Rate-limiting steps in bromide-free TEMPO-mediated oxidation of cellulose-Quantification of the N-Oxoammonium cation by iodometric titration and UV-vis spectroscopy

A iodometric titration method was introduced to study the conversion of 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) to the corresponding N-oxoammonium cation (TEMPO⁺) by hypochlorite in the absence and presence of bromide ion. The validity of the titration was verified with UV-vis spectroscopy combined with a multivariate curve resolution (MCR) algorithm to calculate the concentrations and spectral signatures of the pure components (i.e., TEMPO, Cl(+1) and TEMPO⁺). The formation of the oxoammonium cation was successfully followed during the activation of TEMPO by HOCl and HOBr. It was found that HOBr is a more effective activator for TEMPO than HOCl is. Moreover, the importance of a separate activation step for TEMPO with bromide-free TEMPO oxidations could be identified with this titration method. The content of TEMPO⁺ was also monitored during the TEMPO-mediated oxidation of a cellulosic pulp by hypochlorite in the absence and presence of bromide. It was found that the oxidation of the alcoholic groups by TEMPO⁺ was generally the rate-determining step and much slower than the regeneration of TEMPO⁺ through oxidation of the hydroxylamine by HOCl and HOBr. However, at high pH the latter reaction became rate-limiting.