title: A kinetic and thermodynamic study of seratrodast polymorphic transition by isothermal microcalorimetry.
abstract: The development of isothermal microcalorimetry to a study of the kinetic and thermodynamics of polymorphic transitions in seratrodast ((+/-)-7-(3,5,6-trimethyl-1,4-benzoquinon-2-yl)-7-phenylheptanoic acid) Form II is reported. Sieved samples of Form II were allowed to convert to Form I, in a reaction vessel of an isothermal microcalorimeter, under 13, 31, 63 and 93% relative humidity (RH) between 48 and 65 degrees C. The power (Phi, in Watts) versus time curves from the microcalorimeter were integrated into the heat output (q, in Joules) versus time curves to yield fractional extent of Form I converted versus time curves. The change in enthalpy (-5.70 kJmol(-1)) agreed very closely with that obtained by differential scanning calorimetry and solution calorimetry, which indicated that the power measured by the microcalorimeter was due only to the Form II-to-Form I transition. Application of the theoretical kinetic method [J. Am. Ceram. Soc. 55 (1972) 74] revealed that the transition took place via a two-dimensional growth of nuclei mechanism at all the studied relative humidities and temperatures. The rate constant increased with increasing RH and temperature, and with decreasing the particle size of sample. The activation energies obtained from Arrhenius plots were 292, 290, 280 and 284 kJmol(-1), and the extrapolated rate constants at 25 degrees C were also 3.01 x 10(-10), 3.11 x 10(-10), 9.65 x 10(-10) and 3.84 x 10(-9)s(-1) for 13, 31, 63 and 93% RH, respectively.
authors.affiliation: Medway Sciences, NRI University of Greenwich, Medway University Campus, Chatham Maritime, Kent ME4 4TB, UK.
authors.forename: Koji
authors.initials: K
authors.lastname: Urakami
authors.forename: Anthony E
authors.initials: AE
authors.lastname: Beezer
mesh_terms: D016227:Benzoquinones / Q000737:chemistry*; D002151:Calorimetry; D006538:Heptanoic Acids / Q000737:chemistry*; D006813:Humidity; D007700:Kinetics; D013696:Temperature; D013816:Thermodynamics
chemical_list: D016227:Benzoquinones; D006538:Heptanoic Acids; C060230:seratrodast