Structural Characterization of Large Polycyclic Aromatic Hydrocarbons. Part 1: The Case of Coal Tar Pitch and Naphthalene-Derived Pitch

The different thermal behaviors and solubilities of large and structurally different polycyclic aromatic hydrocarbon (PAH) mixtures featuring coal tar pitch (CP) and naphthalene synthetic pitch (NP) samples could be read in light of their different molecular weight (MW) distribution and spectroscopic features. The number-average MW obtained by mass spectrometry for CP (417 Da) and NP (691 Da) resulted to be lower in comparison to the values evaluated by size-exclusion chromatography (SEC) (796 and 824 Da for CP and NP, respectively) because of the different response of the detector of mass spectrometry to low- and high-MW components. Hence, SEC showed to be more suitable for the analysis of PAH mixtures overlapping and covering a higher mass range in comparison to mass spectrometry. Insights into structural PAH features were given by means of spectroscopic analysis [infrared (IR), ultraviolet-visible (UV-vis), and fluorescence], allowing for the discrimination between different families of PAHs as ortho-fused PAHs and rylenes interspersed with aliphatic (mainly naphthenic) groups, mainly featuring CP and NP, respectively. Besides showing the different aromaticity and aliphatic/aromatic hydrogen distribution, the improvement of Fourier transform infrared (FTIR) and UV-vis absorption analysis put also in evidence the contribution of carbon-rich particle impurities and PAH aggregates in CP and NP, respectively.