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NIST–JANAF Thermochemical Tables for the Bromine Oxides

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NIST–JANAF Thermochemical Tables for the Bromine Oxides NIST–JANAF Thermochemical Tables for the Bromine Oxides Cite as: Journal of Physical and Chemical Reference Data 25, 1069 (1996); https:// doi.org/10.1063/1.555993 Submitted: 25 July 1995 . Published Online: 15 October 2009 M. W. Chase ARTICLES YOU MAY BE INTERESTED IN NIST-JANAF Thermochemical Tables for Oxygen Fluorides Journal of Physical and Chemical Reference Data 25, 551 (1996); https:// doi.org/10.1063/1.555992 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 JANAF Thermochemical Tables, 1982 Supplement Journal of Physical and Chemical Reference Data 11, 695 (1982); https:// doi.org/10.1063/1.555666 Journal of Physical and Chemical Reference Data 25, 1069 (1996); https://doi.org/10.1063/1.555993 25, 1069 © 1996 American Institute of Physics for the National Institute of Standards and Technology. NIST -JANAF Thermochemical Tables for the Bromine Oxides Malcolm W. Chase Standard Reference Data Program, National Institute of Standards and Technology, Gaithersburg, Maryland 20899 Received July 25, 1995; revised manuscript received May I, 1996 The thermodynamic and spectroscopic properties of the bromine. oxide species have been reviewed. Recommended NIST -JANAF Thermochemical Tables are given for six gaseous bromine oxides: BrO, OBrO, BrOO, BrOBr, BrBrO, and Br03' Sufficient information is not available to generate thermochemical tables for any condensed phase species. Annotated bibliographies (over 280 references) are provided for all neutral bromine oxides 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 six 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: bromine oxides; evaluated/recommended data; literature survey; spectroscopic properties; thermodynamic properties. Contents 6.2. OBrO(g)............................. 1094 1. Introduction............................... 1069 6.3. BrOO(g)............................. 1095 1.1. References for the Introduction. .. .. 1071 6.4. Br03(g).............................. 1096 2. Chemical Species Coverage .................. , 1072 6.5. BrOBr(g)............................. 1097 3. Historical Perspective of Bromine Oxide Studies. 1072 6.6. BrBrO(g)............................. 1098 4. Summary of the Data for the Bromine Oxide 7. Conclusions................................ 1099 Species. .. 1073 8. Acknowledgments.......................... 1099 4.1. Spectroscopic Information. .. 1073 9. References-Annotated Bibliographies. .. 1100 4.2. Thermodynamic Information. .. .. 1073 5. Discussion of the Literature Data............. , 1073 5.1. BrO................................. 1074 List of Tables 5.2. OBrO................................ 1079 2.1. Bromine Oxide Species. .. 1072 5.3. BrOO................................ 1085 5.1.1. KotatlOnal Constants tor 131'0. .. .. l.O75 5.4. Br03 ................................ 1085 5.1.2. Rotational.and Electronic State Splitting 5.5. Br04................................ 1086 Constants for BrO. .. 1077 5.6. BrOBr............................... 1086 5L3 Dissociation Energy of BrO. .. 1079 5.7. BrBrO............................... 1088 6. Bromine Oxide Species: Structure and 5.8. Br2(02).............................. 1089 Vibrational Frequencies. .. 1081 5.9. Br203................................ 1089 7.1. Thermodynamic Properties of the Bromine 5.10. BrOBr02............................. 1089 Oxides. .. 1099 5.11. 02BrBr02'" . .. 1090 5.12. 02BrOBrO ........................... 1090 5.13. BrBr04.............................. 1090 1. Introduction 5.14. Br20S ................................ 1090 5.15. Br206 ............................... 1091 5.1fi. Rr207' 1091 As a continuation of previous studies which dealt with the 5.17. Br30g ................................ 1091 thermodynamic properties of the chlorine oxides I and oxy­ 6. NIST-JANAF Thermochemical Tables ......... 1092 gen fluorides,2 this study deals with the neutral bromine ox­ 6.1. BrO(g)............................... 1093 ides. A succeeding article will deal with iodine oxides. We will Hul lli~CllS~ lhe: aSlatine uxilles, as there appears to be only an estimated D~ value reported in the literature for (i) 1996 by tlw C.S. Secretary of Commerce on behalf of the United States. AtO(g). Specifically, this study examines the thermodynamic All rights resem~d. This copyright is assigned to the American Institute of Phy..;j(,<; :lnd rhi' .... meril'an Ch.?mical Society. properties of the neutral oxides. not the gaseous ionic and Reprint~ available from ACS; see Reprints list at back of issue. aqueous ionic species. The main purpose of this article is to 0047 -2689/96/2S( 4)/1 069/43/S14.00 1069 J. Phys. Chern. Ref. Data, Vol. 25, No.4, 1996 1070 MALCOLM W. CHASE generate thermochemic.al tables for bromine oxide species. Russian counterpart by Glushko and Medvedev6 listed values In generaL there are scant data available for the description (C;,HO, S°, and ~"fHO) at 298.15 K for BrO(g), but only an of the spectroscopic and thermodynamic data for any of the enthalpy of formation for Br02(cr). [The NBS Tables also bromine oxides, except for BrO, OBrO, and BrOBr. Al­ listed values for three aqueous ions, Glushko and Medvedev though the prime emphasis was on the diatomic and tri­ listed two aqueous ions.J It should be noted that the NBS atomic species, a thorough search of all bromine oxygen spe­ study was performed in 1964 and the Russian study in 1965, cies was conducted to decide which species had sufficient and were based on the same references. data. There are many NASA-JPL publications on chemical ki­ For the time period 1907 to 1994, there are only 280 cita­ netics in which enthalpy of formation tables are given. Of all tions in Chemical Abstract Services (CAS) dealing with all the bromine oxides, only BrO(g) is listed by NASA-JPL.7 phases of the bromine oxides; of these 147 deal with BrO, 45 These data are presented without citation or reference to the deal with OBrO. and 25 with BrOBr. Of the approximately original source. Most of the recommendations are based 25 oxides mentioned in the literature, however, there is not upon data in the IUPAC Evaluation (Atkinson et al., 1989,S 9 conclusive evidence as to the existence of all of them. 1992 ). Some of the values are different from the current The major interest in the numerous bromine oxides is due IUPAC recommendations. reflecting recent studies that have to the important role these compounds play in stratospheric not yet been accepted and incorporated into that publication. chemistry. For this reason, the spectroscopic characterization IUPAC cites the origin of their values. All citations given by of these species is mandatory in order to explain possible IUPAC are included in this article. reactions thermodynamically and kinetically and to monitor Lewis 10 in 1932 reVIewed the kinetics of reactions that the species in real time. In addition, numerous researchers proceeded with velocities ranging from the flammable region are examining bonding trends within all halogen oxide spe­ to detonation. As part of this review the author summarized cies. There are no commercial uses of the bromine oxides the kinetics of the explosion of ozone as sensitized by bro­ mentioned in the literature. mine. Lewis raised the question as to the possible formation The current study is aimed at providing a complete and of bromine oxides. thorough coverage of the literature for spectroscopic and In a 1963 review article, Schmeisser and Brandle II sum­ thermodynamic information. Although it is not the purpose marized the data pertaining to the properties and chemistry of this article to summarize and critique the chemistry of the of the halogen-oxide compounds. Although these authors did bromine oxides, all such references are provided here. The not discuss BrO, they examined BrOBr and OBrO in detail. references were obtained primarily by use of commercial ab­ A measured enthalpy of formation of OBrO(cr) was noted. stracting services and all NIST Data Centers. (Chemical Ki­ Brief mention was made of BrO 3, Br205, and Br308' al­ netics Data Center; Chemical Thermodynamics Data Center; though it was clear that the authors were not convinced that Ion Kinetics and Energetics Data Center; Molecular Spectra these "compounds" existed. Data Center; Vibrational and Electronic Energy Levels of A 1972 review by Brisdon,12 discussed seven bromine ox­ Small Polyatomic Transient Molecules; Crystal and Electron ide species: BrO, OBrO, BrOO, Br03, BrOBr, Br202. and Diffraction Data Center.) Since the literature survey revealed Br:P4' Whereas there was a complete spectroscopic charac­ so few references in total for all neutral bromine oxides, all terization of BrOBr presented, only a partial identification of citations are listed in Sec. 10 (References Annotated Bibli­ BrO was made. General comments proposing the existence ography). It should be noted that the reading of the indi­ (or nonexistence) of the remaining compounds were made. vidual articles yielded additional references. many of which Clyne and Curran 13 surveyed the reaction kinetics
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