Journal
ANALYTICA CHIMICA ACTA
Volume 522, Issue 2, Pages 247-258Publisher
ELSEVIER SCIENCE BV
DOI: 10.1016/j.aca.2004.07.005
Keywords
NMR titration; pK determination; NMR pH indicator; in situ pH measurement; error analysis
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NMR titration is an efficient method to determine pK(a) values of multiprotic acids in aqueous solution. While modem 1D/2D NMR techniques yield chemical shifts with increasing precision, the glass electrode-based pH measurement becomes the limiting factor to affect the precision of the resulting dissociation constants. The pH in the NMR tube can also be deduced from the actual chemical shift of an appropriate monoprotic indicator molecule. In the present work, the in situ NMR pH measurement has been extended for the entire pH range 0-12 using indicators with overlapping ranges of dissociation. In the first, calibrating H-1/P-31 NMR titration, limiting chemical shifts and pK were determined for each indicator. An analysis of error propagation showed that the accuracy and precision of glass electrodes can be achieved at 1.8 < pH < 12 and even exceeded at pH extremes by NMR indicators, respectively. The assembled set of indicators was applied for in situ pH monitoring in the following electrodeless H-1/P-31 NMR titration of a newly synthesized aminophosphinophosphonic acid. Multivariate nonlinear parameter estimation was used to calculate the pK values that were confirmed by potentiometric titrations. (C) 2004 Elsevier B.V. All rights reserved.
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