31 P nuclear magnetic resonance (NMR) based on the derivatization reagent 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane is a common approach for the hydroxyl group determination of lignins, but the results are sometimes less reproducible compared to other methods. In the present work, common pitfalls in 31 P NMR analysis of kraft lignin (KL) and lignosulfonates (LS) are addressed and the results are compared to those obtained by 1 H NMR spectroscopy. Several experimental parameters are revisited in terms of the reliability of the obtained data, such as the choice of relaxation delay, internal standards, and the best solution technique for the 31 P NMR analysis of LS. For the first time, 31 P NMR data of LS are presented based on a new dissolution protocol. The analytical data of a set of lignins consisting of three KLs, one LS, and one milled wood lignin are presented based on the optimized 31 P NMR approach.Keywords: 1 H NMR of lignin, 31 P NMR of lignin, Indulin AT kraft lignin, internal standard for NMR, lignosulfonate, milled wood lignin (MWL), quantification of hydroxyl groups

The chromophore release and identification method isolates well-defined chromophoric substances from different cellulosic matrices, such as highly bleached pulps, cotton linters, bacterial cellulose, viscose or lyocell fibers, and cellulose acetates. The chromophores are present only in extremely low (ppm to ppb) concentrations. The concept of primary and secondary chromophores is introduced, with primary chromophores arising only from the polysaccharides inherent to cellulosic materials. Secondary chromophores also include atoms from the chemicals used to process the cellulose. Most primary chromophores belong to one of three compound classes: hydroxy-[1,4]-benzoquinones, hydroxy-[1,4]-naphthoquinones, and hydroxyacetophenones. Among them, three individual compounds dominate: 2,5-dihydroxy-[1,4]-benzoquinone, 5,8-hydroxy-[1,4]-naphthoquinone, and 2,5-dihydroxyacetophenones, amounting to more than 80 % of the total isolated chromophores in most cases. In lignin-free cellulosics, these three compounds can thus be regarded as key chromophores. The prevalence of these molecules is due to both exceptionally strong resonance stabilization, as reflected in delocalized double bonds, and their ready reformation from carbohydrate degradation products by recondensation reactions. The findings that (a) most chromophores in lignin-free cellulosic materials belong to only three compound classes and that (b) three chromophore compounds make up the bulk of the chromophore mixtures are foundational for future bleaching research: Based on this knowledge, specific searches for optimized bleaching conditions can now concentrate on these compounds and still cover the vast majority of chromophores.

In this study, a novel approach for isolation and purification of lignosulfonates from spent sulfite liquor was established.

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