Effects of low temperature on aluminum(III) hydrolysis: Theoretical and experimental studies

In this study, the effects of low temperature on aluminum(III) (Al) hydrolysis were examined both theoretically and experimentally by constructing a solubility diagram for amorphous aluminum hydroxide (Al(OH)(3)am)) and a distribution diagram of hydrolyzed Al species. First, thermodynamic data of Al species at 4 degrees C were calculated from that at 25 degrees C. A well confirmed polymeric Al species, AlO4Al12(OH)(24)(7+)(Al-13) was involved in building the diagrams and, correspondingly, the non-linear simultaneous equations with 13 degrees were resolved. Secondly, polarized Zeeman atomic absorption spectrophotometry (AAS), Al-27 nuclear magnetic resonance (NMR) spectroscopy, and ferron-based spectrophotometry were applied for constructing the practical diagrams. The results show that a decrease of temperature from 25 to 4 degrees C caused the AI(OH)3(am) boundary on the solubility diagram to shift toward the alkaline side by about 1.0 pH unit and the minimum solubility of Al(OH)(3)(am) to reduce by 1.0 log unit. The distribution diagram indicates that the monomeric Al, Al-13, and solid-phase AI(OH)3 were alternately the predominant species with the increase of pH value during Al hydrolysis. At 25 degrees C, Al-13 was the dominant species in a pH range of 4.0 to 4.5, whereas at 4 degrees C, Al-13 was the leading species in a pH range spaced from 4.5 to 6.3. The predominant species changed from the monomeric Al to the solid-phase Al(OH)(3) over the range of 1.8 pH units at 4 degrees C in comparison with the range of 0.5 pH unit at 25 degrees C.