Measurement of hydrolysis, polymerization and complexation in dilute aluminum solutions

The nature of chemical reactions taking place during the titration of dilute Al solutions in the presence of either chloride or sulfate were examined by refining the apparent Al hydrolysis products assuming the presence of solution species with n (OH/Al mole ratio) equal to 1, 2, 2.5, 3 and 4. The second and third hydrolysis products for Al were refined by comparison of calculated titration patterns to those observed for 10⁻³, 10⁻⁴ and 10⁻⁵ M Al in 1 M, 0.1 M and 0.01 M KCl. A large degree of polynuclear character of Al solutions was found even at Al concentrations as low as 10⁻⁵ M. The n value and size of the polynuclear complexes are affected by Al concentration. The concentration constant, pQ₁₃ is found to be at least 17.4-17.7. It is concluded that the mononuclear Al(OH)₂ species is never significant. Use of statistical analysis of the data and graphical methods did not result in consistent data for polymer size determinations.

The lower pQ values for mononuclear Al hydrolysis are explained by the structural instability of the mononuclear complexes. The bond strengths required for the bonds in the second and third hydrolysis complexes are often larger than those allowed for octahedral coordination. For that reason, the pQ values would be lower than calculated by extrapolation between the stable first and fourth hydrolysis constants.

A new polynuclear complexation mechanism for Al is proposed to account for the high concentration of high n value polynuclear species in the titration refinements. The proposed linear l double chain structure has a structure consistent with boehmite and diaspore. This structure differs from the linear single chain and ring based polynuclear structures by the presence of rows of three coordinated oxygens in the bond central chain and rows of two and one coordinated oxygens along the plane edges. A rearrangement of internal charge in this structure is proposed in which part of the charge is removed from the three coordinated oxygens to result in an uncharged hydroxyl with the charge shifted to the one coordinated site neutralizing the hydroxyl. This results in a general formula for the polynuclear structure of (Al(OH)₃)_x(Al(OH)₂)₂²⁺. This structure results in a higher n value for a lower number of Al than does the other polynuclear complexation schemes and therefore explains the presence of high n value polymers in unaged Al solutions which would have required polymers of greater than a hundred Al cations.

The observed presence of a second Al plateau on titration patterns with Al concentrations greater than 5 x10⁻⁵ M could not be the result of the onset of precipitation as earlier proposed. It is proposed that at a pH in the 6 to 7 range, a change of some of the one coordinated sites on the edge of the larger polynuclear and precipitant structures from water to hydroxyls results in a change in net edge charge from net positive to net negative which causes an increased rate of crystal growth due to the unlike charge between the edges and the smaller polynuclear and mononuclear complexes.

The refinement of Al titration data in K₂SO₄, provide pQ values one to three pQ units lower than those obtained from equivalent KCl solutions. A catalytic mechanism is proposed in which Al polymerization is facilitated by the formation of mononuclear Al hydroxy sulfate complexes which combine together to form nonsulfate containing polynuclear complexes. The increased hydrolyzed concentration and lower ionic charge resulting from these complexes would increase the rate of polymerization in these systems.

Evidence for the presence of mononuclear hydroxy sulfate complexes comes from the better fit for titration patterns in sulfate systems which would not have been observed for increased polymerization alone.