Chapitre d'équation 1 Section 1NMR relaxometry to monitor chromium (VI) reduction by hydrogen peroxide, ascorbic acid and aluminum powder.

The reduction of K 2 Cr 2 O 7 solutions by H 2 O 2 was studied by NMR relaxometry and UV-Vis spectroscopy in HCl/KCl buffer (pH2), NaCl/Glycine/HCl buffer (pH3) and sodium acetate/acetic acid buffer (pH4). Because of Cr (III) paramagnetism, 1/T 1 and 1/T 2 of the solutions increase during the reduction of diamagnetic Cr (VI). This increase is proportional to the produced Cr (III) concentration. Using different initial H 2 O 2 concentrations, partially reduced Cr (VI) samples were prepared and studied by T 1 and T 2 relaxometry and by UV-Vis spectroscopy. The correlation between the relaxation rates and the concentration of Cr (VI) remaining in the sample, measured by spectroscopy, was excellent. It was possible, thanks to the measurement of T 2 , to study the kinetics of the reduction of K 2 Cr 2 O 7 by H 2 O 2 in the pH3 and pH4 buffers. The reduction of Cr (VI) by ascorbic acid was successfully monitored by NMR relaxometry in the pH2 buffer. The presence of complexing molecules/ions was shown to drastically influence the Nuclear Magnetic Relaxation Dispersion profiles of reduced K 2 Cr 2 O 7 solutions: both relaxation rates are divided by ~5 when citrate or acetate ions are present and by ~3 in the presence of ascorbic acid. Therefore, the comparison of relaxation results obtained in different reaction mixtures must be done carefully. When all the solutions are set to pH0, which prevents any complexation, the longitudinal and transverse relaxation rates of all samples become comparable. Finally, as a proof of concept for a turbid solution, the kinetics of the reduction of a K 2 Cr 2 O 7 solution by aluminum powder in the pH2 buffer was successfully monitored.