The specific locations of the double bonds in linear olefins can facilitate olefin catalytic synthetic reactions to improve the quality of target olefin products. We developed a simple and efficient approach based on single photon ionization time-of-flight mass spectrometry (SPI-TOFMS) combined with online ozonolysis to identify and quantify the linear olefin double bond positional isomers. The online ozonolysis cleaved the olefins at the double bond positions that led to formation of corresponding characteristic aldehydes. The aldehydes were then detected by SPI-TOFMS to achieve unique spectrometric "fingerprints" for each linear olefin to successfully identify the isomeric ones. To accurately quantify the isomeric components in olefin mixtures, an algorithm was proposed to quantify three isomeric olefin mixtures based on characteristic ion intensities and their equivalent ionization coefficients. The relative concentration errors for the olefin components were lower than 2.5% while the total analysis time was less than 2 min. These results demonstrate that the online ozonolysis SPI-TOFMS has the potential for real-time monitoring of catalytic olefin synthetic reactions.
Keywords: Double bond position; Olefin; Ozonolysis; Time-of-flight mass spectrometry.