Acid-dissociation constant proton-transfer reactions

The values listed in Tables 8.7 and 8.8 are the negative (decadic) logarithms of the acidic dissociation constant, i.e., — logj, For the general proton-transfer reaction... 

The neutral carboxyl group is not very effective in increasing the reduction rate of the complex. However, when the proton is removed from the carboxyl, the effect can increase and is greatest when the carboxyl ion is in a configuration favorable to chelation. Thus, the inverse (H+) path is not even observable for acid succinate in the same acidity range as that for which this path is important in the acid malonato reaction. The acid dissociation constants are known well enough so that the behavior difference between acid malonato and acid succinato can not be entirely ascribed to different acidities of the complexes. The results obtained with the acid malonate complexes, as reported in Table II, incidentally provide no support for the hypothesis (22) that electron transfer takes place by remote attack across hydrogen bonds. 

It is also common to measure by voltammetry the thermodynamic properties of purely chemical reactions that are in some way coupled to the electron transfer step. Examples include the determination of solubility products, acid dissociation constants, and metal-ligand complex formation constants for cases in which precipitation, proton transfer, and complexation reactions affect the measured formal potential. Also in these instances, studies at variable temperature will afford the thermodynamic parameters of these coupled chemical reactions. 

If a proton-transfer reaction is visualized as a three-body process (Bell, 1959b), a linear free energy relationship is predicted between the acid dissociation constant, Aha, and the catalytic coefficient for the proton-transfer reaction, HA. Figure I shows the relationships between ground-state energies and transition-state energies. This is a particular case of the Bronsted Catalysis Law (Bronsted and Pedersen, 1924) shown in equation (9). The quantities p and q are, respectively, the number of... 

One can draw a useful analogy between acid-base and oxidation-reduction reactions. Both involve the transfer of a species from a source, the donor, to a sink, the acceptor. The source and sink nomenclature implies that the tendency of the proton (in the case of acids) or of the electron (for reducing agents) to undergo transfer is proportional to the fall in free energy. From the relation AG° = RTIn Ka. you can see that the acid dissociation constant is a measure of the fall in free energy of the proton when it is transferred from a donor HA to the solvent H2O, which represents the reference (zero) free energy level of the proton in aqueous solution. 

When HX is a carbon acid the value of the rate coefficient, ) for a thermodynamically favourable proton transfer rarely approaches the diffusion limit. Table 1 shows the results obtained for a few selected carbon acids which are fairly representative of the different classes of carbon acids which will be discussed in detail in Sect. 4. For compounds 1—10, the value of k i is calculated from the measured value of k, and the measured acid dissociation constant and, for 13, k, is the measured rate coefficient and k1 is calculated from the dissociation constant. For 11 and 12, both rate coefficients contribute to the observed rate of reaction since an approach to equilibrium is observed. Individual values are obtained using the measured equilibrium constant. In Table 1, for compounds 1—10 the reverse reaction is between hydronium ion and a carbanion whereas for 11, 12 and 13 protonation of unsaturated carbon to give a carbonium ion is involved. For compounds 1—12 the reverse reaction is thermodynamically favourable and for 13 the forward reaction is the favourable direction. The rate coefficients for these thermodynamically favourable proton transfers vary over a wide range for the different acids. In the ionization of ketones and esters, for which a large number of measurements have been made [38], the observed values of fe, fall mostly within the range 10s—101 0 1 mole-1 sec-1. The rate coefficients observed for recombination of the anions derived from nitroparaffins with hydronium ion are several orders of magnitude below the diffusion limit [38], as are the rates of protonation and deprotonation of substituted azulenes [14]. For disulphones [65], however, the recombination rates of the carbanions with hydronium ion are close to 1010 1 mole-1 sec-1. Thermodynamically favourable deprotonation by water of substituted benzenonium ions with pK values in the range —5 to —9 are slow reactions [27(c)], with rate coefficients between 15 and 150 1 mole-1 sec-1 (see Sect. 4.7). 

Hence, equation (116) expresses the rate coefficient for proton transfer in terms of the equilibrium constant of the reaction using various parameters fa, WP, and X which relate to the detailed mechanism of the three step reaction (109). It often happens that the overall standard free energy (AG°) or equilibrium constant (K) for the reaction is not known, for example, where rate coefficients have been measured for reaction of a substrate HA of unknown p/fH a with a series of bases B with known pKB h In this case eqn. (116) can be modified to relate the experimental rate coefficient to the acid dissociation constant of the bases (XBH ) by including an unknown constant KHA, the acid dissociation constant of the substrate where K = KH a/Kq h. ... 

Acidic/Basic Lewis acidity/basicity determines the solvent s abihty to demate or accept a pair of electrons to form a coordinate bond with solute and/or between solvent molecules. A scale for this acid/base pre ierty was proposed by Gutman (DN and AN -donor and acceptor number, reflectively) based on caleuimetric determination. The complete proton transfer reaction with femnatiem of protonated ions is determined by proton affinity, gas phase acidity, acid or base dissociation constants. Both concepts differ in terms of net chemicsd reactiem. 

Many organic reactions occur by one or more steps in which a proton is added to a basic site or is removed from an acidic site. It turns out that we can predict the position of an acid-base reaction from the pAf values of the two acids that participate in the proton transfer steps. The equilibrium constant for the general equilibrium between two acids, HA and HB, is given by the ratio of the acid dissociation constants,... 

Proton transfer reactions (proton association and dissociation) in the excited state of aromatic compounds are elementary processes in both chemistry and biochemistry. The acid-base properties in the excited state of aromatic compounds are closely related to electronic structure, which is considerably different from that in the ground state. A large number of studies on the acidity constants pK in the excited state of aromatic compounds have shown that the pK values are markedly different from the acidity constants pK in the ground state [1-31]. 

All these reactions are thermodynamically favourable in the direction of proton transfer to hydroxide ion but the rate coefficients are somewhat below the diffusion-limited values. In broad terms, the typical effect of an intramolecular hydrogen bond on the rate coefficient for proton removal is to reduce the rate coefficient by a factor of up to ca 105 below the diffusion limit. Correspondingly the value of the dissociation constant of the acid is usually decreased by a somewhat smaller factor from that of a non-hydrogen-bonded acid. There are exceptions, however. 

Proton transfer is one of the prominent representatives of an ion-molecule reaction in the gas phase. It is employed for the determination of GBs and PAs (Chap. 2.11.2) by either method the kinetic method makes use of the dissociation of proton-bound heterodimers, and the thermokinetic method determines the equilibrium constant of the acid-base reaction of gaseous ions. In general, proton transfer plays a crucial role in the formation of protonated molecules, e.g., in positive-ion chemical ionization mass spectrometry (Chap. 7). 

Pairs of conjugated acids and bases are always involved in proton exchange reactions (see p.30). The dissociation state of an acid-base pair depends on the concentration. Usually, it is not this concentration itself that is expressed, but its negative decadic logarithm, the pH value. The connection between the pH value and the dissociation state is described by the Henderson-Hasselbalch equation (below). As a measure of the proton transfer potential of an acid-base pair, its pKa value is used—the negative logarithm of the acid constant Kg (where a stands for acid). 

Although the first of these reactions has the larger equilibrium constant, we can t consider it to be the principal reaction because the reactants and products are identical. Proton transfer from acetic acid to its conjugate base is constantly occurring, but that reaction doesn t change any concentrations and therefore can t be used to calculate equilibrium concentrations. Consequently, the principal reaction is dissociation of acetic acid. 

H -tetramethylbenzidine in anionic-cationic mixed micelles has been studied in detail by ESR . The photochemistry of the semi-oxidised forms of eosin Y and rose bengal have been investigated in colloidal solutions. Relevant to the fluorescence of proteins is a study of fluorescence quenching of indolic compounds by amino-acids in SOS, CTAB, and CTAC micelles O Rate constants for proton transfer of several hydroxyaromatic compounds have been measured in a variety of surfactant solutions. Photoprotolytic dissociation does not require exit of the reactant molecules from the micelles. Micellar solutions can be used to improve the fluorescence determination of 2-naphthol by inhibiting proton transfer or proton inducing reactions z2. jpe decay of the radical pair composed of diphenylphosphonyl and 2,4,6-trimethyl benzoyl radicals in SDS is affected by magnetic... 

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