Thermodynamic model of Ni(II) solubility, hydrolysis and complex formation with ISA

摘要

The solubility of β–Ni(OH)2(cr) was investigated at T=(22±2)°C in the absence and presence of α-isosaccharinic acid (ISA), the main degradation product of cellulose under alkaline pH conditions. Batch solubility experiments were performed from undersaturation conditions under inert gas (Ar) atmosphere. Solubility experiments in the absence of ISA were conducted in 0.5 and 3.0 M NaCl–NaOH solutions at 7.5≤ pHm ≤13 (with pHm=–log10[H+]). XRD analyses of selected solid phases collected after completing the solubility experiments (≈300 days) confirmed that β–Ni(OH)2(cr) remains as solid phase controlling the solubility of Ni(II) in all investigated conditions. Based on the slope analysis (log10[Ni] vs. pHm) of the solubility data and solid phase characterization, the equilibrium reactions β–Ni(OH)2(cr)+2 H+?Ni2++2 H2O(l) and β–Ni(OH)2(cr)?Ni(OH)2(aq) were identified as controlling the solubility of Ni(II) within the investigated pHm region. The conditional equilibrium constants determined from the solubility experiments at different ionic strengths were evaluated with the specific ion interaction theory (SIT). In contrast to the current thermodynamic selection in the NEA–TDB, solubility data collected in the present work does not support the formation of the anionic hydrolysis species Ni(OH)3? up to pHm ≤13.0. Solubility experiments in the presence of ISA were conducted in 0.5 M NaCl–NaOH–NaISA solutions with 0.01 M≤[NaISA] ≤0.2 M and 9≤ pHm ≤13. XRD analyses confirmed that β–Ni(OH)2(cr) is also the solid phase controlling the solubility of Ni(II) in the presence of ISA. Solubility data of all investigated systems can be properly explained with chemical and thermodynamic models including the formation of the complexes NiOHISA(aq), Ni(OH)2ISA? and Ni(OH)3ISA2?. The reported data confirm the low solubility (<10?7 M) of Ni(II) in hyperalkaline pH conditions representative of cementitious environments (10≤ pH ≤13), which increases to up to 10?5 M