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Volatility and chemical stability of chromium, molybdenum, and tungsten hexacarbonyls

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Abstract

The sublimation vapor pressures of three metallic (group 6) hexacarbonyls, Cr(CO)6, Mo(CO)6, and W(CO)6, were measured using the Knudsen mass-loss effusion method. The standard (po = 0.1 MPa) molar enthalpies, entropies, Gibbs energies, and heat capacity difference between the gas and solid state, at T = 298.15 K, were derived from the experimental results combined with selected literature ones covering a wide range of temperature. The temperatures and molar enthalpies of fusion of those compounds were measured using differential scanning calorimetry. The thermodynamic stability of the hexacarbonyls was evaluated taking into account the standard Gibbs energies of formation in the crystalline and gaseous phases. Gas-phase absolute entropies, heat capacities, and enthalpies of formation of the three compounds studied as well as the bond distances M–C and C–O were calculated.

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Acknowledgements

This work is dedicated to the memory of the late Prof. Manuel A. V. Ribeiro da Silva. Thanks are due to FCT, Project UID/QUI/00081/2013 and to FEDER (COMPETE 2020), Projects POCI-01-0145-FEDER-006980 and NORTE-01-0145-FEDER-000028. A.R.R.P.A. thanks FCT and the European Social Fund for the award of the postdoctoral fellowship (SFRH/BPD/97046/2013).

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  1. Centro de Investigação em Química (CIQUP), Department of Chemistry and Biochemistry, Faculty of Science, University of Porto, Rua do Campo Alegre, 4169-007, Porto, Portugal

    Manuel J. S. Monte & Ana R. R. P. Almeida

  2. Instituto de Química Física “Rocasolano”, CSIC, Serrano 119, 28006, Madrid, Spain

    Rafael Notario

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  1. Manuel J. S. Monte
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Correspondence to Manuel J. S. Monte.

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Monte, M.J.S., Almeida, A.R.R.P. & Notario, R. Volatility and chemical stability of chromium, molybdenum, and tungsten hexacarbonyls. J Therm Anal Calorim 132, 1201–1211 (2018). https://doi.org/10.1007/s10973-018-7033-1

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