A theoretical prediction of thermodynamic properties of chlorine fluorides

Correlation between the HOFs obtained from the formation reactions (HOF(FR)) and modified formation reactions (HOF(MFR)). [Display omitted] ► We calculate the heats of formation of nine chlorine fluorides – ClF, ClF 3, ClF 5, ClFO, ClFO 2, ClFO 3, ClF 3O 2, ClF 3O, and ClF 5O. ► The formation reaction in conjunction with the G3 theory can give accurate results. ► ClF, ClF 3, ClF 5 and ClF 3O are stable at the room temperature. ► ClFO 2, ClF 3O 2 and ClF 5O may be stable at lower temperature. The heats of formation of ClF, ClF 3, ClF 5, ClFO, ClFO 2, ClFO 3, ClF 3O 2, ClF 3O, and ClF 5O 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, ClF 3, ClF 5 and ClF 3O are stable at the room temperature, and ClFO 2, ClF 3O 2, and ClF 5O may be stable at lower temperature.