Browsing by Author "Tummala, Gopi Krishna"
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- Rate-limiting steps in bromide-free TEMPO-mediated oxidation of cellulose-Quantification of the N-Oxoammonium cation by iodometric titration and UV-vis spectroscopy
A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä(2015) Pääkkönen, Timo; Bertinetto, Carlo; Pönni, Raili; Tummala, Gopi Krishna; Nuopponen, Markus; Vuorinen, TapaniA 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.