Abstract
Quantitative 1H NMR spectroscopy was used to study chemical equilibria and reaction kinetics of both the formation and decomposition of 1,3,5-trioxane in aqueous formaldehyde solutions. The reaction was homogeneously catalyzed with up to 0.10 g g−1 sulfuric acid at temperatures between 360 and 383 K so that most of the experiments had to be carried out pressurized. The studied mixtures were complex due to the formation of methylene glycol and poly(oxymethylene) glycols in aqueous formaldehyde and the presence of considerable amounts of ionized species. Most common internal standards are decomposed by the hot sulfuric acid and external standards were not applicable using the flow NMR probe or pressurizable NMR sample tubes. Therefore, for the quantification of the small trioxane signals, a novel procedure was applied, in which electronically generated NMR signals were used as highly stable Virtual References (VR). The NMR decoupler channel with wave-form generator was used as the source of the reference signal, which was irradiated into the probe using the lock coil. Details on the experimental procedure are presented. It is shown that the presented method yields reliable quantitative reaction data for the complex studied mixtures.
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Acknowledgements
The authors gratefully acknowledge the contributions of Florian Zieker, Johanna Schell, and Reeta Nording, Stuttgart, both for the experiments and their evaluation. Thanks are due also to Wolf Hiller, Varian Deutschland, Darmstadt, for help in implementing the Virtual Reference method. Financial support for this work by BASF AG, Ludwigshafen, is gratefully acknowledged.
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Maiwald, M., Grützner, T., Ströfer, E. et al. Quantitative NMR spectroscopy of complex technical mixtures using a virtual reference: chemical equilibria and reaction kinetics of formaldehyde–water–1,3,5-trioxane. Anal Bioanal Chem 385, 910–917 (2006). https://doi.org/10.1007/s00216-006-0477-3
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DOI: https://doi.org/10.1007/s00216-006-0477-3