters to organize student treatment of equilibrium in aqueous solutions that contain weak or strong ionic solutes and their mixtures—acids, bases, and salts. 

C. Concentrations were in moles per 1000 g of liquid HF, i.e., molalities. The specific conductance L was derived from Lmeasured l-soivent- According to these authors, this expression did not represent the actual relationship because of interaction between the solvent and solute. A large part of the solvent conductance was attributed to traces of water and salts. Water was described as a strong electrolyte in liquid hydrogen fluoride, and also as a strong base therefore, it will interfere with the acid-base equilibrium under examination. 

Solutions of Salts of Polyprotic Acids 17-6 Acid-Base Equilibrium Calculations A Summary... 

In this solvent the reaction is catalyzed by small amounts of trimethyl-amine and especially pyridine (cf. 9). The same effect occurs in the reaction of iV -methylaniline with 2-iV -methylanilino-4,6-dichloro-s-triazine. In benzene solution, the amine hydrochloride is so insoluble that the reaction could be followed by recovery. of the salt. However, this precluded study mider Bitter and Zollinger s conditions of catalysis by strong mineral acids in the sense of Banks (acid-base pre-equilibrium in solution). Instead, a new catalytic effect was revealed when the influence of organic acids was tested. This was assumed to depend on the bifunctional character of these catalysts, which act as both a proton donor and an acceptor in the transition state. In striking agreement with this conclusion, a-pyridone is very reactive and o-nitrophenol is not. Furthermore, since neither y-pyridone nor -nitrophenol are active, the structure of the catalyst must meet the conformational requirements for a cyclic transition state. Probably a concerted process involving structure 10 in the rate-determining step... 

To calculate the pH of a salt solution, we can use the equilibrium table procedure described in Toolboxes 10.1 and 10.2—an acidic cation is treated as a weak acid and a basic anion as a weak base. However, often we must first calculate the Ka or Kh for the acidic or basic ion. Examples 10.10 and 10.11 illustrate the procedure. 

An aqueous solution of a soluble salt contains cations and anions. These ions often have acid-base properties. Anions that are conjugate bases of weak acids make a solution basic. For example, sodium fluoride dissolves in water to give Na, F, and H2 O as major species. The fluoride anion is the conjugate base of the weak acid HF. This anion establishes a proton transfer equilibrium with water ... 

The comparison of I —> N and N —> I may also be explained by the buffered pH in the diffusion layer and leads to an interesting comparison between a process under kinetic control versus one under thermodynamic control. Because the bulk solution in process N —> I favors formation of the ionized species, a much larger quantity of drug could be dissolved in the N —> I solvent if the dissolution process were allowed to reach equilibrium. However, the dissolution rate will be controlled by the solubility in the diffusion layer accordingly, faster dissolution of the salt in the buffered diffusion layer (process I—>N) would be expected. In comparing N—>1 and N —> N, or I —> N and I —> I, the pH of the diffusion layer is identical in each set, and the differences in dissolution rate must be explained either by the size of the diffusion layer or by the concentration gradient of drug between the diffusion and the bulk solution. It is probably safe to assume that a diffusion layer at a different pH than that of the bulk solution is thinner than a diffusion layer at the same pH because of the acid-base interaction at the interface. In addition, when the bulk solution is at a different pH than that of the diffusion layer, the bulk solution will act as a sink and Cg can be eliminated from Eqs. (1), (3), and (4). Both a decrease in the h and Cg terms in Eqs. (1), (3), and (4) favor faster dissolution in processes N —> I and I —> N as opposed to N —> N and I —> I, respectively. 

Br0nsted-Lowery acids are H+ donors and bases are H+ acceptors. Strong acids dissociate completely in water. Weak acids only partially dissociate, establishing an equilibrium system. Weak acid and base dissociation constants (Ka and Kb) describe these equilibrium systems. Water is amphoteric, acting as both an acid or a base. We describe water s equilibrium by the Kw expression. A pH value is a way of representing a solution s acidity. Some salts and oxides have acid-base properties. A Lewis acid is an electron pair acceptor while a Lewis base is an electron pair donor. 

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