Binary halogen oxides

The structures of some binary halogen oxides are listed in Table 17.4.1. 

M. Jansen and T. Kraft, The structural chemistry of binary halogen oxides in the solid state. Chem. Ber, 130, 307-15 (1997). 

A large number of binary halogen oxides are known, from shock-sensitive liquids to rather stable solids. Similarly, a large number of oxoacids and oxoacid salts are also known. 

A significant advance in flame retardancy was the introduction of binary systems based on the use of halogenated organics and metal salts (6,7). In particular, a 1942 patent (7) described a finish for utilizing chlorinated paraffins and antimony(III) oxide [1309-64-4]. This type of finish was invaluable in World War II, and saw considerable use on outdoor cotton fabrics in both uniforms and tents. 

It will be convenient to describe first the binary. sulfur nitrides SjN,. and then the related cationic and anionic species, S,Nv. The sulfur imides and other cyclic S-N compounds will then be discus.sed and this will be followed by sections on S-N-halogen and S-N-O compounds. Several compounds which feature i.solated S<—N, S-N, S = N and S=N bonds have already been mentioned in the. section on SF4 e.g. F4S NC,H, F5S-NF2. F2S = NCF3, and FiS=N (p. 687). Flowever. many SN compounds do not lend themselves to simple bond diagrams, - and formal oxidation states are often unhelpful or even misleading. 

The (compositionally) simplest mineral class comprises the native elements, that is, those elements, either metals or nonmetals that occur naturally in the native state, uncombined with others. Native gold, silver, and copper, for example, are metals that naturally occur in a ductile and malleable condition, while carbon - in the form of either graphite or diamond -and sulfur are examples of nonmetallic native elements. Next in compositional complexity are the binary minerals composed of two elements a metal or nonmetallic element combined with oxygen in the oxides, with a halogen - either fluorine, chlorine bromine, or iodine - in the halides, or sulfur, in the sulfides. The oxide minerals, for example, are solids that occur either in a somewhat hard, dense, and compact form in mineral ores and in rocks, or as relatively soft, unconsolidated sediments that melt at moderate to... 

Their unique characteristics are a result of their outer shells having seven electrons, and thus requiring only one electron to become complete. This -1 oxidation state makes them extremely reactive with both metals and some nonmetal elements that form negative ions, and they may form either ionic or covalent bonds. They can also form compounds with each other these binary compounds of the halogens are called halides. ... 

Iron reacts with nonmetals forming their binary compounds. It combines readily with halogens. Reaction is vigorous with chlorine at moderate temperature. With oxygen, it readily forms iron oxides at moderate temperatures. In a finely divided state, the metal is pyrophoric. Iron combines partially with nitrogen only at elevated temperatures. It reacts with carbon, sulfur, phosphorus, arsenic, and silicon at elevated temperatures in the absence of air, forming their binary compounds. 

The chemical properties of selenium fall between sulfur and tellurium. Thus, selenium reacts with oxygen similarly to sulfur, forming two oxides, selenium dioxide, Se02 and trioxide, SeOs. The metal combines with halogens forming their halides. With nonmetals, selenium forms binary compounds exhibiting oxidation states +4 and -i-6. 

In contrast to fluorine, which can form binary fluorides in very high oxidation states such as six, even seven, and perhaps eight (see Fluorine Inorganic Chemistry), few hexahalides are known for the other halogens there are three chlorides, WCle, ReCle, and UCle, and only one bromide, WBre. 

The immense number of chemical compounds formed by the halogens provides chemists with an extraordinary database from which numerous chemical and physical phenomena can be correlated with respect to various periodic trends. From databases like Inorganic Crystal Structure Data (ICSD, http //www.fiz-karlsruhe.de ) and International Centre for Diffraction Data (ICDD, http //www.icdd.com) with 67 000 and 25 000 entries, respectively, one can easily make out that halides are one of the dominant classes of compounds besides oxides. Even within the subset of inorganic solids, there is tremendous diversity of composition, stracture, and properties and to summarize this would create its own encyclopedia. Therefore, the discussion in this article is limited primarily to binary halides, their structures, and some of their properties, except halides of elements which are nonmetals. Binary actinide hahdes are discnssed elsewhere see Actinides Inorganic Coordination Chemistry). Complex hahdes (sohd phases containing two or more kinds of metal ions), ... 

Several iodine nitrates in the oxidation state +III are known I(0N02)3 and CF3l(0N02)2- The other halogens do not form binary nitrates in the oxidation state +III. Iodine (III) nitrates are available by substitution of iodine(III)compounds... 

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