Ionization constant water

Acidic ionization constants (water, 25°C) and pH values at the isoelectric points are reported. Source Refs. 11, 12. 

It can be seen from Table 2 that the intrinsic values of the pK s are close to the model compound value that we use for Cys(8.3), and that interactions with surrounding titratable residues are responsible for the final apparent values of the ionization constants. It can also be seen that the best agreement with the experimental value is obtained for the YPT structure suplemented with the 27 N-terminal amino acids, although both the original YPT structure and the one with the crystal water molecule give values close to the experimentally determined one. Minimization, however, makes the agreement worse, probably because it w s done without the presence of any solvent molecules, which are important for the residues on the surface of the protein. For the YTS structure, which refers to the protein crystallized with an SO4 ion, the results with and without the ion included in the calculations, arc far from the experimental value. This may indicate that con-... 

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... 

Polynitroparaffkis are stronger acids than the corresponding mononitroparaffins. Thus 1,1-dinitroethane has an ionization constant of 5.6 x 10 in water at 20°C trinitromethane is a typical strong acid with an ionization constant ki the range of 10 to 10 . Neutralization of these substances occurs rapidly, and they may be titrated readily. 

Carbon dioxide, the final oxidation product of carbon, is not very reactive at ordinary temperatures. However, in water solution it forms carbonic acid [463-79-6] H2CO2, which forms salts and esters through the typical reactions of a weak acid. The first ionization constant is 3.5 x 10 at 291 K the second is 4.4 x 10 at 298 K. The pH of saturated carbon dioxide solutions varies from 3.7 at 101 kPa (1 atm) to 3.2 at 2,370 kPa (23.4 atm). A soHd hydrate [27592-78-5] 8H20, separates from aqueous solutions of carbon dioxide that are chilled at elevated pressures. 

The ionization eonstant should be a function of the intrinsic heterolytic ability (e.g., intrinsic acidity if the solute is an acid HX) and the ionizing power of the solvents, whereas the dissoeiation constant should be primarily determined by the dissociating power of the solvent. Therefore, Ad is expeeted to be under the eontrol of e, the dieleetrie eonstant. As a consequenee, ion pairs are not deteetable in high-e solvents like water, which is why the terms ionization constant and dissociation constant are often used interchangeably. In low-e solvents, however, dissociation constants are very small and ion pairs (and higher aggregates) become important species. For example, in ethylene chloride (e = 10.23), the dissociation constants of substituted phenyltrimethylammonium perchlorate salts are of the order 10 . Overall dissociation constants, expressed as pArx = — log Arx, for some substanees in aeetie acid (e = 6.19) are perchloric acid, 4.87 sulfuric acid, 7.24 sodium acetate, 6.68 sodium perchlorate, 5.48. Aeid-base equilibria in aeetie acid have been earefully studied beeause of the analytical importance of this solvent in titrimetry. 

The term is also called an ionization constant because it states the extent to which a substance forms ions in water. The relatively low value of for acetic acid reveals that the un-ionized form, CH3COOH, predominates over H and CH3COO in aqueous solutions of acetic acid. Viewed another way, CH3COO, the acetate ion, has a high affinity for H. ... 

Protonation of pyrazine A-oxides takes place at the unsubstituted ring nitrogen as revealed by examination of their UV spectra and ionization constants in water. The same holds for unsubstituted quinoxaline A-oxide and the 3-amino derivative. Pyrazine and quinoxaline di-A-oxides are protonated at one A-oxide oxygen atom (74KGS1554). 

Hence for the ionization of water, the equilibrium constant expression can be written ... 

The equation just written is the reverse of that for the ionization of water, so the equilibrium constant can be calculated by using the reciprocal rule (Chapter 12). 

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 ... 

Values were selected from the 47 entries given in Ref. 19. The rate constants were determined in acetone-water at 25.0 °C. and the ionization constants in water at 25.0 °C. 

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) ... 

In the presence of a base B, water acts as an acid by donating a proton, and the equiiibrium constant for the transfer of a proton from water to a base is caiied the base ionization constant (Zjj) ... 

It is important to note that each hydrogen ion is accompanied by a hydroxy ion, so that in neutral solution the concentrations of these two ions are equal to each other, and therefore from the equation, 11 l+][OI I = Kw, each of these concentrations is equal to (Kv)"5. It is worthwhile adding additional fundamentals pertaining to the ionization of water. The equilibrium constant (Kr) of the ionization reaction of water as shown above is ... 

The ionization of water is so important in the study of aqueous equilibria that the equilibrium constant is given the special symbol, Kw. It can be seen that, Kw, like all equilibrium constants, depends on temperature. Since Kw is larger (the forward reaction is encouraged) at higher temperatures, the forward reaction must consume heat, so the ionization of water must be endothermic. 

Oumada et al. [148] described a new chromatographic method for determining the aqueous pKa of dmg compounds that are sparingly soluble in water. The method uses a rigorous intersolvent pH scale in a mobile phase consisting of a mixture of aqueous buffer and methanol. A glass electrode, previously standardized with common aqueous buffers, was used to measure pH online. The apparent ionization constants were corrected to a zero-cosolvent pH scale. Six sparingly soluble nonsteroidal antiinflammatory weak acids (diclofenac, flurbiprofen, naproxen, ibu-profen, butibufen, fenbufen) were used successfully to illustrate the new technique. 

Shedlovsky, T Kay, R. L., The ionization constant of acetic acid in water-methanol mixtures at 25°C from conductance measurements, J. Am. Chem. Soc. 60,151-155 (1956). 

Long, F. A. Ballinger, P, Acid ionization constants of alcohols in the solvents water and deuterium oxide, in Pesce, B. (ed.), Electrolytes, Pergamon Press, New York, 1962, pp. 152-164. 

Wooley, E. M. Tomkins, J. Hepler, L. G., Ionization constants for very weak organic acids in aqueous solution and apparent ionization constants for water in aqueous organic mixtures, J. Solut. Chem. 1, 341-351 (1972). 

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