Quantitative in-situ monitoring of parahydrogen fraction using Raman spectroscopy

Parrott, Andrew J. and Dallin, Paul and Andrews, John and Richardson, Peter M. and Semenova, Olga and Halse, Meghan E. and Duckett, Simon B. and Nordon, Alison (2018) Quantitative in-situ monitoring of parahydrogen fraction using Raman spectroscopy. Applied Spectroscopy. ISSN 0003-7028 (https://doi.org/10.1177/0003702818798644)

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Raman spectroscopy has been used to provide a rapid, non-invasive and non-destructive quantification method for determining the parahydrogen fraction of hydrogen gas. The basis of the method is the measurement of the ratio of the first two rotational bands of hydrogen at 355cm−1 and 586cm−1 corresponding to parahydrogen and orthohydrogen, respectively. The method has been used to determine the parahydrogen content during a production process and a reaction. In the first example, the performance of an in-house liquid nitrogen cooled parahydrogen generator was monitored both at-line and on-line. The Raman measurements showed that it took several hours for the generator to reach steady state and hence, for maximum parahydrogen production (50 %) to be reached. The results obtained using Raman spectroscopy were compared to those obtained by at-line low-field NMR spectroscopy. While the results were in good agreement, Raman analysis has several advantages over NMR for this application. The Raman method does not require a reference sample, as both spin isomers (ortho and para) of hydrogen can be directly detected, which simplifies the procedure and eliminates some sources of error. In the second example, the method was used to monitor the fast conversion of parahydrogen to orthohydrogen in-situ. Here the ability to acquire Raman spectra every 30s enabled a conversion process with a rate constant of 27.4 × 10−4 s−1 to be monitored. The Raman method described here represents an improvement on previously reported work, in that it can be easily applied on-line and is approximately 500 times faster. This offers the potential of an industrially compatible method for determining parahydrogen content in applications that require the storage and usage of hydrogen.