TY - JOUR
T1 - Temperature isomeric interplay in the 2-pyridone-2-hydroxypyridine system
T2 - thermodynamically consistent treatment
AU - Slanina, Zdeněk
AU - Adamowicz, Ludwik
N1 - Funding Information:
The study was carried out during a researchs tay by one of us at the Max-Planck-Institut fiir Chemie {Otto-Hi-Institut) supported by the Alexander von Humboldt-Stiftung.T he support, as well as the valuable discussionsw ith ProfessorK arl Heinzingera nd his kind hospitalitya nd that of his group, are gratefullya cknowledgedT. he other of us is equallyg rateful for the support of the study by an institutional grant from the National CancerI nstitute.
PY - 1991/4/1
Y1 - 1991/4/1
N2 - The tautomeric system of 2-pyridone (P2) and 2-hydroxypyridine (HP2) is described by partition functions supplied with molecular parameters from recent advanced computations. In contrast to other isomeric systems studied within the approach, the simple Boltzmann factors represent here a reasonable approximation to isomeric relative populations derived from thermodynamically consistent (i.e., including rotational-vibrational motions if relevant) treatment. At moderate temperatures the HP2 structure clearly prevails; however, in the high temperature limit the P2 species also becomes significant. Its presence is manifested in the isomeric enhancement of heat capacity, which at ≈ 640 K reaches its maximum value of 3.1 J K-1 mol-1. The relationship to interpretation or simulation of molecular spectra is discussed.
AB - The tautomeric system of 2-pyridone (P2) and 2-hydroxypyridine (HP2) is described by partition functions supplied with molecular parameters from recent advanced computations. In contrast to other isomeric systems studied within the approach, the simple Boltzmann factors represent here a reasonable approximation to isomeric relative populations derived from thermodynamically consistent (i.e., including rotational-vibrational motions if relevant) treatment. At moderate temperatures the HP2 structure clearly prevails; however, in the high temperature limit the P2 species also becomes significant. Its presence is manifested in the isomeric enhancement of heat capacity, which at ≈ 640 K reaches its maximum value of 3.1 J K-1 mol-1. The relationship to interpretation or simulation of molecular spectra is discussed.
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U2 - 10.1016/0040-6031(91)80088-Z
DO - 10.1016/0040-6031(91)80088-Z
M3 - Article
AN - SCOPUS:4243612392
VL - 177
SP - 101
EP - 107
JO - Thermochimica Acta
JF - Thermochimica Acta
SN - 0040-6031
IS - C
ER -