Stability constant, apparent

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. 

Apparent indicator constant 264, 267 Apparent stability constant 59 Aqua regia 111 Arc alternating current, 764 direct current, 763, 771 sensitivities of elements, (T), 766 Aromatic hydrocarbons analysis of binary mixtures, 715 Arsenates, D. of (ti) 357 Arsenic, D. of as silver arsenate, (ti) 357 as trisulphide, (g) 448 by iodine, (am) 634, (ti) 397 by molybdenum blue method, (s) 681 by potassium bromate, (ti) 406 by potassium iodate, (ti) 401 in presence of antimony, (s) 724 Arsenic(III) oxide as primary standard, 261... 

The chelate HgY2 must be considerably more stable than MY( l 4)+ if necessary one can mask M"+ to a certain desirable extent by means of a selective com-plexing agent A, so that KM becomes an apparent stability constant,... 

From a plot of the internalisation flux against the metal concentration in the bulk solution, it is possible to obtain a value of the Michaelis-Menten constant, Am and a maximum value of the internalisation flux, /max (equation (35)). Under the assumption that kd kml for a nonlimiting diffusive flux, the apparent stability constant for the adsorption at sensitive sites, As, can be calculated from the inverse of the Michaelis-Menten constant (i.e. A 1 = As = kf /kd). The use of thermodynamic constants from flux measurements can be problematic due to both practical and theoretical (see Chapter 4) limitations, including a bias in the values due to nonequilibrium conditions, difficulties in separating bound from free solute or the use of incorrect model assumptions [187,188],... 

However, the equilibrium constant must still be considered as pure and dimensionless numbers (according to the classical relation —AG° = RT In Ks). All molar concentrations in the expression of Ks should thus be interpreted as molar concentrations relative to a standard state of 1 mol dm-3 i.e. they are the numerical values of the molar concentrations5 . If the solution is not dilute enough, the equilibrium constants can still be written with concentrations but they must be considered as apparent stability constants. 

Apparent stability constants for interactions between l-chloro-2,4-dinitrobenzene and benzene or mesitylene were found to be 0.76 and 0.96 (moD1 dm3) respectively, and between 4-chloro-3-nitrotrifluoromethylbenzene and benzene or mesitylene the values were 0.96... 

TABLE 1. Apparent stability constant (Kc) of complexes between aromatic amines and l-fluoro-2,4-dinitrobenzene (unless otherwise indicated) at 40 °C... 

Recently262, the apparent stability constants of the complexes between aromatic fluoro derivatives and amines (shown in equilibrium 31, Kc in moL1 dm3) in toluene- were evaluated by 19F chemical shift measurements. 

TABLE 13. Apparent stability constants of molecular complexes between 2-hydroxypyridine and some aromatic nitro derivatives in hen/enevA at 25 °C125. Reproduced by permission of societa chimica Italiana from Reference 125... 

The study of molecular complexation was then extended to other aromatic nitro derivatives125. Although, as was described before, one of the more frequent methods of studying the formation of molecular complexes is by UV-visible spectrophotometry, the author did not observe detectable differences in the UV-visible absorbance spectra between the 2-hydroxypyridine-l-fluoro-2,4-dinitrobenzene (FDNB) mixtures and the sum of their separate components. The author observed that the signals of the 1II NMR spectra of FDNB in apolar solvents were shifted downward by the addition of 2-hydroxypyridine from solutions where [2-hydroxypyridine] [FDNB] he calculated the apparent stability constants, which are shown in Table 13. 

Taking into account these apparent inconsistencies between the values, which are rather higher than the stated errors given as standard deviations, results in suspicions us regarding the whole way of calculating of the stability constants. 

To put hydroxypyranonate and hydroxypyridinonate complexes in context, stability constants for kojate and l,2-dimethyl-3-hydroxy-4-pyridinonate complexes of Mg, Al, Fe, and Gd are compared with stability constants for complexes of these cations with a few other ligands in Table III. That these hydroxypyranonate and hydroxyp5rr-idinonate ligands form stable complexes is immediately apparent. In this section we shall present and discuss a generous, but far from... 

Table XVI shows a selection of stability constants and redox potentials for iron(II) and iron(III) complexes. This Table covers a wide range of the latter, showing how the relative stabilities of the iron(II) and iron(III) complexes are refiected in. B (Fe /Fe ) values. A more detailed illustration is provided by the complexes of a series of linear hexadentate hydroxypyridinonate and catecholate ligands, where again high stabilities for the respective iron(III) complexes are refiected in markedly negative redox potentials (213). The combination of the high stabilities of iron(III) complexes of hydrox5rpyridinones, as of hydroxamates, catecholates, and siderophores, and the low stabilities of their iron(II) analogues is also apparent in Fig. 8. Here redox potentials for hydroxypyranonate and hydroxypyridinonate complexes of iron are placed in the overall context of redox potentials for iron(III)/iron(II) couples. The -(Fe /Fe ) range for e.g., water, cyanide, edta, 2,2 -bipyridyl, and (substituted) 1,10-phenanthrolines is...

Although there is no controversy about the basic definition of stability constants, physical chemists and biochemists handle the concepts involved and the resulting calculations differently. Physical chemists think in terms of reactive species and biochemists in terms of total concentrations of components, A further source of confusion is the differing definitions of apparent constant. To a physical chemist the stability constant for MgATP formation... 

Table 5-3 shows the order of reactivity of monomers in propagation. It is not a simple matter to explain the order of propagation rate constants for a set of monomers because there are variables—the reactivity of the monomer and the reactivity of the carbocation. For example, carbocation stability is apparently the more important feature for isopropyl vinyl ether and results in decreasing its propagation reactivity compared to isobutylene. 

For complex formation between aldehydes and S(IV) to be important in the troposphere, the aldehydes not only must have high solubility but also be present in air at significant concentrations and form stable adducts with S(IV) at a sufficiently fast rate that it can occur during the lifetime of a typical cloud or fog event. Table 8.4 gives the rate constants /c,4 and kt5 for formation of the S(IV) complexes as well as the stability constants Ku and apparent stability constant K p, defined as... 

O stability constant of DBQP-Cu complexes (determined by Langmir s eq.), a apparent formation rate constant of DBQP-Cu (Jfc f),... 

Thiocyanate. — On the basis of /-orbital hybridization Diamond [351] predicted the formation of stronger actinide complexes with thiocyanate ion than for the rare earths. Subls and Chopfin [352] have studied the ion exchange behaviour of many actinide and rare earth thiocyanate complexes and have shown that europium is eluted much sooner than americium from Dowex-1 with ammonium thiocyanate. The stability constants for the formation of MSCN2+ and M(SCN)2 complexes for Nd3+, Eus+, Pu3+, Am3+, Cm3+, and Cf34 have been measured [353] and are tabulated in Table 25. It is apparent from the table that the formation... 

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