Characterization of coal by matrix‐assisted laser desorption ionization mass spectrometry. I. The argonne coal samples

The Argonne set of coals cover the rank range from lignite to semi‐anthracite; these samples have been studied by matrix‐assisted laser desorption mass spectrometry (MALDI‐MS) in a time‐of‐flight mass spectrometer equipped with a nitrogen laser at 337 nm, using sinapinic acid as matrix. The coal particle size was less than 5 microns. The characteristics of the MALDI‐MS spectra of the set of coals were found to be rank‐related; desorption from high‐rank coals was found to take place with greater relative ease than from low‐rank coals. Two major features were found in all spectra: a homologous series of peaks in the 200–500 u mass range and an intense peak between 1000 and 5000 u, the particular shape of the peak depending on coal rank. A continuum of lower intensity peaks extending to very large molecular masses was found in all spectra, the upper limit of molecular masses increasing with coal rank at the same laser fluence. The effect of changes in laser power on spectra was investigated: upper mass limits were found to increase with power up to the detection limit of the instrument but low‐mass parts of spectra were found to distort, possibly due to detector overloading. A maximum laser fluence value acceptable over the coal‐rank range represented by these samples could therefore not be easily defined. None of the mass spectra showed evidence of the presence of either carbon clusters or fullerene formation, indicating that laser fluences did not reach intensities high enough to induce substantial secondary reactions. Comparing molecular mass distributions detected by MALDI of coal pyrolysis tars and directly from coals suggests the MALDI and pyrolytic mechanisms of volatile release to be structurally different; in particular, the preferential evaporation of lighter species which occurs during pyrolytic tar evolution (and during field‐ionization mass spectroscopy) appears to evole material with a more restricted range of molecular masses compared to laser desorption mechanisms.