BROADBAND MICROWAVE SPECTROSCOPY OF LIGNIN, BIOFUELS AND THEIR PYROLYSIS INTERMEDIATES
thesisposted on 03.01.2019, 20:41 by Alicia O. Hernandez-CastilloAlicia O. Hernandez-Castillo
The chemical complexity of hydrocarbon fuels and the fast-expanding list of potential plantderived biofuels pose a challenge to the scientific community seeking to provide a molecular understanding of their combustion. More refined spectroscopic tools and methodologies must be developed to selectively detect and characterize the widening array of fuel components and combustion reactive intermediates. The direct relationship between molecular structure and rotational frequencies makes rotational spectroscopy highly structural specific; therefore, it offers a powerful means of characterizing pyrolysis ntermediates. This thesis describes experimental work using broadband microwave spectroscopy to address a number of challenging problems in the spectroscopy of gas complex mixtures.
Usually, the observed rotational spectra contain contributions from many distinct species, creating a complicated spectrum with interleaved transitions that make spectral assignment challenging. To assist with the process, a protocol called “strong-field coherence breaking” (SFCB) has been developed. It exploits multi-resonance effects that accompany sweeping the microwave radiation under strong-field conditions to output a set of transitions that can confidently be assigned to a single component in a mixture, thereby reducing the spectral assignment time.
The broadband chirped pulse Fourier transform microwave (CP-FTMW) spectra of guaiacol, syringol, 4-methyl guaiacol, 4-vinyl guaiacol were recorded under jet- cooled conditions over the 2-18 GHz frequency range. Using data from the 13C isotopomers the r0 structure of guaiacol was determined by means of a Kraitchman analysis. The tunneling due to OH hindered rotation was observed in syringol and the V2 barrier was deduced to be 50% greater than phenol’s barrier. This is due to the intramolecular H-bonding between the hydroxy and the methoxy groups. The internal rotation barrier for the methyl group for 4-methyl guaiacol was also determined. Moreover, the spectral assignment of the two conformers of 4-vinyl guaiacol was sped-up by using SFCB. The main structural insight from these lignin-related molecules was that polar substituents dictate the magnitude and type of structural shift that occurs relative to that of the unsubstituted aromatic ring.
In the next part of my work, the pyrolysis of 2-methoxy furan was carried out over the 300-1600 K temperature range, with microwave detection in the 2-18 GHz frequency range, using hightemperature flash pyrolysis micro-reactor coupled with a supersonic expansion. The SFCB technique was used to analyze and speed up the line assignment. The 2-furanyloxy radical, a primary, resonance-stabilized radical formed by loss of a methyl group in the pyrolysis of 2-methoxy furan, was detected and its molecular parameters were determined.
Finally, a unique setup that combines the high-resolution spectroscopic data provided by chirped pulse Fourier transform microwave (CP-FTMW) spectroscopy with photoionization mass spectra from a vacuum ultraviolet (VUV) time-of-flight mass spectrometer (TOF-MS) was used to find optimal conditions to detect reactive intermediates and make full assignments for the microwave spectra of phenoxy radical and o-hydroxy phenoxy radical over the 2-18 GHz range. Phenoxy radical was generated through the pyrolysis of anisole and allyl phenyl ether. Using a combination of data from 13C isotopomers and fully deuterated phenoxy radical, in combination with high level ab initio calculations, a near-complete r0 structure for the radical was obtained. The structural data point to the radical being a primarily carbon-centered rather than oxygencentered radical. Using guaiacol as precursor, we studied the spectroscopy of the o-hydroxy phenoxy radical, whose structural data is compared with that of phenoxy to understand the role played by the hydroxyl group in modifying the resonance stabilization of the radical.