The rates of solvent swelling of the Argonne Premium Sample coals have
been measured in
various organic solvents at various temperatures. The results show
that the extents of swelling,
when experiments are carried out in liquid solvents, are independent of
the temperature, within
the temperature range studied here (10−60 °C).
Thermodynamically, this requires that
equilibrium swelling should occur with a near-zero enthalpy, as
generally required for absence
of a temperature effect on equilibrium. This conclusion is
consistent with a number of other
recently published results. The rates of swelling of the coals do
not correlate with rank. The
nature of the swelling process varies from relaxation controlled to
Fickian diffusion controlled.
The activation energies for the kinetics of swelling are
consistent with other recently published
values, but again, a correlation with rank could not be substantiated.
The activation energies
all fall in the range from 20 to 60 kJ/mol, suggesting that the
activation barrier may be associated
with the breakage of internal electron donor−acceptor (e.g., hydrogen
bonding) interactions.
Thermal pretreatment of some of the coals to 350 °C had
significant effects on their swelling
behaviors. The effect was generally to increase the rate of
swelling, and in some cases, the extent
of swelling. The activation energies for swelling were, however,
unaffected. This is interpreted
as consistent with the hypothesis that the activation energy barrier is
determined by donor−acceptor interactions which are unaffected by pretreatment but that
other thermally dissociable
coal−coal interactions may serve to stiffen its
structure.
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