Enthalpies of sublimation of ferrocene and nickelocene measured by calorimetry and the method of Langmuir

► Calorimetric enthalpies of sublimation of ferrocene and nickelocene are supplied. ► Sublimation enthalpies of both metallocenes were also obtained by indirect Langmuir’s method. ► Calorimetric and indirect enthalpies of sublimation are comparable in accuracy and dispersion. ► Sublimation enthalpie...

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Bibliographic Details
Published in:The Journal of chemical thermodynamics 2011-11, Vol.43 (11), p.1738-1747
Main Authors: Rojas, Aarón, Vieyra-Eusebio, María Teresa
Format: Article
Language:English
Subjects:
Calorimetry
Calvet calorimetry
Chemical thermodynamics
Chemistry
Differential scanning calorimetry
Elements, mineral and organic compounds
Enthalpy
Enthalpy of melting
Exact sciences and technology
Ferrocenes
General and physical chemistry
Heat capacity
Langmuir’s equation
Mathematical analysis
Specific heat
Sublimation
Thermodynamic properties
Vapor pressure
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Summary:► Calorimetric enthalpies of sublimation of ferrocene and nickelocene are supplied. ► Sublimation enthalpies of both metallocenes were also obtained by indirect Langmuir’s method. ► Calorimetric and indirect enthalpies of sublimation are comparable in accuracy and dispersion. ► Sublimation enthalpies are congruent with both compounds being monoclinic and isostructural. A quick and accurate methodology that is based on Langmuir’s equation and that is developed by utilising a DSC7 device is proposed for the measurement of the enthalpies of sublimation of substances characterised by vapour pressures of approximately 1.0Pa at room temperature. The procedure was applied to ferrocene and nickelocene; the accuracy and uncertainty associated with the experimental results show that the reliability of the developed indirect method is comparable to the direct calorimetric measurements also performed in this work. Furthermore, the melting data and crystal-phase heat capacities for both metallocenes were calorimetrically measured, whereas the gas-phase heat capacity for each metallic bis(cyclopentadienyl) was theoretically estimated by DFT calculations.
ISSN:0021-9614
1096-3626
DOI:10.1016/j.jct.2011.06.001