Thermodynamics Research Center / ThermoML | Journal of Chemical Thermodynamics

Knudsen cell mass spectrometric study of the Cs2IOH(g) molecule thermodynamics

Roki, F.-Z., Ohnet, M.-N., Fillet, S., Chatillon, C., Nuta, I.
J. Chem. Thermodyn. 2013, 65, 247-264
ABSTRACT
The gas phase of the CsI + CsOH system is analyzed by high temperature Knudsen cell mass spectrometry in order to confirm the existence of the Cs2IOH(g) complex molecule. The mass spectrometric analysis is quite complex since such molecules undergo dissociative ionization into fragment ions that mix with the same ions from dimers of the pure compounds in the same vapor phase. Varying the chemical conditions for vaporization by using different CsI + CsOH mixture contents showed that the ionization of the Cs2- IOH(g) molecule led to five different fragment ions, Cs2OH+, Cs2I+, Cs+, CsOH+ and CsI+. This complex ionization pattern was studied in relation with previous assessed values for the vaporization of CsOH and CsI pure compounds in which monomer and dimer molecules are predominant. The equilibrium constant for the reaction CsI(g) + CsOH(g) = Cs2IOH(g) was determined and, after modeling the structure of the Cs2IOH molecule, the enthalpy of formation was determined using the third law of thermodynamics, as follows: [delta]Hf(Cs2IOH, g, 298.15 K) = 578 +- 14.7 kJ/mole.
Compounds
# Formula Name
1 CsI cesium iodide
2 CsHO cesium hydroxide (Cs(OH))
3 Cs2HIO cesium hydroxide iodide
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
  • 3
  • Molar heat capacity at constant pressure, J/K/mol ; Ideal gas
  • Temperature, K; Ideal gas
  • Pressure, kPa; Ideal gas
  • Ideal gas
  • statistical thermodynamics
  • 29
  • POMD
  • 3
  • Molar enthalpy, kJ/mol ; Ideal gas
  • Temperature, K; Ideal gas
  • Pressure, kPa; Ideal gas
  • Ideal gas
  • statistical thermodynamics
  • 29
  • POMD
  • 3
  • Molar entropy, J/K/mol ; Ideal gas
  • Temperature, K; Ideal gas
  • Pressure, kPa; Ideal gas
  • Ideal gas
  • statistical thermodynamics
  • 29
  • RXND
  • 1
  • 2
  • 3
  • Thermodynamic equilibrium constant
  • Knudsen cell mass spectrometry
  • 12