NIST-JANAF Thermochemical Tables for Oxygen Fluorides Cite as: Journal of Physical and Chemical Reference Data 25, 551 (1996); https://doi.org/10.1063/1.555992 Submitted: 13 October 1995 . Published Online: 15 October 2009 M. W. Chase ARTICLES YOU MAY BE INTERESTED IN JANAF thermochemical tables, 1975 supplement Journal of Physical and Chemical Reference Data 4, 1 (1975); https://doi.org/10.1063/1.555517 JANAF Thermochemical Tables, 1982 Supplement Journal of Physical and Chemical Reference Data 11, 695 (1982); https:// doi.org/10.1063/1.555666 NIST–JANAF Thermochemical Tables for the Iodine Oxides Journal of Physical and Chemical Reference Data 25, 1297 (1996); https:// doi.org/10.1063/1.555994 Journal of Physical and Chemical Reference Data 25, 551 (1996); https://doi.org/10.1063/1.555992 25, 551 © 1996 American Institute of Physics for the National Institute of Standards and Technology. NI~T-JANAF Thermochemical Tables for the oxygen Fluorides Malcolm W. Chase Standard Reference Data Program, National Institute of Standards and Technology, Gaithersburg, MD 20899-0001 Received October 13. 1995; revised manuscript received December 18. 1995 The thermodynamic and spectroscopic properties of the oxygen fluoride species have been reviewed. Recommended thermochemical tables are given for five gaseous oxygen fluorides: OF, OFO, FOO, FOF, and 02F2. Sufficient information is not available to generate thermochemical tables for any condensed phase species. Annotated bibliogra­ phies (over 600 references) are provided for all neutral oxygen fluorides which have been reported in the literature. There are needs for additional experimental and theoretical data to reduce the uncertainties in the recommended values for these five species. Of all the species mentioned in the literature, many have not been isolated and characterized. In fact, some do not exist. Throughout this paper, uncertainties attached to recommended values correspond to the uncertainty interval, equal to twice the standard deviation of the mean. ©1996 American Institute of Physics and American Chemical Society. Key words: evaluated/recommended data; literature survey; oxygen fluorides; spectroscopic properties; thermo­ dynamic properties. Contents 1. Introduction............................... 551 5.24. O~2(FOOOOOOF). 580 1.1. References for the Introduction. 553 5.25. 07F2 • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 580 2. Chemical Species Coverage. 554 5.26. OsF2 • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 580 3. Historical Perspective of Oxygen Fluoride Studies 555 5.27. OF3 • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 580 3.1. References for Historical Perspective . 555 6. NIST-JANAF Thermochemical Tables. 580 4. Summary of the Data for the Oxygen Fluoride 6.1. OF(g) .. .. .. .. .. .. .. .. .. .. .. 581 Species . 555 6.2. FOO(g)............................. 582 4.1. Spectroscopic Information . 555 6.3. OFO(g)............................. 583 4.2. Thermodynamic Information. 555 6.4. FOF(g).............................. 584 5. Discussion of the Literature Data. 555 6.5. 02F2(g).............................. 585 5.1. OF(g) .. .. .. .. .. .. .. .. .. .. .. .. .. .. 556 7. Conclusions............................... 586 5.2. 180F................................ 561 8. Acknowledgments.......................... 586 5.3. 02F................................. 561 9. References - Annotated Bibliography. 587 5.4. O I7OF....................... ·........ 566 5.5. 1700F........... ;................... 566 List of Tables 5.6. 1702F............................... 566 5.7. OI80F............................... 566 2.1. Oxygen fluoride species ................. 554 5.8. 1802F............................... 566 5.1.1. Vibrational/rotational structure ........... 557 5.9. OFO................................ 566 5.1.2. Dissociation energy/enthalpy of formation .. 558 5.10. 03F...... .... .. ...... .............. 566 5.3.1. ESR spectra assigned to FOO ............ 562 5.11. O~.... .. .. .... .. ..... ...... ........ 567 5.3.2. Rotational constants/structure ............ 562 5.12. OF2•••• •• •• •••• •••••• •••• •••••• ••••• 567 5.3.3. Vibrational frequencies ................. 564 5.13. 170F2 . 573 5.3.4. Enthalpy of formation .................. 564 5.14. 1HOF2 .. .... .. .... .... .. .... ......... 573 5.12.1. Spectroscopy/vibrational frequencies ...... 569 5.15. FFO . 573 5.12.2. Geometry and structure ................. 570 5.16. 02F2. 573 5.12.3. Dissociation energy .................... 571 5.17. 1702F2 •• • . • . • . • • • • • • • • • • • • • • • . • • . • • 577 5.12.4. Enthalpy of formatIon .................. 572 5.18. 1X02F2............................... 577 5.16.1. Vibrational frequencies ................. 574 5.19. 03F2' . 577 5.16.2. Geometry and structure ................. 575 5.20. O~2' . 578 5.16.3. Enthalpy of formation .................. 576 5.21. OsF 2 • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • 579 7.1. Thermodynamic properties of the oxygen 5.22. OsF 2(FOOOOOF) . 579 fluorides ............................. 586 5.23. O~2' . 579 1. Introduction S 1996 by the U.S. Secretary of Commerce on behalf of the United States. This copyright is assigned to the American Institute of Physics and the This study of the neutral oxygen fluorides is the first of four American Chemical Society. critical reviews on the thermodynamic and spectroscopic Reprints available from ACS: see Reprints List at back of issue. properties of the halogen oxides. An earlier partial study on 0047 -2689/96/25(2)/551/53/$16.00 551 J. Phys. Chern. Ref. Data, Vol. 25, No.2, 1996 552 MALCOLM W. CHASE the chlorine oxides l has already been reported. Subsequent fluorides in 1910, in depth studies began in the late 1920s. articles will deal with bromine oxides and iodine oxides. We Even though many citations are not relevant to this study, will not discuss the astatine oxides, as there appears to be only future investigators will not have to search the past literature, an estimated Dg value reported in the literature for AtO(g). but simply concentrate on the publications since 1994. Specifically, this study examines the thermodynamic proper­ The current version (1985) of the JANAF Thermochemical ties of the neutral oxides, not the gaseous ionic or aqueous Tablesl includes three oxygen fluorides (OF, FOO, FOF), ionic species. The main purpose of this article is to generate whereas the 1989 version of the Thermochemical Properties thermochemical tables for oxygen fluoride species. In gen­ of Individual Substances (TPIS)3 only contains information eral, there is scant data available for the description of the on OF and FOF. For the JANAF Thermochemical Tables, the spectroscopic and thermodynamic data for any of the oxygen data evaluations were actually performed in 1966 for OF and fluorides, except for OF, FOO, FOF, and OlF2. Although the 02F and in 1969 for OF2. For TPIS, the analysis for OF is prime emphasis was on the diatomic and triatomic species, a based on data up to 1973, however a footnote referring to a thorough search of all oxygen fluorides was conducted to 1979 reference was included. The most recent reference for decide which species had sufficient data. FOF was 1966. There is sufficient new data available to For the time period 1907 to 1994, there are 882 citations in warrant revisions to these tabulations, although the numeric Chemical Abstract Services (CAS) dealing with the oxygen changes are not large. The NBS Tables of Chemical Thermo­ Duuriul::S uf which lhl:rl: arl: 15 Duuriul:s anu 9 isutopumers. dynamic Propenies4 and its Russian coumerpart by Glushko 484 citations deal with OFl , 133 deal with 02Fl, 78 deal with and Medvedev5 listed values (C;, HO, S°, and D.rHO) at FOO, and 69 with OF. The remaining 118 references deal 298.15 K for OF(g) and OF2(g), but only D. fH(298 K) for with 11 fluorides and 9 isotopomers. Of the 24 fluorides 02F2(g) and 03F2(g). In addition. Glushko and Medvedev mentioned, however, there is not conclusive evidence as to include an enthalpy of formation value for OSF2(g). [Neither the existence of all of them. of these latter two publications provide any data on aqueous The present· interest in the numerous oxygen fluorides is ions.] It should be noted that the NBS study was performed due to the important role these compounds play in strato­ prior to 1Y64, whIle the RUSSIan study, pnor to I Y6.). spheric chemistry and as strong fluorinating agents. For this There are many NASA-JPL publications on chemical ki­ reason, the spectroscopic characterization of these species is netics in which enthalpy of formation tables are given. Of all mandatory in order to explain possible reactions thermody­ the oxygen fluorides, only OF, OFl , 02F, and OlF2 were listed namically and kinetically. In addition, numerous researchers by NASA-JPL.6 These data were presented without citation or are examining bonding trends within all halogen oxide spe­ reference to the original source. Most of the recommendations cies. There appears to be no commercial uses of the oxygen were based upon data in the IUPAC evaluations (Atkinson 7 8 fluorides mentioned in the literature. In the past, the dominant etal. 1989 , 1992 ). Some of the values were different from use of oxygen fluorides was in rocket industry as propellants, the current IUP AC recommendations, reflecting more recent due to the fact that they are strong oxidizers. There is also studies that have not yet been accepted and incorporated into mention of the use