A theoretical prediction of thermodynamic properties of chlorine fluorides

The heats of formation of ClF, ClF3, ClF5, ClFO, ClFO2, ClFO3, ClF3O2, ClF3O, and ClF5O have been calculated with the help of atomization reaction (AR), formation reaction (FR), and modified formation reaction (MFR) at the G3 and G3X (X = B3, MP2, and MP2B3) levels. FR or MFR in conjunction with the G3 theory can give accurate results close to experimental values. The standard thermodynamic functions of the title compounds have also been evaluated and the results agree well with the available experimental data. Results show that ClF, ClF3, ClF5 and ClF3O are stable at the room temperature, and ClFO2, ClF3O2, and ClF5O may be stable at lower temperature.

Correlation between the HOFs obtained from the formation reactions (HOF(FR)) and modified formation reactions (HOF(MFR)).Figure optionsDownload as PowerPoint slideHighlights
► We calculate the heats of formation of nine chlorine fluorides – ClF, ClF3, ClF5, ClFO, ClFO2, ClFO3, ClF3O2, ClF3O, and ClF5O.
► The formation reaction in conjunction with the G3 theory can give accurate results.
► ClF, ClF3, ClF5 and ClF3O are stable at the room temperature.
► ClFO2, ClF3O2 and ClF5O may be stable at lower temperature.