Acids and bases dissociation

Determination of the dissociation constants of acids and bases from the change of absorption spectra with pH. The spectrochemical method is particularly valuable for very weak bases, such as aromatic hydrocarbons and carbonyl compounds which require high concentrations of strong mineral acid in order to be converted into the conjugate acid to a measurable extent. 

Polyprotic bases, like polyprotic acids, also have more than one base dissociation reaction and base dissociation constant. 

Tabulating Values for K and Kb A useful observation about acids and bases is that the strength of a base is inversely proportional to the strength of its conjugate acid. Consider, for example, the dissociation reactions of acetic acid and acetate. 

This relationship between and Kb simplifies the tabulation of acid and base dissociation constants. Acid dissociation constants for a variety of weak acids are listed in Appendix 3B. The corresponding values of Kb for their conjugate weak bases are determined using equation 6.14. 

KIFg [20916-97-6] which are both stable, white, crystalline soflds (3,94,95). These compounds dissociate at 200°C to KF and the corresponding halogen fluoride. Other salts are formed similarly (71,95—99). Some of the acids and bases of these systems are Hsted ia Table 2. 

A schematic of the production of acid and base by electrodialytic water dissociation is shown in Fig. 22-61. The bipolar membrane is inserted in the ED stack as shown. Salt is fed into the center compartment, and base and acid are produced in the adjacent compartments. The bipolar membrane is placed so that the cations are paired with OH" ions and the anions are paired with H. Neither salt ion penetrates the bipolar membrane. As is true with conventional elec trodialysis, many cehs may be stacked between the anode and the cathode. 

FIG. 22-61 Electrodialysis water dissociation (water splitting) membrane inserted into an ED stack. Starting with a salt, the device generates the corresponding acid and base by supplying and OH" from the dissociation of water in a bipolar membrane. CouHesy Elsevier.)... 

D.D. Perrin, Dissociation Constants of Inorganic Acids and Bases in Aqueous Solution, Butterworths, London, 1969. 

Acids and bases (see later) are inteiTclated. Traditionally, acids are compounds which contain hydrogen and which dissociate in water to form hydrogen ions or protons, H", commonly written as ... 

An inflection point in a pH-rate profile suggests a change in the nature of the reaction caused by a change in the pH of the medium. The usual reason for this behavior is an acid-base equilibrium of a reactant. Here we consider the simplest such system, in which the substrate is a monobasic acid (or monoacidic base). It is pertinent to consider the mathematical nature of the acid-base equilibrium. Let HS represent a weak acid. (The charge type is irrelevant.) The acid dissociation constant, = [H ][S ]/[HS], is taken to be appropriate to the conditions (temperature, ionic strength, solvent) of the kinetic experiments. The fractions of solute in the conjugate acid and base forms are given by... 

Hydrogen was recognized as the essential element in acids by H. Davy after his work on the hydrohalic acids, and theories of acids and bases have played an important role ever since. The electrolytic dissociation theory of S. A. Arrhenius and W. Ostwald in the 1880s, the introduction of the pH scale for hydrogen-ion concentrations by S. P. L. Sprensen in 1909, the theory of acid-base titrations and indicators, and J. N. Brdnsted s fruitful concept of acids and conjugate bases as proton donors and acceptors (1923) are other land marks (see p. 48). The di.scovery of ortho- and para-hydrogen in 1924, closely followed by the discovery of heavy hydrogen (deuterium) and... 

Acids and bases. An acid may be defined as a substance which, when dissolved in water, undergoes dissociation with the formation of hydrogen ions as the only positive ions ... 

Scheme (b) includes reactions formerly described by a variety of names, such as dissociation, neutralisation, hydrolysis and buffer action (see below). One acid-base pair may involve the solvent (in water H30+ —H2OorH20 — OH ), showing that ions such as HsO+ and OH- are in principle only particular examples of an extended class of acids and bases though, of course, they do occupy a particularly important place in practice. It follows that the properties of an acid or base may be greatly influenced by the nature of the solvent employed. 

The values of Ka and Kb for different acids and bases vary through many powers of ten. It is often convenient to use the dissociation constant exponent pK defined by... 

For very weak or slightly ionised electrolyes, the expression a2/( 1 — a) V = K reduces to a2 = KV or a = fKV, since a may be neglected in comparison with unity. Hence for any two weak acids or bases at a given dilution V (in L), we have a1 = y/K1 V and a2 = yjK2V, or ol1/ol2 = Jk1/ /K2. Expressed in words, for any two weak or slightly dissociated electrolytes at equal dilutions, the degrees of dissociation are proportional to the square roots of their ionisation constants. Some values for the dissociation constants at 25 °C for weak acids and bases are collected in Appendix 7. 

This shows that the pM value of the solution is fixed by the value of K and the ratio of complex-ion concentration to that of the free ligand. If more of M is added to the solution, more complex will be formed and the value of pM will not change appreciably. Likewise, if M is removed from the solution by some reaction, some of the complex will dissociate to restore the value of pM. This recalls the behaviour of buffer solutions encountered with acids and bases (Section 2.20), and by analogy, the complex-ligand system may be termed a metal ion buffer. 

Diphenylcarbazide as adsorption indicator, 358 as colorimetric reagent, 687 Diphenylthiocarbazone see Dithizone Direct reading emission spectrometer 775 Dispensers (liquid) 84 Displacement titrations 278 borate ion with a strong acid, 278 carbonate ion with a strong acid, 278 choice of indicators for, 279, 280 Dissociation (ionisation) constant 23, 31 calculations involving, 34 D. of for a complex ion, (v) 602 for an indicator, (s) 718 of polyprotic acids, 33 values for acids and bases in water, (T) 832 true or thermodynamic, 23 Distribution coefficient 162, 195 and per cent extraction, 165 Distribution ratio 162 Dithiol 693, 695, 697 Dithizone 171, 178... 

Ionic strength adjuster buffer 565, 570 Ionisation constants of indicators, 262, (T) 265 of acids and bases, (T) 832, 833, 834 see also Dissociation constants Ionisation suppressant 793 Iron(II), D. of by cerium(IV) ion, (cm) 546 by cerium(IV) sulphate, (ti) 382 by potassium dichromate, (ti) 376 by potassium permanganate, (ti) 368 see also under Iron... 

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. 

We express the relative strengths of weak acids and bases in terms of their dissociation constants. Shown... 

In this review, CPOs constructed by covalent bonds are mainly focused on however, stable coordination bonds comparable to the stability of the covalent bonds have potential for future enhanced molecular design of novel CPOs. One representative is the bond between pyridine-type nitrogen and metal, which is widely used in supramolecular chemistry, that is, the cyclic supramolecular formation reaction between pyridine-substituted porphyrin and metal salts (Fig. 6d) [27,28]. Palladium salts are frequently used as the metal salts. From the viewpoint of the hard and soft acid and base theory (HSAB), this N-Pd coordination bond is a well-balanced combination, because the bonds between nitrogen and other group X metals, N-Ni and Ni-Pt coordination bonds, are too weak and too strong to obtain the desired CPOs, respectively. For the former, the supramolecular architectures tend to dissociate into pieces in the solution state, and for the latter. 

The first substantial constitutive concept of acid and bases came only in 1887 when Arrhenius applied the theory of electrolytic dissociation to acids and bases. An acid was defined as a substance that dissociated to hydrogen ions and anions in water (Day Selbin, 1969). For the first time, a base was defined in terms other than that of an antiacid and was regarded as a substance that dissociated in water into hydroxyl ions and cations. The reaction between an acid and a base was simply the combination of hydrogen and hydroxyl ions to form water. 

Water as the solvent is essential for the acid-base setting reaction to occur. Indeed, as was shown in Chapter 2, our very understanding of the terms acid and base at least as established by the Bronsted-Lowry definition, requires that water be the medium of reaction. Water is needed so that the acids may dissociate, in principle to yield protons, thereby enabling the property of acidity to be manifested. The polarity of water enables the various metal ions to enter the liquid phase and thus react. The solubility and extent of hydration of the various species change as the reaction proceeds, and these changes contribute to the setting of the cement. 

Segments 4 and 5 reflect the chemical equilibria of acid and base dissociation of Zn(OH)2, yielding Zn + and HZnO ions, respectively. 

The theory of electrolytic dissociation also provided the possibility for a transparent definition of the concept of acids and bases. According to the concepts of Arrhenius, an acid is a substance which upon dissociation forms hydrogen ions, and a base is a substance that forms hydroxyl ions. Later, these concepts were extended. 

The third group of solvents comprises the hydrocarbons and their halogen derivatives. They are not of interest for electrochemistry, since the solubilities and dissociation of salts, acids, and bases in them are low. Systems with protic or aprotic polar solvents are used in practice and have been investigated widely. 

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