pp-03-25-new dots.qxd 10/23/02 2:16 PM Page 136 136 BROMIC ACID / BROMINE BROMIC ACID [7789–31–3] Formula: HBrO3; MW 128.91 Uses Bromic acid is used as an oxidizing agent; and also as intermediate in the preparation of dyes and pharmaceuticals . Physical Properties Unstable compound; stable only in dilute aqueous solutions; solution turns yellow on standing; decomposes when heated to 100°C. Preparation Bromic acid is prepared by adding sulfuric acid to barium bromate. Ba(BrO3)2 + H2SO4 → 2HBrO3 + BaSO4 The product is distilled and absorbed in water. A 50% solution may be obtained by slow evaporation of the dilute solution in vacuum at –12°C. Toxicity Contact with skin and eyes can cause severe irritation. BROMINE [7726–95–6] Symbol Br; atomic number 35; atomic weight 79.904; a halogen group ele- ment; electron affinity 3.36359 eV; electronegativity 2.8; electron configura- tion [Ar] 3d104s24p5; most stable valence states –1 and +5, less stable valence states +1 and +3; a diatomic molecule (Br2) in liquid and vapor states over a wide range of temperature; two stable isotopes, Br–79 (50.57%) and Br–81 (49.43%). Occurrence and Uses Bromine occurs in nature as bromide in many natural brine wells and salt deposits. It also is found in seawater at a concentration of 85 mg/L. The ele- ment was discovered by A. J. Balard and C. Lowig, independently in 1826. Bromine is used in bleaching fibers and as a disinfectant for water purifica- tion. Other applications are in organic synthesis as an oxidizing or brominat- ing agent; in the manufacture of ethylene dibromide, methyl bromide and other bromo compounds for dyes and pharmaceutical uses; as a fire retardant for plastics; and in chemical analysis. Ethylene dibromide is used in anti- pp-03-25-new dots.qxd 10/23/02 2:16 PM Page 137 BROMINE 137 knock fluids in motor fuels. Over 80% of the bromine produced is consumed in the manufacture of this compound. Physical Properties Dark reddish-brown liquid; the only nonmetallic element that is a liquid at ambient temperatures; strong disagreeable odor; volatilizes; density 3.12 g/mL at 20°C; vapor density 7.59 g/L; refractive index 1.6475; boils at 58.8°C; solidifies at –7.2°C; vapor pressure 64 torr at 0°C and 185 torr at 22°C; criti- cal temperature 315°C; critical pressure 102 atm; critical volume 127 cm3/mol; surface tension 39.8 dynes/cm at 25°C; electrical resistivity 6.5 x 1010 ohm–cm at 25°C; sparingly soluble in water (2.31 g/100g at 0°C and 3.35 g/100g at 25°C); soluble in common organic solvents. Thermochemical Properties ∆Hƒ ° (Βr2) 0.0 kcal/mol ∆Hƒ ° (g) 26.74 kcal/mol ∆Gƒ ° (g) 19.69 kcal/mol S° (g) 41.82 cal/degree mol Cρ (g) 4.97 cal/degree mol Cρ (l) 8.56 cal/degree mol Production Bromine is obtained from natural brines, salt beds and seawater. The bro- mide salts extracted from these sources are oxidized by chlorine to yield bromine: 2NaBr + Cl2 → 2NaCl + Br2 The bromine vapors are swept out into current of air or stream from the reac- tion chamber and trapped in an alkaline or reducing solution. Chlorine is removed over a stripping column. Bromine is purified in a fractionating col- umn. Reactions Most reactions of bromine are similar to other halogens. Its reactivity falls between chlorine and iodine. It readily attacks a number of metals including alkali and alkaline earth metals, palladium, platinum, aluminum, copper, antimony and tin, forming their bromides. These reactions can be vigorous to violent. It oxidizes a number of substances, including metal carbides, car- bonyls, hydrides, and organic substances. It combines with hydrogen to form hydrogen bromide. Organic compounds, such as olefins, aromatics and alka- nes undergo addition or substitution reactions yielding bromoderivatives. While the addition reaction with ethylene produces ethylene dibromide, bromination of benzene in the presence of iron as catalyst produces a substi- tution product, bromobenzene. Reaction with aqueous acetone and sodium chlorate at 40°C forms bromoacetone. Substitution reactions with alkanes yield alkyl bromides. Bromine combines with fluorine at room temperature pp-03-25-new dots.qxd 10/23/02 2:16 PM Page 138 138 BROMINE forming bromine trifluoride, BrF3. The reaction produces luminous flame. Diluted with nitrogen, bromine vapor and fluorine react on heating at 200°C to form bromine trifluoride, BrF3, or the pentafluoride, BrF5. Reaction with iodine produces iodine monobromide, IBr. Bromine reacts with phosphorus to form phosphorus tribromide, PBr3 or phosphorus pentabromide, PBr5. The pentabromide forms in the presence of excess bromine. Bromine oxidizes hydrogen sulfide to sulfur: Br2 + H2S → S + 2HBr Bromine liberates iodine from iodide solution: Br2 + 2I¯ → 2Br¯ + I2 Combination reactions occur with several nonmetals. With sulfur, it forms sulfur monobromide, S2Br2. With the addition of selenium, products are sele- nium monobromide, Se2Br2, and selenium tetrabromide, SeBr4. It yields unstable tellurium monobromide, Te2Br2, and a stable tetrabromide, TeBr4,with tellurium. In aqueous solution, bromine hydrolyzes slightly, forming unstable hypo- bromous acid, HOBr, which decomposes to hydrobromic acid and oxygen, causing the bleaching action of bromine water. The decomposition is acceler- ated by light. Br2 + H2O → HOBr + HBr HOBr light→ HBr + O Bromine water oxidizes aldose to lactones which hydrolyze to alfonic acids. Bromine combines with rubidium and cesium bromides forming solid poly- bromo complexes that can be crystallized from aqueous solutions. The com- plexes are soluble in liquid bromine. Bromine reacts with cold nitric oxide forming nitrosyl bromide, NOBr, and nitrosyl tribromide, NOBr3. Hazard Most reactions of bromine are highly exothermic which can cause incan- descence or sudden increase in pressure and rupture of reaction flasks. There are a number of cases of explosions documented in the literature. (NFPA. 1986. Fire Protection Guide on Hazardous Materials, 9th ed. Quincy, MA: National Fire Protection Association) Reactions of liquid bromine with most metals (or any metal in finely divided state), metal hydrides, carbonyls and nitrides can be explosive. Many oxides and halides of nonmetals, such as nitrogen triiodide or phosphorus trioxide, react explosively or burst into flame in contact with liquid bromine. Bromine is moderately toxic by all routes of exposure. It is an irritant to the eye and respiratory tract. Inhalation can cause dizziness, headache, coughing pp-03-25-new dots.qxd 10/23/02 2:16 PM Page 139 BROMINE PENTAFLUORIDE 139 and lacrimation. A short exposure to 1,000 ppm for 15 minutes can be fatal to humans. (Patnaik, P. 1999. A Comprehensive Guide to the Hazardous Properties of Chemical Substances, 2nd edition. New York: John Wiley & Sons). Ingestion produces nausea, abdominal pain and diarrhea. The liquid is corrosive to skin. BROMINE PENTAFLUORIDE [7789–30–2] Formula: BrF5; MW 174.896 Uses Bromine pentafluoride is used as an oxidizer in liquid rocket propellants; and as a fluorinating agent in the processing of uranium. Physical Properties Colorless to pale yellow liquid; fumes in air; density 2.466 g/mL at 25°C; boils at 40.8°C; decomposes above 460°C; solidifies at –60.5°C; reacts violent- ly with water. Thermochemical Properties ∆Hƒ° (l) –109.6 kcal/mol ∆Hƒ° (g) –102.5 kcal/mol ∆Gƒ° (l) –84.1 kcal/mol S° (l) 53.8 cal/degree mol S° (g) 76.5 cal/degree mol Cρ (g) 23.8 cal/degree mol ∆Hfus 1.355 kcal/mol ∆Hvap (at bp) 7.31 kcal/mol Preparation Bromine pentafluoride is prepared by fluorination of bromine at 200°C. The reac- tion is carried out in an iron or copper vessel. The halogens are diluted in nitrogen. Hazard Bromine pentafluoride is a highly reactive compound combining explosive- ly or with ignition with most elements and their compounds. Spontaneous explosion or flaming can occur when mixed with water, organic compounds, metal powder, metal halides, metal oxides, metal sulfides and chlorine (upon warming) (Patnaik, P. 1999. A Comprehensive Guide to the Hazardous Properties of Chemical Substances, 2nd ed. New York: John Wiley). The liquid is dangerously corrosive to skin. The vapors are highly irritating to eyes, skin and mucous membranes. pp-03-25-new dots.qxd 10/23/02 2:16 PM Page 140 140 BROMINE TRIFLUORIDE / CADMIUM BROMINE TRIFLUORIDE [7787–71–5] Formula: BrF3; MW 136.90 Uses Bromine trifluoride is used as a fluorinating agent; and an electrolytic sol- vent for fluoride. Physical Properties Colorless liquid; hygroscopic; density 2.803 g/mL; boils at 125.8°C; solidifies at 8.8°C; vapor pressure 8 torr at 21°C; decomposes violently in water. Thermochemical Properties ∆Hƒ° (l) –71.9 kcal/mol ∆Hƒ° (g) –61.1 kcal/mol ∆Gƒ° (l) –57.5 kcal/mol ∆Gƒ° (g) –54.8 kcal/mol S° (l) 42.6 cal/degree mol S° (g) 69.9 cal/degree mol Cρ (l) 29.78 cal/degree mol Cρ (g) 15.92 cal/degree mol ∆Hvap 11.37 kcal/mol Preparation Bromine trifluoride may be prepared by fluorination of bromine at 80°C. The halogen mixtures may be diluted in nitrogen or an inert gas. Hazard Bromine trifluoride is a highly reactive compound. It ignites or explodes in contact with a wide array of substances including water, finely divided met- als, metal oxides and salts and organics. See Bromine Pentafluoride. Skin contact with liquid can burn tissues. Vapors can damage eyes, lungs and respiratory tract. CADMIUM [7440–43–9] Symbol Cd; atomic number 48; atomic weight 112.41; a Group IIB (Group 12) metallic element; ionization potential 8.994eV; electron configuration [Kr]4d105s2; valence state +2; standard electrode potential, E° –0.40V.