13C NMR and electrospray ionization mass spectrometric study of sucrose aqueous solutions at high pH: NMR measurement of sucrose dissociation constant

The 13C NMR technique is used for the measurement of the first dissociation constant of sucrose (HL) in highly alkaline solutions. In 1.0 M NaCl/NaOH medium and for 25 °C, the concentration dissociation constant (pK1) was 13.1 ± 0.3; and, for 60 °C, pK1 = 12.30 ± 0.05. The β-d-fructofuranosyl ring was found to be responsible for dissociation. The NMR data reveal no clear evidence of the second dissociation step below pH 14, either at 25 °C or at 60 °C. In the solutions with 4–10 mol dm−3 NaOH content the 13C NMR technique indicated the chemical shift changes, treated as the second dissociation step of sucrose and a sodium complex formation. A very rough estimation, for variable ionic strength, gives the value: pK2 ∼ 15.8 ± 0.8. The anionic species L− and NaH−1L− have been registered by electrospray ionization time-of-flight mass spectrometry (ESI-ToF MS) for 0.01 M sucrose solutions with initial pH 13.