0
THE BEHAVIOR OF METAL COMPLEXES IN AQUEOUS SOLUTIONS' ARTHUR E. MARTELL Clark University, Worcester, Massachusetts
THIS paper is a survey of the various ways in which the properties of aqueous metal ions are affected by complex formation, with special reference to the formation of chelate compounds. The topics selected for discussion are solubility, electrical conductance, interaction with hydrogen ions, absorption spectra, I I and oxidation potential. These properties are fundaH2 0 HO mental ones and offer an insight into the basis for many (I) Hexa aqno metal ion (11) Hydrolyzed metal ion (dihydroxide) new and valuable applications of chelate compounds, which are pointed out in the course of the discussion. Many functions of coordination compounds, such as tion number is often assigned and a dynamic equilibcatalytic activity, are of a special nature. These are rium involving a distribution of forms is assumed. so varied and specialized that they defy classification The chemical reactions of the aquo ion may take into a few simple categories. Hence a discussion of place by changing the sheath of coordinated water these special properties is beyond the scope of this molecules in some manner. One of the simplest reacpaper. Of particular interest t o investigators in this tions which takes place is hydrolysis, which merely field in recent years is the stahility of metal complexes involves the ionization of a proton. Formula I1 shows and chelates, as measured by the equilibrium constants a dihydroxide formed by the removal of two protons. of the formation reaction. Stabilities are mentioned When the charge is reduced t o zero by such a reaction, in connection with the various properties to be discussed the normal metal hydroxide is produced. These hut a detailed account of stahility and the principles "hydrous oxides" are usually insoluble because of a involved cannot be given here. polymeric structure formed by a network of hydrogen bonds which bind the coordination groups together.? GENERAL CONCEPTS I t is seen that the properties of aquo ions are deterIn order to visualize how a metal ion in aqueous solu- mined by the effect of the ion on the hydration sphere. tion may be changed by complex formation it is neces- These properties are altered by complex formation, sary t o keep in mind that the aqueous metal ion is which may be considered as the replacement of one surrounded by a sheath of aqueous ions very much as or more water molecules by substitute donor groups. in formula. I. The coordination requirements of the Binding of the metal with such donors may differ metal ion are thus saturated by water molecules, the greatly from the bond type in the "water complex" number of such donors being about six in the case of and the properties of the metal ion are therefore altered. most metals, but it may vary considerably above and Further, the donors themselves may have special propbelow this figure. Large, highly charged ions such as erties, modified, of course, by the presence of the metal Zr+4,Hf+(, and M o + ~are known to have coordination ion. numbers of 8. Many metals such as Cu++, Zn++, and A typical metal complex in which all the water moleMg++ are considered t o have coordination numbers cules are replaced by another donor is illustrated by of 4. Certain metals such as Hg++ and Agf have formula 111. The cobalt ammines, in which A is NH, coordination requirements of two in many of their are examples of such complexes. When two or more complexes. In the case of the less basic metals the A groups are tied together into a single molecule the bond to the oxygen donor may have considerable compound is said t o be a metal chelate compound. covalent character, whereas with basic metals such as An example of this type of complex is illustrated by the alkali and alkaline earth metals the bonds are formula IV, in which the donor groups are tied together primarily of the ion-dipole type. When the covalent in groups of two. When chelating agents possess two, character is considerable the number of water mole- three, four, five, and six donor groups they are said cules as well as their directional distribution is relatively to be bidentate, tridentate, quadridentate, quinqnifixed. For the more basic metal ions the reverse is dentate, and sexadentate, respectively. Thus a metal true, and no definite structure or formula can be as- ion of coordination number 6 requires three bidentate signed t o the ion. In such cases an "average" hydraPresented to the Western Connecticut Section of the American Chemical Society, Stamford, Conn., October 16,1951.
a A more stable linkage resulting in polymer formation is frequently ~roducedby the dehydration of hydroxide groups on different metal atomsgiving rise to oxide bridges.
JUNE. 1952
solubility, however, is now controlled by the nature of the groups attached t o the donor molecules. HN
\\ C-0 H2N-C / \ / HN Ni \m \ / \ / C-NH, 0-C // (111) Octahedral metal complex
(IV) Octahedral metal complex with bidentate ligands
donors, two tridentate donors, or one sexadentate donor. Provided that the bond types are similar and that the steric requirements can be met by the donors, chelate compounds are generallymore stable than simple complexes, and the larger the number of rings the more stable the chelate. Thus the equilibrium in the reactions of the type Z
Z
,---.
Z
.c
HN \NH (VII) Bisguanylure%Ni (11)
"
CO
lies far t o the right, i. e . , the formation of the chelate is favored over that of the complex.
(VIII) Trisglyeinc-Co (11)
SOLUBILITY
Metal ions owe their aqueous solubility to the weakening of interionic attractions by the protective sheath of coordinated water molecules and to the fact that these hydrophyllic groups allow the metal t o fit into the solvent structure more easily than the corresponding salts. Replacement of these water molecules by other groups makes it possible to surround the ion by almost any desired environment, and thus to alter the solubility at will. A simple example of this is iflustrated by formulas V and VI. Reaction of the aquo ferric ion with 3 bidentate anions of 8-hydroxyquinoline (oxine) results in the chelate (V) which is neutral and presents a sheath of hydrophobic hydrocarbon groups to
I I 0-Fe/3 (V) Tris-oxino-Fe(II1)
I I 0-Fe/3 (VI) Sodium tris-6sulfooxinc-Few)
the surrounding aqueous medium. The resulting com~ o u n is d therefore insoluble in water and ureciuitates. or may be extracted by organic solvents such as chloroform. By substitution of certain groups it is possible to further modify the solubility of the complex. Thus the substitution of a sulfonic acid group on oxine results in the formation of a water-soluble chelate illustrated by formula VI. There is little difference in the stabilities of the two chelate compounds, and the properties of the metal ion are about the same. The
. .
0% (IX) Metal chelate of ammoniatriacetate ion
272
JOURNAL OF CHEMICAL EDUCATION
Examples of stable water-soluble chelate compounds are illustrated by formulas VII-X. I n these compounds the number of oxygens and other polar groups far outweigh the effect of the hydrocarbon groups present. The result is high solubility in aqueous solution, and, in the case of I X and X, the complexes are highly chelated and hence highly stable. The corresponding organic complexing agents, ethylenediaminetetraacetic acid in particular, are manufactured in large amounts a t the present time as sequestering agents, i. e., water-soluble metal ion deactivators. On these two properties, high stability and high solubility, depend their uses as detergent additives, clarification agents for liquid soaps and various aqueous preparations, the inhibition of oxidation reactions catalyzed by metal ions, prevention of trace metal effects on dyes, and many other applications. An important use of the organic-soluble chelates is solvent extraction of metal ions for analytical or largescale separations. The principles involved in such separations have been outlined by Calvin (1). Best results are apparently obtained when the metal chelate is soluble in the oreanic solvent and relativelv insoluble in water, while the unchelated metal species present are insoluble in the organic solvent employed. These bidealized conditions may be expressed by the equilibrium:
chelates of acetylacetone and TTA are illustrated schematically by formulas X I and XII.
p
CH,
s/\
\
'
2-O, CH M/n
\
/
C=O
2-O\ C\H C=O
/
CHI ( X I ) Metal chelate of acetylacetone
/MIn
/
CFs (XII) Metal chelate of T T A
When intermediate (stepwise) complexes are formed, or when the metal ion is in equilibrium with other species such as hydrolytic and polymeric forms, in aqueous solutions, the idealized equations given above for solvent extraction equilibria are greatly complicated. For solvent systems involving hydrolysis (2) and polymeric forms (3) the reader is referred t o the recent work of Connick and co-workers, while relationships for solvent extraction involving intermediate complexes have been given by Irving and Williams (4).
u
M"(w)
+ nHKe(o) = MKe,(o) + nH+(ur)
The equilibrium constant for this reaction is:
The two terms on the left of the quotient represent the distribut,ion rat,io of the metal between organic and water solutions, D(o/w). Since this is the quantity usually measured, equation (1) is best rearranged to
ELECTRICAL CONDUCTANCE
The disappearance or formation of ions in solution, a phenomenon closely related t o complex formation, may be followed easily by observing changes in electrical conductance of the solution. Although this method was used as a powerful tool in the investigation of the nature of complex salts by Werner ( 5 ) , the effect of the formation of coordination compounds on conductance has not been studied to the extent that one would expect. Probably the first observation of the special properties of chelate compounds was reported by Ley (6), who based his conclusions on the change in electrical conductance of the solution. Because of the very low electrical conductance observed, he proposed that' bisglycino copper (11) involved the formation of two 5-membered rings with the glycinate ion:
Equation (2) indicates that the extraction of a particular metal by the organic solvent will be improved by COhigh concentration of the chelating agent in the organic phase and opposed by high hydrogen ion conCHS-NH1 L C 0 centration in the aqueous phase. Hence, the extrac( X I I I ) Bisglycino-Cu (11) tion of a metal from a mixture may be made selective In a later paper (7) he made interesting comparisons by varying the pH of the aqueous solution, the strongly complexed metals (large value of K ) being readily between the electrical conductances of cupric acetate extracted a t low pH, but the more weakly complexed and various amino acid chelates involving rings of metals are extractable only a t higher pH. Acetylace- varying size. Some of his results are listed in Table 1. tone, a very well-known complexing agent which forms stable non-ionic complexes with most metals, has the TABLE 1 disadvantage as a solvent extraction agent of too high Molar Conductances of Cumic Chelates aqueous solubility of both the complexing agent and Cu(Ac)r Cu(Ac)? CU(AC)~ the metal complexes. Calvin and co-workers have glycine 8-alanzne ramznobudeveloped a complexing agent thenoyltrifluoroacetone Dilution Cu(Ae). lyric aezd A A A A (TTA) which forms chelates of high organic solubility without sacrificing too much in stability of the chelate. / 40.6 20.8-19.7 36.6-3.9 42.4+1.8 '/M 49.6 25.3 -23.3 43.2 - 6 . 4 50.9 f 1 . 3 This compound has been widely used in recent years '/LZS 59.4 30.4 -29.0 50.3 - 9 . 0 for metal separations by solvent extraction. Typical
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