A study of the metal binding capacity of saccharinic acids formed during the alkali catalysed decomposition of cellulosic materials: nickel complexation by glucoisosaccharinic acids and xyloisosaccharinic acids

• A one to one complex of nickel and β-glucoisosaccharinate (GISA) is formed at pH 7.
• The stability constant for Niβ-GISA (log10β = 1.94) is similar to that of Niα-GISA.
• Xyloisosaccharinic acid (XISA) forms a Ni.XISA complex at pH 7 (log10β = 0.83).
• At high pH (>13) β-GISA, α-GISA and XISA all form Ni2(L)(OH)4 complexes
• Ni2.β-GISA(OH)4 (log10β = 30.6) is more stable than Ni2.α-GISA(OH)4 (log10β = 29.0).

The stoichiometry of the metal complexes formed between nickel and the ligand β-glucoisosaccharinic acid (β-GISA) and a racemic mixture of enantiomers of xyloisosaccharinic acid (XISA) has been determined at both neutral and alkaline pHs. Bjerrum plots, Job's plots and conductance measurements indicated that for each of the systems one to one Ni(ligand) complexes were formed at near neutral pHs (<7.5). At intermediate alkaline pHs (7.5–13) there is evidence to support the formation and precipitation of Ni2(ligand)(OH)3 complexes, finally, at high pH (>13) sparingly soluble Ni2(ligand)(OH)4 complexes were formed. The stability constants for the Ni(β-GISA), Ni(α-GISA) and Ni(XISA) complexes formed at neutral pH were determined under identical conditions using polarographic studies. The measured stability constants for Ni(β-GISA) (log10 β = 1.94 ± 0.15) and for Ni(α-GISA)(log10 β = 2.07 ± 0.13) are very similar; the value measured for the Ni(XISA) complex (log10 β = 0.83) was an order of magnitude smaller. The stability constants for the Ni2(Ligand)(OH)4 complexes formed at highly alkaline pHs were determined using the Schubert method. The measured stability constant for Ni2(β-GISA)(OH)4 (log10 β = 30.6 ± 0.5) was an order of magnitude bigger than the value for Ni2(α-GISA)(OH)4 (log10 β = 29.0 ± 0.5) measured under identical conditions. Attempts to measure the stability constant for Ni2(XISA)(OH)4 were unsuccessful; Ni2(XISA)(OH)4 complexes were not present in significant amounts at high pH to allow the log10β value to be determined by the Schubert method.

Comparison of the metal binding capacity of beta-glucoisosaccharinic acid (β-GISA), alpha-glucoisosaccharinic acid (α-GISA), and xyloisosaccharinic acid.Figure optionsDownload as PowerPoint slide