Metal cations, acid-dissociation constants

Considering that heavy and transition metals may reach subsurface water as hydrated cations at neutral pH, they may behave as acids, due to formation of a hydration shell surrounding the cation. The acidity of hydrated cations depends on the acid dissociation constant (pK ) values. The lower the pK value of the metal, the lower the pH at which precipitates are formed. Values of pK for major heavy metals are presented in Table 5.5. 

Metal cations, M"+, constitute another common class of weak acids.20 Figure 6-8 shows acid dissociation constants for the reaction... 

The definition of pH is pH = —log[H+] (which will be modified to include activity later). Ka is the equilibrium constant for the dissociation of an acid HA + H20 H30+ + A-. Kb is the base hydrolysis constant for the reaction B + H20 BH+ + OH. When either Ka or Kb is large, the acid or base is said to be strong otherwise, the acid or base is weak. Common strong acids and bases are listed in Table 6-2, which you should memorize. The most common weak acids are carboxylic acids (RC02H), and the most common weak bases are amines (R3N ). Carboxylate anions (RC02) are weak bases, and ammonium ions (R3NH+) are weak acids. Metal cations also are weak acids. For a conjugate acid-base pair in water, Ka- Kb = Kw. For polyprotic acids, we denote the successive acid dissociation constants as Kal, K, K, , or just Aj, K2, A"3, . For polybasic species, we denote successive hydrolysis constants Kbi, Kb2, A"h3, . For a diprotic system, the relations between successive acid and base equilibrium constants are Afa Kb2 — Kw and K.a Kbl = A w. For a triprotic system the relations are A al KM = ATW, K.d2 Kb2 = ATW, and Ka2 Kb, = Kw. 

TABLE 16.6 Acid-Dissociation Constants for Metal Cations in Aqueous Solution at 25 C... 

The formation of a single complex species rather than the stepwise production of such species will clearly simplify complexometric titrations and facilitate the detection of end points. Schwarzenbach2 realised that the acetate ion is able to form acetato complexes of low stability with nearly all polyvalent cations, and that if this property could be reinforced by the chelate effect, then much stronger complexes would be formed by most metal cations. He found that the aminopolycarboxylic acids are excellent complexing agents the most important of these is 1,2-diaminoethanetetra-aceticacid (ethylenediaminetetra-acetic acid). The formula (I) is preferred to (II), since it has been shown from measurements of the dissociation constants that two hydrogen atoms are probably held in the form of zwitterions. The values of pK are respectively pK, = 2.0, pK2 = 2.7,... 

The kinetics of formation and dissociation of the Ca2+, Sr2+ and Ba2+ complexes of the mono- and di-benzo-substituted forms of 2.2.2, namely (214) and (285), have been studied in water (Bemtgen et al., 1984). The introduction of the benzene rings causes a progressive drop in the formation rates the dissociation rate for the Ca2+ complex remains almost constant while those for the Sr2+ and Ba2+ complexes increase. All complexes undergo first-order, proton-catalyzed dissociation with 0bs — kd + /ch[H+]. The relative degree of acid catalysis increases in the order Ba2+ < Sr2+ < Ca2+ for a given ligand. The ability of the cryptate to achieve a conformation which is accessible to proton attack appears to be inversely proportional to the size of the complexed metal cation in these cases. 

Tetracycline antibiotics are closely related derivatives of the polycyclic naphtha-cenecarboxamide. They are amphoteric compounds with characteristic dissociation constants corresponding to the acidic hydroxyl group at position 3 (pK about 3.3), die dimethylamino group at position 4 (pK, about 7.5), and the hydroxyl group at position 12 (pK about 9.4). In aqueous solutions of pH 4-7, tetracyclines exist as dipolar ions, but as the pH increases to 8-9 marked dissociation of the dimethylamine cation occurs. They are soluble in acids, bases, and alcohols but are quite insoluble in organic solvents such as chloroform. Their ultraviolet spectra show strong absorption at around 270 and 360 nm in neutral and acidic solutions. Tetracyclines are readily transformed into fluorescent products in the presence of metal ions or under alkaline conditions. 

The first chelating resins that were found to be really suitable for application in the field of selective cation absorption were those based on the aminodiacetate functional group.380 The first commercial resin based on this functional group, Dowex Al, was shown381 to have an affinity for a range of metals which was similar to the order of dissociation constants of the metal complexes with ethylenediaminetetraacetic acid (EDTA), i.e. 

Charged metals (cations) in water behave as Lewis acids (willing to accept electrons). Water on the other hand, because it is willing to share its two unshared oxygen-associated pair of electrons, behaves as a Lewis base. Strong H2Q-metal (Lewis base-Lewis acid) interactions allow H+ on the water molecule to dissociate, hence, low pH water is produced. The degree of dissociation of water interacting with a cation (Mn+) is described by the metal hydrolysis constant (Table 2A)... 

The Lewis bases for each of the superacid systems are the conjugate bases of the acids themselves, namely F, SO3F- and CF3SOJ. If enhanced basicity of one of the acids is required for specific speciation of a solute in a synthetic reaction, for example, it is easily achieved by direct quantitative addition of the base F, SO3F and CF3SO3 as the appropriate alkali metal cation or ammonium salts which dissociate completely in these media of high dielectric constant. 

Electron configurations of the elements of the three li-transition series are given in Table 25-1 and in Appendix B. Most li-transition metal ions have vacant d orbitals that can accept shares in electron pairs. Many act as Lewis acids by forming coordinate covalent bonds in coordination compounds (coordination complexes, or complex ions). Complexes of transition metal ions or molecules include cationic species (e.g., [Cr(OH2)( ]5+, [Co(NH3)g]3 +, [Ag(NH3)2]+), anionic species (e.g., [Ni(CN4)]2-, [MnCl ] ), and neutral species (e.g., [Fe(CO)5], [Pt(NH3)2Cl2]). Many complexes are very stable, as indicated by their low dissociation constants, (Section 20-6 and Appendix 1). 

This procedure of expressing the acids as oxo-hydroxo complexes of water is in full agreement with the corresponding reactions occurring with, e.g., the transition metal cations in aqueous solutions. Table 8.5 provides the dissociation constants for acids expressed in this unconventional way. °... 

From what we have said above, it follows that the acid-base equilibrium in the solutions containing metal cations and oxide ions in different sections of the titration curve is described either by the dissociation constant (in unsaturated solutions) or by the values of solubility product (in saturated solutions). In Refs. [175, 330] we proposed a method based on the analysis of the scatter in the calculated equilibrium parameters corresponding to the titration process. Indeed, in the unsaturated solution section there is no oxide precipitation and the calculated value of the solubility product increases monotonously (the directed shift) whereas the calculated value of the dissociation constant fluctuates about a certain value, which is the concentration-based dissociation constant of the studied oxide. 

As mentioned in Section 3.7.1.2, there is a considerable scatter of solubility product values obtained in the molten KCl-NaCl eutectic using different methods of solubility determination. This disagreement in the solubility parameters may be explained by differences in the sizes of oxide particles whose solubility is to be determined. The difference in size causes the scatter of the solubility data according to the Ostwald-Freundlich equation and the employment of the isothermal saturation method, which implies the use of commercial powders (often pressed and sintered), leads to values which are considerably lower than those obtained by the potentiometric titration technique where the metal-oxides are formed in situ. Owing to this fact, the regularities connected with the effect of physico-chemical parameters of the oxides or the oxide cations should be derived only from solubility data obtained under the same or similar experimental conditions. However, this does not concern the dissociation constants of the oxides, since homogeneous acid-base equilibria are not sensitive to the properties of the solid phase of... 

The apparent dissociation constants Kj(/9tO 7) which were compiled from the literature are given in Table 3.4 and they are presented together with the corresponding apparent Gibbs free energies AG =-R7 ln[Kj(/ 0 7)]. Similarly as with dissociation constants of citric acid in pnre water, differences in reported values of constants can be attributed not only to precision of experiments, but also to differences in applied speciation models, differences in mathematical form of equations used for activity coefficients and the choice of concentration scales (molar or molal). One aspect which was found to be extremely important was that earlier assumption that alkali metal cations do not form complexes with citrate anions is only partially correct. It was established that these cations form weak complexes with citrate anions and sometimes this interfering effect was even taken into account in calculation of Ki(/ 0 7) values [16, 21, 22]. 

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