A combination of solid-state 13C NMR, X-ray photoelectron spectroscopy (XPS) and sulfur X-ray absorption
near edge structure (S-XANES) techniques are used to characterize organic oxygen, nitrogen, and sulfur species
and carbon chemical/structural features in kerogens. The kerogens studied represent a wide range of organic
matter types and maturities. A van Krevelen plot based on elemental H/C data and XPS derived O/C data
shows the well established pattern for type I, type II, and type III kerogens. The anticipated relationship between
the Rock−Eval hydrogen index and H/C is independent of organic matter type. Carbon structural and lattice
parameters are derived from solid-state 13C NMR analysis. As expected, the amount of aromatic carbon, measured
by both 13C NMR and XPS, increases with decreasing H/C. The correlation between aromatic carbon and
Rock−Eval T
max, an indicator of maturity, is linear for types II and IIIC kerogens, but each organic matter
type follows a different relationship. The average aliphatic carbon chain length (Cn‘) decreases with an increasing
amount of aromatic carbon in a similar manner across all organic matter types. The fraction of aromatic carbons
with attachments (FAA) decreases, while the average number of aromatic carbons per cluster (C) increases
with an increasing amount of aromatic carbon. FAA values range from 0.2 to 0.4, and C values range from 12
to 20 indicating that kerogens possess on average 2- to 5-ring aromatic carbon units that are highly substituted.
There is basic agreement between XPS and 13C NMR results for the amount and speciation of organic oxygen.
XPS results show that the amount of carbon oxygen single bonded species increases and carbonyl−carboxyl
species decrease with an increasing amount of aromatic carbon. Patterns for the relative abundances of nitrogen
and sulfur species exist regardless of the large differences in the total amount of organic nitrogen and sulfur
seen in the kerogens. XPS and S-XANES results indicate that the relative level of aromatic sulfur increases
with an increasing amount of aromatic carbon for all kerogens. XPS show that the majority of nitrogen exists
as pyrrolic forms in comparable relative abundances in all kerogens studied. The direct characterization results
using X-ray and NMR methods for nitrogen, sulfur, oxygen, and carbon chemical structures provide a basis
for developing both specific and general average chemical structural models for different organic matter type
kerogens.
This paper presents data on the 15N chemical shift
tensor principal values in a series of
15N-enriched
heterocycles. Compounds that are liquids at room temperature were
frozen, and the principal values of all compounds
studied were measured from static powder patterns. Four different
types of nitrogen tensors are described, consisting
of protonated and nonprotonated nitrogens in both five- and
six-membered rings. The principal values were
oriented
on the molecular frame using the DFT quantum mechanical calculations of
the 15N chemical shielding tensors. The
agreement between the calculated and experimental principal values is
adequate to make these assignments, but the
relative scatters are greater than those observed in similar
13C chemical shift calculations. The largest shift
component,
δ11, is always oriented in the radial direction to the
ring for substituted nitrogens but is tangential to the ring for
the
nonsubstituted nitrogens. The large variations observed in the
nitrogen chemical shift tensors upon changing the
nitrogen hybridization can be explained using qualitative arguments on
the localization of the smallest bonding-antibonding or HOMO−LUMO gap in the molecule. The orientation of
the largest shift component is always found
in the plane of the molecule and is approximately perpendicular to the
plane containing the bonding−antibonding or
HOMO−LUMO pair of orbitals with the smallest energy gap.
A new method is described for numerically computing theoretical NMR powder patterns which achieves a many-fold increase in speed and accuracy over previous techniques. The method incorporates a simple and efficient technique for selecting the set of crystal orientations over which the spectral frequencies are calculated. The orientation selection technique is then integrated with an interpolation scheme which transfers the intensities at these frequencies to the computed spectrum. The method will be useful whenever an average over a sphere is computed numerically. The new efficiency of the method makes practical least squares fitting of theoretical spectra to experimental NMR data. The fits provide unbiased estimates of the NMR parameters and their errors. The technique is illustrated by extracting chemical shift tensors from a proton decoupled carbon-13 NMR spectrum.
Soot samples, including the associated organics, produced from an Illinois No. 6 coal (five
samples) and two model compounds, biphenyl (three samples) and pyrene (two samples), have
been studied by 13C NMR methods. The coal soot data served as a guide to selection of the
temperature range that would be most fruitful for investigation of the evolution of aerosols
composed of soot and tars that are generated from model compounds. The evolution of the different
materials in the gas phase followed different paths. The coal derived soots exhibited loss of
aliphatic and oxygen functional groups prior to significant growth in average aromatic cluster
size. Between 1410 and 1530 K, line broadening occurs in the aromatic band, which appears to
have a Lorentzian component that is observable at the lower temperature and is quite pronounced
at the higher temperature. The data indicate that the average aromatic cluster size (the number
of carbon atoms in an aromatic ring system where the rings are connected through aromatic
bridgehead carbon atoms) may be as large as 80−90 carbons/cluster. The data obtained for the
biphenyl samples exhibit a different path for pyrolysis and soot growth. A significant amount of
ring opening reactions occurs, followed by major structural rearrangements, after the initial ring
opening and hydrogen transfer phase. The cluster size not only grows significantly, but the cross-linking structure also increases, indicating that soot growth in biphenyl soots consists not only
of cluster size growth but also cluster cross-linking. The evolution of pyrene aerosol samples
follows still another path. Little evidence is noted for ring opening reactions. Major ring growth
has not occurred at 1410 K but cross-linking reactions are noted, indicating the formation of
dimer/trimer structures. Although a significant amount of ring growth is noted, the data are
inconclusive regarding the mechanism for ring growth in the pyrene aerosols between 1410 and
1460 K.
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