Chlorine oxides, fluorination

Chlorine reacts with most elements, both metals and non-metals except carbon, oxygen and nitrogen, forming chlorides. Sometimes the reaction is catalysed by a trace of water (such as in the case of copper and zinc). If the element attacked exhibits several oxidation states, chlorine, like fluorine, forms compounds of high oxidation state, for example iron forms iron(III) chloride and tin forms tin(IV) chloride. Phosphorus, however, forms first the trichloride, PCI3, and (if excess chlorine is present) the pentachloride PCI5. 

Copper Acetylene and alkynes, ammonium nitrate, azides, bromates, chlorates, iodates, chlorine, ethylene oxide, fluorine, peroxides, hydrogen sulflde, hydrazinium nitrate... 

Iodine Acetaldehyde, acetylene, aluminum, ammonia (aqueous or anhydrous), antimony, bromine pentafluoride, carbides, cesium oxide, chlorine, ethanol, fluorine, formamide, lithium, magnesium, phosphorus, pyridine, silver azide, sulfur trioxide... 

Lead(ll) oxide Chlorinated rubber, chlorine, ethylene, fluorine, glycerol, metal acetylides, perchloric acid... 

Nitric oxide Aluminum, BaO, boron, carbon disulflde, chromium, many chlorinated hydrocarbons, fluorine, hydrocarbons, ozone, phosphine, phosphorus, hydrazine, acetic anhydride, ammonia, chloroform, Fe, K, Mg, Mn, Na, sulfur... 

Phosphorus pentachloride Aluminum, chlorine, chlorine dioxide, chlorine trioxide, fluorine, magnesium oxide, nitrobenzene, diphosphorus trioxide, potassium, sodium, urea, water... 

In the diaziridine field many compounds are known bearing N-YL, A/-alkyl and A-acyl groups, but here no dramatic changes in reactivity are caused by A-substituents. N-Aryldiaziridines are underrepresented. The ring carbon is in the oxidation state of a carbonyl compound or, in the diaziridinones (5) and the diaziridinimines (6) that of carbonic acid. In single cases, diaziridine carbon bears chlorine or fluorine. 

Hydrogen peroxide, nitric acid, or any other oxidant Fluorine, chlorine, bromine, chromic acid, peroxides... 

Chlorine dioxide Copper Fluorine Hydrazine Hydrocarbons (benzene, butane, propane, gasoline, turpentine, etc) Hydrocyanic acid Hydrofluoric acid, anhydrous (hydrogen fluoride) Hydrogen peroxide Ammonia, methane, phosphine or hydrogen sulphide Acetylene, hydrogen peroxide Isolate from everything Hydrogen peroxide, nitric acid, or any other oxidant Fluorine, chlorine, bromine, chromic acid, peroxide Nitric acid, alkalis Ammonia, aqueous or anhydrous Copper, chromium, iron, most metals or their salts, any flammable liquid, combustible materials, aniline, nitromethane... 

Halogens, See also Bromine (Br) Chlorine (Cl) Fluorine (F) Iodine (I) higher aliphatic alcohols, 2 5 in N-halamines, 13 98 reactions with acetaldehyde, 1 105 reactions with acetone, 1 163 reactions with acetylene, 1 180 reactions with alkanolamines from olefin oxides and ammonia, 2 125—126 reactions with aluminum, 2 284—285, 349-359... 

Oxygenation of a chlorine fluoride, if possible, would be more attractive than fluorination of the shock-sensitive chlorine oxides. A process for FCIO2 has been claimed by Faust et al. (97) furnishing FCIO2 in about 50% yield by simply heating a mixture of GIF and O2 to 80°-90°G. However, attempts in our laboratory (70) to verify this synthesis failed. It appears, that the FGIO2 observed by Faust et al. (S7) in their experiments was due to hydrolysis of CIF (9, 36, 70). 

Chlorine trifluoride dioxide resembles chlorine fluorides and oxy-fluorides in its corrosive and oxjidizing properties. It must be handled in systems consisting of corrosion-resistant metals, Teflon, or sapphire. It appears to be marginally stabli in a well-passivated system at ambient temperature, It is a strong oxidative fluorinator as evidenced by its... 

Chlorine monofluoride oxide, 18 328-330 force field of, 18 329, 330 infrared spectrum of, 18 328, 329 stretching force constants for, 18 330 synthesis of, 18 328 Chlorine nitrate fluorination of, 18 332 preparation of, 5 54 Chlorine oxides, 46 109-110, 158 fluorination of, 18 348 Chlorine oxyfluorides, 18 319-389, see also specific compounds adduct formation, 18 327, 328 amphoteric nature of, 18 327, 328 bond lengths, 18 326 bond strengths, 18 323-327 geometry of, 18 320-323 ligand distribution, 18 323 reactivity of, 18 327, 328 stretching force constants, 18 324-327 Chlorine pentafluoride oxide, 18 345, 346 Chlorine trifluoride, reaction with difluoramine, 33 157... 

Room temperature sensors based on a V2O5-graphite cathode and a polyethylene oxide-based electrolyte were reported by Sathiyamoorthi etal. [55]. The gas is sampled through the porous cathode and for both chlorine and fluorine good sensitivity and rapid response times were observed. 

Chlorine Trifluoride, ClF3, mw 92.46 nearly colorless orpalegrn gas fr p —83°, bp +11.3°. Extremely reactive, comparable to fluorine reactions with org compds and with w take place with expl violence. Can be prepd in 99% purity by reaction of chlorine and fluorine at 280° and condensation of the product at —80°. Used as oxidizer in pioplnts, in incendiaries and for cutting oil well tubes Refs 1) Gmelin-Kraut,-not found 2) Lange (1961), 240 3) CondChemDict (1961),... 

Arsenic(III) fluoride, like antimony(III) fluoride (see Section 12.1.), is used to substitute fluorine for chlorine, bromine and iodine not only at carbon but also at other atoms, such as phosphorus, boron or metals. Chlorophosphanes undergo oxidative fluorination with arsenic(III) fluoride [or antimony(III) fluoride] to trifluoro-A5-phosphanes 1. 

Difluorotri(phenyl)-/.5-stibane, the most readily accessible among the aromatic anti-mony(V) fluorides, can be synthesized by several alternate methods in addition to those described above, i.e. by substitution of fluorine for chlorine in dichlorotri(phenyl)-/i5-stibane with potassium fluoride109 or hydrogen fluoride,110 and by oxidative fluorination of triphenylstibane with fluorine (in chloroform),111 perfluoro-l-fluoropiperidine,112 (difluoroiodo)ben-zene,107 or xenon difluoride.10 1... 

Based on their relative positions in the periodic table, which might you expect to be a stronger oxidizing agent, chlorine or fluorine Why ... 

Many reactions thut cannol lake place in aqueous solutions because of the reactivity of water may be performed readily in molten sails. Both chlorine and fluorine react with water (the latter vigorously), and so the use of these oxidizing agents in aqueous solution produces hydrogen halides, etc., in addition lo the desired oxidation products. The use of the appropriate molten halide obviates this difficulty. Even more important is the use of molten halides in the preparation of these halogens ... 

On the other hand, oxidizing fluorinating agents like silver difluoride, xenon difluoride, or bromine trifluoride replace one chlorine group and then cleave the sulfur-nitrogen bond [5(5]. 

Chlorine Dioxide See under Chlorine Oxides Chlorine Fluorides Although in 1891, H. Moissan (cited in Ref 2) easily prepd bromine iodine fluorides by direct action of the corresponding elements, he claimed that it was impossible to obt any chlorine fluoride. Other investigators among them Lebeau(1906, cited in Ref 2) and Ruff Zedner(1909 cited in Ref 2) also tried, but failed. It was not until 1928 that Ruff et al (Ref 3) succeeded in prepg the monocompd Chlorine Monofluoride, C1F, mw 54.46 colorless gas, fr p -154, bp 100.8, d 1.62 at -100° critical temp -14°, Q evapn 2.27 kcal/mol was prepd by action of si moist chlorine on fluorine at RT if the gases are dry they do... 

---