Solution , 110 Stability constant

An electrophoretic method was described by Srivastava et al. [40] to study equilibria of the cited mixed ligand complex systems in solution. Stability constants of the Zn(II) and Cd(II) complexes were 5.36 and 5.18 (log K values), respectively, at an ionic strength of 0.1 and a temperature of 35 °C. 

Proton nmr halide anion titrations reveal that the ethyl- [79], propyl-[80] and butyl- [81] linked derivatives (Fig. 43) form complexes of 1 1 stoichiometry in acetonitrile solution. Stability constant determinations suggest that the ethyl derivative [79] exhibits selectivity for the chloride anion in preference to bromide or iodide. As the chain length increases, so the selectivity for chloride decreases and also the magnitude of the stability constant which is evidence for an anionic chelate effect with the chloride anion. Receptors containing larger aryl [81], [83], [84] and alkylamino spacers [85] (Fig. 43) form complexes of 2 1 halide anion receptor stoichiometry. 

Job plots have established the stoichiometry of several iron(III)-3-hydroxy-2-methyl-4(l//)-pyridinone systems in aqueous solution.Stability constants have been determined for 1,2-dimethyl-, 1,2-diethyl-, and several other 3-hydroxy-4-pyridinonato-iron(III) complexes. " These data supplement and update the long-standing set of log / 3 values for... 

A majority of the host systems mentioned so far have been shown to encapsulate halide guests as a consequence of the symmetrical nature of their binding pockets, which readily adapt to the spherical symmetry of the halide ion. A study of the bis-tren macrobicyclic ligand 19-6H, however, has revealed that, in addition to accommodating halide anions, it is also able to encapsulate azide, N, within its cylindrical cavity. Solution stability constant measurements indicate that the host... 

The rubidium and cesium complexes of [2.2.2] are isomorphous with approximate D3 symmetry and a crystallographic twofold rotation axis (41). While the rubidium cation is complexed almost without strain, the Cs+ is accommodated only by enlarging the cavity, increasing the mean C—C torsion angle to 71° (compared with 54° for the potassium cryptate). The ligand deformations required to complex Na+ and Cs + are reflected in their lower solution stability constants with respect to the K+ and Rb+ cryptates (see Section III,D). 

Aqueous solution stability constants for the aryl substituted complexes have been determined. The ML3 complexes are highly stable at 25 °C the overall stability constant (/Ss) for the parent complex (17) R = H is 10 . At ligand to metal ratios > 1, the hgands prevent gallium hydrolysis even at millimolar concentrations and under slightly basic conditions the effective formation constant for ML3... 

Fluoride. For equilibrium calculations in acid solutions, stability constants are needed for HF°, HF2, and (HF) species. These species become important when the pH drops below 4.5 and fluoride concentration rises above 5 x 10 M. Several... 

The anion-binding properties of a series of highly cationic metallated calix[4]arenes have also been investigated. Host 88, in which the calix[4]arene is coordinated to four Ru(77 -/)-cymene) units, was found by H NMR titration to bind GP, Br I , and NOs in aqueous solution. Stability constants were determined with. a = 551, 133, 51, and 49M respectively. 

Table 1. The dimerization 2 H2P

A calorimetric and a pH method have been used to measure the solution stability constants of borate complexes of pentitols and hexitols. ... 

The solubility of cassiterite leads directly to the formation of Sn(OH)4(aq) due to the very negative solubility constant of the tin(IV) oxide phase. At alkaline pH, first the formation of Sn(OH)5 has been observed and then Sn(OH)g . Similar behaviour for plattnerite has also been observed however, for this phase due to a greater solubility at low pH, there may be potential for the formation of cationic monomeric hydrolysis species although none appear to have been reported. Like tin(IV), lead(IV) also forms the negatively charged Pb(OH)g in alkaline solutions. Stability constants for the singly charged anionic complex Pb(OH)j have not been reported. 

A significant achievement of Anatoly K. Babko was in the area of systematic physicochemical research of complex compounds in solution based on their photometric properties. Anatoly K. Babko showed the stability constants of complexes to be highly important, and demonstrated the relevance of the stepwise character of the dissociation of complex compounds. 

Chaput, Jeminet and Juillard measured the association constants of several simple polyethylene glycols with Na", K", Cs", and Tl". Phase transfer catalytic processes and most biological processes are more likely to involve the first two cations rather than the latter two, so we will confine the discussion to these. Stability constants for the dimethyl ethers of tetra-, penta-, hexa-, and heptaethylene glycols were determined poten-tiometrically in anhydrous methanol solution and are shown in Table 7.1. In the third column of the table, the ratio of binding constants (Ks/K s) is calculated. Note that Simon and his coworkers have referred to this ratio as the selectivity constant. ... 

The macrocyclic hexamine [18]aneN6 was further found to recognize catechol, catecholamines and biologically relevant compounds (see Chart II)64). It interacts with all of these donor compounds in neutral pH solutions to form 1 1 complexes, which were determined polarographically. The stability constants pL are summarized in Table 6. 

In equation (q) only the fully ionised form of EDTA, i.e. the ion Y4 , has been taken into account, but at low pH values the species HY3, H2Y2, H3 Y and even undissociated H4Y may well be present in other words, only a part of the EDTA uncombined with metal may be present as Y4. Further, in equation (q) the metal ion M"+ is assumed to be uncomplexed, i.e. in aqueous solution it is simply present as the hydrated ion. If, however, the solution also contains substances other than EDTA which can complex with the metal ion, then the whole of this ion uncombined with EDTA may no longer be present as the simple hydrated ion. Thus, in practice, the stability of metal-EDTA complexes may be altered (a) by variation in pH and (b) by the presence of other complexing agents. The stability constant of the EDTA complex will then be different from the value recorded for a specified pH in pure aqueous solution the value recorded for the new conditions is termed the apparent or conditional stability constant. It is clearly necessary to examine the effect of these two factors in some detail. 

The factor at can be calculated from the known dissociation constants of EDTA, and since the proportions of the various ionic species derived from EDTA will be dependent upon the pH of the solution, a will also vary with pH a plot of log a against pH shows a variation of logoc = 18 at pH = 1 to loga = 0 at pH = 12 such a curve is very useful for dealing with calculations of apparent stability constants. Thus, for example, from Table 2.4, log K of the EDTA complex of the Pb2+ ion is 18.0 and from a graph of log a against pH, it is found that at a pH of 5.0, log a = 7. Hence from equation (30), at a pH of 5.0 the lead-EDTA complex has an apparent stability constant given by ... 

The extent of hydrolysis of (MY)(n 4)+ depends upon the characteristics of the metal ion, and is largely controlled by the solubility product of the metallic hydroxide and, of course, the stability constant of the complex. Thus iron(III) is precipitated as hydroxide (Ksal = 1 x 10 36) in basic solution, but nickel(II), for which the relevant solubility product is 6.5 x 10 l8, remains complexed. Clearly the use of excess EDTA will tend to reduce the effect of hydrolysis in basic solutions. It follows that for each metal ion there exists an optimum pH which will give rise to a maximum value for the apparent stability constant. 

EDTA is a very unselective reagent because it complexes with numerous doubly, triply and quadruply charged cations. When a solution containing two cations which complex with EDTA is titrated without the addition of a complex-forming indicator, and if a titration error of 0.1 per cent is permissible, then the ratio of the stability constants of the EDTA complexes of the two metals M and N must be such that KM/KN 106 if N is not to interfere with the titration of M. Strictly, of course, the constants KM and KN considered in the above expression should be the apparent stability constants of the complexes. If complex-forming indicators are used, then for a similar titration error KM/KN z 108. 

In a similar manner, in a solution containing the species Hg2+, HgY2-, MY,n 4)+ and M"+, where Y is the complexing agent EDTA and M"+ is a metallic ion which forms complexes with it, the concentration of the mercury ion is controlled by the stability constants of the complex ions MYhigh stability constant), and the concentration of the metal ions M"+. Hence, a mercury electrode placed in this solution will acquire a potential which is determined by the concentration of the ion M"+. 

Discussion. Salicylic acid and iron(III) ions form a deep-coloured complex with a maximum absorption at about 525 nm this complex is used as the basis for the photometric titration of iron(III) ion with standard EDTA solution. At a pH of ca 2.4 the EDTA-iron complex is much more stable (higher stability constant) than the iron-salicylic acid complex. In the titration of an iron-salicylic acid solution with EDTA the iron-salicylic acid colour will therefore gradually disappear as the end point is approached. The spectrophotometric end point at 525 nm is very sharp. 

Concentrated acids D. of strength, (ti) 296 Concentration of aqueous solutions common acids and ammonia, (T) 829 Concentration cells 63, 549 overpotential, 506 polarisation, 506 e.m.f. of, 506 Condenser current 595 Conditional stability constant 59 Conductance 519... 

Some suggested calculation procedures and the variation in results obtained from different calculation methods for evaluation of concentration stability constants of metal ion complexes in aqueous solution. A. M. Bond, Coord. Chem. Rev., 1971,6, 377-405 (43),... 

Measurement of the stability constants of plutonium complexes is hampered by difficulties of maintaining a particular oxidation state. Formation of complexes of Pu+3, except in very acid solutions, is accompanied and often obscured by complexation catalyzed oxidation to Pu+lt. Study of complexation of Pu+lt is often confused by competition with hydrolysis above pH 1-2. 

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