Acids, ionization

According to the Arrhenius definitions an acid ionizes m water to pro duce protons (H" ) and a base produces hydroxide ions (HO ) The strength of an acid is given by its equilibrium constant for ionization m aqueous solution... 

The equilibrium constant for the overall reaction is related to an apparent equilibrium constant Ki for carbonic acid ionization by the expression... 

Metal ion extraction with crown ethers containing linear lateral groups capable of acid ionization 98PAC2393. 

S-Poly(L-malic acid) ionizes readily in water giving rise to a highly soluble polyanion. Thus, a 2% solution of the free acid of the polymer from Aureobasidium sp. A-91 showed a pH 2.0 [5]. The ionic constants have been determined to be pKa = 3.6 for the polymer from Aureo-basidumsp. A-9 [5] and pKa (25°C) = 3.45 for/3-poly(L-malic acid) of Mw 24 kDa from F. polycephalum (Valussi and Cesaro, unpublished results) Thus, the polymer is highly charged under physiological conditions (pH 7.0). 

There are two types of acids, strong and weak, which differ in the extent of their ionization in water. Strong acids ionize completely, forming H+ ions and anions. A typical strong acid is HC1. It undergoes the following reaction on addition to water ... 

Click Coached Problems for a self-study module on acid ionization. 

Certain weak acids are polyprotic they contain more than one ionizable hydrogen atom. Such acids ionize in steps, with a separate equilibrium constant for each step. Oxalic acid, a weak organic acid sometimes used to remove bloodstains, is diprotic ... 

As pointed out in Chapter 13, strong acids ionize completely in water to form H30+ ions strong bases dissolve in water to form OH- ions. The neutralization reaction that takes place when any strong acid reacts with any strong base can be represented by a net ionic equation of the Bronsted- Lowry type ... 

Presto, a third-order rate law This multiplication should not be taken as representing a chemical event or as carrying such implications it is only a valid mathematical manipulation. Other similar transformations can be given,2 as when one multiplies by another factor of unity derived from the acid ionization equilibrium of HOC1. (The reader may show that this gives a second-order rate law.) These considerations illustrate that it is the rate law and not the reaction itself that has associated with it a unique order. 

A reactant may be present in two forms, or even three, that coexist. The components are related by one (or two) reactions that, we shall assume, equilibrate very rapidly compared to the rate of product buildup. The proportion in each form may be changed by some variable that the investigator keeps constant in a single experiment but later varies among a series of determinations. One instance in which this arises is that of a rapid protonation equilibrium. For example, suppose that the reactant A is partially protonated, and that it is the protonated form of the substrate, AH+, that is converted to product. This can be diagrammed in more than one way here we choose the form in which the protonation equilibrium is written as an acid ionization, which is the usual convention ... 

Assume that the reaction occurs between the two uncharged species, MNNG and Am, with a rate constant kN. Express ks as a function of tN, K m, Kan, and [H. Sketch the anticipated pH profile. Actually, this situation is further complicated because kN, although constant over some pH range, shows a further variation that can be attributed to an acidic intermediate. Derive an expression for kN as a function of [H + ] from the scheme shown, denoting the acid ionization constant of the steady-state intermediate as Knl. 

For the purpose of systematizing kinetic and equilibrium data, for literally hundreds of reactions, it is desirable to have a single reference series for all. Hammett adopted as the standard the acid ionization constants for substituted benzoic acids in aqueous solution at 25 °C. This choice was fortunate because the compounds are stable and for the most part readily available. Also, their pA"a s can easily and precisely be measured for nearly every substituent. Thus, one constructs a plot according to either of the following equations, in which Eq. (10-4) constitutes a further example ... 

The values of Hn and E are zero for water, by virtue of the constants 1.74 and 2.60. In these definitions, pKa refers to the acid ionization constant of the conjugate acid of the nucleophile, and E° to the standard electrode potential for the two-electron half-reaction ... 

Hydroxyl radicals. The acid ionization constant of the short-lived HO transient is difficult to determine by conventional methods but an estimate can be made because HO, but not its conjugate base, O -, oxidizes ferrocyanide ions HO + Fe(CN) — OH- + Fe(CN)g . Use the following kinetic data26 for the apparent second-order rate constant as a function of pH to estimate Ka for the acid dissociation equilibrium HO + H20 =... 

Ka is also widely called the acid ionization constant or acid dissociation constant. 

When nitronium salts are used, NOj is of course present to begin with. Esters and acyl halides of nitric acid ionize to form NOj. Nitrocyclohexadienones are converted to NO2 and the corresponding phenol." ... 

Acidic modifier Trifluoroacetic acid Formic acid Propionic acid Acetic acid Ionization completely suppressed Good separation/ionization Good separation/ionization Best separation/ionization... 

The Pi sequence for the former is similar to that for the latter (and for the benzoic acid ionizations of Table XXVII), but the pn sequence is not. 

One of the most important types of aqueous equilibrium involves proton transfer from an acid to a base. In aqueous soiutions, water can act as an acid or a base. In the presence of an acid, symbolized HA, water acts as a base by accepting a proton. The equilibrium constant for transfer of a proton from an acid to a water molecule is caiied the acid ionization constant (Zg) ... 

The strength of a weak acid is measured by its acid ionization constant,. This equilibrium constant can be calculated from the measured pH of the solution, as illustrated in Example. ... 

As the pH of the aqueous phase rises, the poly(alkenoic acid) ionizes and most probably creates an electrostatic field which aids the migration of liberated cations into the aqueous phase. 

As the poly(alkenoic acid) ionizes, polymer chains unwind as the negative charge on them increases, and the viscosity of the cement paste increases. The concentration of cations increases until they condense on the polyadd chain. Desolvation occurs and insoluble salts precipitate, first as a sol which then converts to a gel. This represents the initial set. 

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