Thermodynamic properties of the methylpyridines. Part 2. Vapor pressures, heat capacities, critical properties, derived thermodynamic functions between the temperatures 250 K and 560 K, and equilibrium isomer distributions for all temperatures >= 250 K
Rd. Chirico et al., Thermodynamic properties of the methylpyridines. Part 2. Vapor pressures, heat capacities, critical properties, derived thermodynamic functions between the temperatures 250 K and 560 K, and equilibrium isomer distributions for all temperatures >= 250 K, J CHEM THER, 31(3), 1999, pp. 339-378
Results are reported for measurements leading to the calculation of standar
d thermodynamic properties for temperatures from T = 250 K to T = 560 K for
the methylpyridines (Chemical Abstracts registry numbers: 4-methylpyridine
, 108-89-4; 2-methylpyridine, 109-06-8; 3-methylpyridine, 108-99-6). The st
andard state is defined as the ideal gas at the pressure p = p(O) = 101.325
kPa. Vapor pressures were measured by comparative ebulliometry for the pre
ssure range p approximate to 4 kPa to p = 270 kPa. Two-phase (liquid + vapo
r) heat capacities were measured for the temperature range approximate to 3
10 (T/K) approximate to 590 with a differential scanning calorimeter (d.s.c
.), and saturation heat capacities C-sat were derived. The critical tempera
ture T, was determined experimentally by d.s.c., and the critical pressure
and critical density were derived. Densities for the liquid phase of 3-meth
ylpyridine at saturation pressure were measured with a vibrating-tube densi
meter for the temperatures 323 (T/K) < 473. The enthalpy of combustion for
3-methylpyridine was determined to resolve a discrepancy in the literature.
Enthalpies of vaporization were calculated for all compounds. Literature v
alues for enthalpy increments and entropies for the condensed phases by adi
abatic heat-capacity calorimetry and the energies of combustion were combin
ed with the present results to derive standard entropies, enthalpy incremen
ts, and molar Gibbs free energies of formation for temperatures between T =
250 K and T = 560 K. Comparisons with standard entropies calculated statis
tically provide corroboration for the calorimetrically derived values and a
re used to demonstrate thermodynamic consistency for properties related thr
ough identities and correlations. Isomerization distributions derived with
standard molar Gibbs free energies of formation are used to aid interpretat
ion of literature fossil fuel characterization and pyridine methylation cat
alysis studies. (C) 1999 Academic Press.