Thermodynamics Research Center / ThermoML | Thermochimica Acta

Combined experiments to measure low sublimation pressures and diffusion coefficients of organometallic compounds

Siddiqi, M. A., Atakan, B.[Burak]
Thermochim. Acta 2007, 452, 2, 128-134
ABSTRACT
Vapor pressures and sublimation pressures of organometallic (metalorganic) compounds are needed in several processes like chemical vapor deposition (CVD). Thermobalances at ambient pressures are often used to study the evaporation of such compounds. At least three strategies are found in the literature to evaluate the results using different theoretical approaches. In some of the frequently used approaches the diffusion out of a crucible is neglected. We present a simple theoretical approach which describes the interrelation between the observed mass transfer rate and the physical variables of typical TGA set-ups. It turns out that the mass transfer rate at a given total pressure and temperature is mainly a function of the diffusion coefficient and the vapor pressure of the sublimating substance. The vapor pressures may be determined from an independent measurement using the Knudsen cell and combined with the TGA to obtain the diffusion coefficients. Experiments have been performed with two well studied substances naphthalene and phenanthrene to check the present strategy. Further measurements were then performed for the metal organic CVD relevant compounds: ferrocene and Tris(2,2,6,6-tetramethyl-3,5-heptanedianato)cobalt III [Co(tmhd)3].
Compounds
# Formula Name
1 C14H10 phenanthrene
2 C10H8 naphthalene
3 C10H10Fe ferrocene
4 N2 nitrogen
5 He helium
Datasets
The table above is generated from the ThermoML associated json file (link above). POMD and RXND refer to PureOrMixture and Reaction Datasets. The compound numbers are included in properties, variables, and phases, if specificied; the numbers refer to the table of compounds on the left.
Type Compound-# Property Variable Constraint Phase Method #Points
  • POMD
  • 1
  • 4
  • Binary diffusion coefficient, m2/s ; Gas
  • Temperature, K; Gas
  • Pressure, kPa; Gas
  • Mole fraction - 1; Gas
  • Gas
  • Open capillary
  • 3
  • POMD
  • 1
  • 5
  • Binary diffusion coefficient, m2/s ; Gas
  • Temperature, K; Gas
  • Pressure, kPa; Gas
  • Mole fraction - 1; Gas
  • Gas
  • Open capillary
  • 3
  • POMD
  • 2
  • 4
  • Binary diffusion coefficient, m2/s ; Gas
  • Temperature, K; Gas
  • Pressure, kPa; Gas
  • Mole fraction - 2; Gas
  • Gas
  • Open capillary
  • 3
  • POMD
  • 2
  • 5
  • Binary diffusion coefficient, m2/s ; Gas
  • Temperature, K; Gas
  • Pressure, kPa; Gas
  • Mole fraction - 2; Gas
  • Gas
  • Open capillary
  • 3
  • POMD
  • 3
  • 4
  • Binary diffusion coefficient, m2/s ; Gas
  • Temperature, K; Gas
  • Pressure, kPa; Gas
  • Mole fraction - 3; Gas
  • Gas
  • Open capillary
  • 6
  • POMD
  • 3
  • 5
  • Binary diffusion coefficient, m2/s ; Gas
  • Temperature, K; Gas
  • Pressure, kPa; Gas
  • Mole fraction - 3; Gas
  • Gas
  • Open capillary
  • 4