Association quotients of aluminum sulphate complexes in NaCl media from 50 to 125 C: Results of a potentiometric and solubility study
- Univ. of Nebraska, Lincoln, NE (United States). Dept. of Geology
- Oak Ridge National Lab., TN (United States). Chemical and Analytical Sciences Div.
The speciation and molal formation quotients for the complexation of aluminum with sulphate were measured based on potentiometric and solubility experiments. Potentiometric titrations, utilizing a hydrogen-electrode concentration cell, were performed from 50 to 125 C at ionic strengths of 0.1, 0.3 and 1.0 molal in aqueous NaCl media. Two aluminum-sulphate species, AlSO{sub 4}{sup +} and Al(SO{sub 4}){sub 2}{sup {minus}}, were identified from the titration data and the formation quotients for these species were modeled by empirical equations to describe their temperature and ionic strength dependencies. Thermodynamic parameters for the complexation reactions were obtained by differentiating the empirical equations with respect to temperature. The thermodynamic quantities obtained for the formation of AlSO{sub 4}{sup +} at 50 C and infinite dilution are: logK{sub 1} = 3.7 {+-} 0.4, {Delta}H{sub 1}{degree} = {minus}10 {+-} 30 kJ/mol, {Delta}S{sub 1}{degree} = 40 {+-} 100 J/K{center_dot}mol and {Delta}C{sub p 1}{degree} = 1900 {+-} 800 J/K{center_dot}mol; whereas the values for Al(SO{sub 4}){sub 2}{sup {minus}} are: logK{sub 2} = 5.6 {+-} 0.7, {Delta}H{sub 2}{degree} = 10 {+-} 50 kJ/mol, {Delta}S{sub 2}{degree} = 100 {+-} 100 J/K{center_dot}mol and {Delta}C{sub p 2}{degree} = 2800 {+-} 800 J/K{center_dot}mol. A solubility study, which was undertaken to verify the 50 C potentiometric data, was performed by reacting powdered gibbsite (Al(OH){sub 3}) with sulphate solutions at 10{sup {minus}3.5} and 10{sup {minus}4} molal H{sup +}, total sulphate concentrations from 0.005 to 0.080 molal, and 0.1 and 1.0 molal ionic strength in aqueous NaCl media. The results of the solubility study are in good agreement with the potentiometric data and establish that Al-sulphate complexation substantially enhances the equilibrium solubility of gibbsite.
- Sponsoring Organization:
- USDOE, Washington, DC (United States); National Science Foundation, Washington, DC (United States)
- DOE Contract Number:
- AC05-96OR22464
- OSTI ID:
- 355669
- Journal Information:
- Geochimica et Cosmochimica Acta, Vol. 63, Issue 3-4; Other Information: PBD: Feb 1999
- Country of Publication:
- United States
- Language:
- English
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