The combination of inorganic phosphate and pyrophosphate ³¹P-NMR for the electrodeless pH determination in the 5-12 range

Potentiometry is the primary pH measurement method, but alternatives are sought beyond glass electrodes operative limitations. In nuclear magnetic resonance (NMR) experiments, electrodeless pH sensing is important to track changes along titrations, during chemical reactions or inside compartmentalized environments inaccessible to electrodes, for instance. Although several interesting NMR pH indicators have been already presented, the potential of inorganic phosphate is overlooked, despite its common presence in NMR samples as the buffer main component. Its use for electrodeless pH determination can be expanded by exploiting all its three proton dissociations. This study was aimed at verifying the use of inorganic phosphate P-31 chemical shift to sense pH variations, and at exploring the complementary use of pyrophosphate ions to cover a wide pH range. A simple set of equations is presented to utilize both phosphate and pyrophosphate P-31 chemical shift in combination for accurate pH determination without a glass electrode over the 5-12 pH range, and without affecting the spectrum of other nuclei. The present study demonstrated an average deviation of 0.09 (maximum <0.2) pH unit from glass electrode measurements. The trimethylphosphate can be used as a suitable chemical shift reference for both P-31 and H-1 (also C-13), with its hydrolysis being significant only at pH > 12. The method was also demonstrated by determining the pKa of three distinct molecules in a mixture and by comparing the results to those obtained when the glass electrode was used to measure the pH. The approach shown here can be easily tuned to different experimental conditions.