Nitrogen" Suppt. Vol. B 1 describes the compounds of nitrogen with noble gases and, in the major part, binary compounds composed of one nitrogen atom and hydrogen. Nitrogen hydrogen compounds with two and more nitrogen atoms are covered in "Nitrogen" Suppt. Vol. 82. There is some information on various nitrogen-noble gas species, to a large extent because of the interest in their bonding behavior. Experimental data have been obtained chiefly for some singly charged cations, particularly those formed by argon Like ArN + and ArNi. The existence of others has only been established by mass spectrometry. The binary compounds of nitrogen and hydrogen comprise NH, NH , NH , NH , the corre 2 4 5 sponding ions, and some adducts. NH and NH1 are not treated. The predominant part 3 of the volume covers the description of the molecules NH and NH . 8oth species are present 2 in photolytic processes in the atmosphere. They play an essential role in combustion systems regardless of whether the nitrogen stems from the nitrogen-containing fuel or from the air. Thus, much work has been devoted to the understanding of the nitrogen chemistry in combustion and in the atmosphere. The production and detection methods as weiL as the reactions have been comprehensively described. ln addition detailed information is given on the spectral behavior, the knowledge of which is important for detecting the mole cules and for studying their kinetics.
The volume describes all compounds that consist of bromine and fluorine and/or chlorine and may additionally contain noble gases, hydrogen, oxygen, and nitrogen. The description of chemical and physical properties of binary compounds between bromine and fluorine takes up most of the volume, because this class of compounds includes BrF3 and BrF5 which have considerable technical interest. Especially the the oxidizing and fluorinating properties of BrF3 make it a convenient reactant for the preparation of inorganic fluorides. On the other hand, the diatomic molecule BrF is well-characterized by spectroscopic methods, but its chemistry is less known because of its instability. Other neutral species, such as Br2F, Br2F2, BrF2, and BrF6, only exist in matrices at low temperatures, and the existence of BrF4 and BrF7 is even doubted. Some of the ions, including BrF2+, BrF2-, Br3F10-, BrF4+, BrF4-, BrF6+, and BrF6-, can be stabilized as salts.
Some years ago the Gmelin Institute started to supplement the volumes on halogens and halogen compounds. For the elements chlorine and fluorine these supplementary volumes have already been finished. For the element bromine the volume A 1 is also available. Now the volume B 1 will be published starting with the description of the compounds of bromine. The present volume describes the compounds of bromine with rare gases and with hydrogen. The volume is dominated by the description of HBr and its aqueous solution, hydrobromic acid. Chemical and physical properties of the diatomic molecule HBr are extremely well studied by modern methods. Thus detailed descriptions are given of gas-phase properties, spectra, and properties of condensed phases. Emphasis is laid on elementary reaction processes such as energy transfer and single reaction steps for HBr formation and decomposition. These studies have become classics of modern reaction kinetics. Likewise, elementary reactions of HBr and Br- with nonmetallic compounds are described comprehensively.
This volume C 1 is the first supplement volume to "Phosphor" C which was published in 1965 and covers the compounds of phosphorus. Starting with the binary species formed between phosphorus and hydrogen, the present volume deals with the neutral mononuclear compounds PH through PH ; the ions featuring the same stoichiometric composition are s covered in separate sections. PH and PH are the major initial gaseous decomposition products of PH and, thus, also 2 J intermediates in many of its gas-phase reactions. Both molecules and their ions have been thoroughly investigated by a variety of modern, high-resolution spectroscopic methods during the last three decades. The coverage of their physical, and mostly molecular, properties re presents the largest part of the first two chapters (PH and ions pp. 2 to 47; PH and ions pp. 47 2 to 111). PH is the only compound described in this volume which is thermally stable under normal J conditions. It is the phosphorus analog of ammonia, but exhibits, however, a quite different chemical behavior towards most elements and compounds. The majority of its physical, and in particular spectroscopic, properties have been determined in great detail since the sixties, partially in regard to spectroscopic investigations of the atmospheres of the outer planets.
The volume describes the chemical and physical properties of the approximately 80 known bromine compounds and ions which contain oxygen and/or nitrogen, and which may include hydrogen as well. The class of bromine-oxygen and bromine-oxygen-hydrogen compounds comprises several well-known species. Their description accounts for approximately three-quarters of the volume. The BrO radical and the BrO3 ion are the most and best studied among all binary bromine-oxygen species. BrO was recently recognized to play a role in some reaction sequences depleting the ozone concentration in the stratosphere. Bromate-ion-driven chemical oscillator systems have attracted much interest in recent decades. Thus data on single reaction steps which involve BrO3, BrO2, and the oxoacides of bromine - HBrO, HBrO2, and HBrO3 - are reviewed in detail; a comprehensive description of the oscillating systems, however, is beyond the scope of this volume. The remaining one-quarter of the volume is devoted to bromine-nitrogen and bromine-nitrogen-oxygen compounds. Bromine azide and nitrosyl bromide are the most comprehensively studied of these, accounting for almost half of this section.
The volume provides complete and up-to-date information on the few chemical species composed of silicon, fluorine, and noble gases and in the major part on the species composed of silicon, fluorine, and hydrogen. Among the numerous experimentally confirmed and theoretically predicted monosilicon Si-H-F species with Si coordination numbers 2, 3, and 4, the most prominent and best investigated molecules by far are Si H3F, Si H2F2, and Si H F3. Even more has been reported about aqueous solutions of hexafluorosilicic acid, "H2Si F6", a system which is not yet completely understood. Some of the isomers of partially fluorinated di-, tri-, and tetrasilanes are known to some extent, but information on the higher acyclic and cyclic polysilanes is increasingly sparce.
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