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Alcohols and Polyols mixed with
Oxidizing Agents, Strong

Hazard Predictions

• Corrosive: Reaction products may be corrosive
• Explosive: Reaction products may be explosive or sensitive to shock or friction
• Flammable: Reaction products may be flammable
• Generates gas: Reaction liberates gaseous products and may cause pressurization
• Generates heat: Exothermic reaction at ambient temperatures (releases heat)
• Intense or explosive reaction: Reaction may be particularly intense, violent, or explosive
• Toxic: Reaction products may be toxic

Potassium superoxide reacts violently and exothermically with ethanol, causing gas evolution and potentially producing a fire hazard (Health and Safety Information. 1967. U.S. Army Environmental Command, Washington. pp. 251.).

Calcium hypochlorite may ignite, cause an explosion, or form explosive compounds with alcohols, including glycerol, monomethyl diethylene glycol, polyethylene glycol, ethanol, and methanol (Fawcett, H.H. 1959. Industrial and Engineering Chemistry Research 51(4):90A.), possibly with production of flammable gases (Kirkbride, K.P. et al. 1991. Journal of Forensic Science 36620(3):902.).

Many organic solvents, including some alcohols, explode on contact with permanganic acid (Fire and Explosion Risks, von Schwartz, E., London, Griffin, 1918, p. 327.).

Ethanol explodes in contact with F2O2 even at cryogenic temperatures (Streng, A.B. 1963. Chemical Reviews 63:615.).

Ethanol explodes on contact with FNO3 (Handbook of Preparative Inorganic Chemistry, Brauer, G., (Translation Ed. Riley, R.F.), London, Academic Press, Vol. 1, 1963. pp. 189.).

CrO3 vigorously oxidizes and ignites C1-C6 alcohols (Newth, F.H. et al. 1964. Chemistry and Industry 1482.).

Alcohols are exothermically oxidized by Na2O2, possibly causing fire or explosion (Fire and Explosion Hazards of Peroxy Compounds, Special Publication No. 394, Castrantas, H. M., Banerjee, D.K., Noller, D. C., Philadelphia, ASTM, 1965, p. 4.).

Reaction of isopropanol or ethanol with acidified sodium dichromate is highly exothermic, potentially explosive, and may pose a fire hazard (Annable, E.H. 1951. School Science Review 32(117):249; Urben, P.G. 1995. Bretherick's Handbook of Reactive Chemical Hazards, 5th Edition. Oxford: Butterworth-Heinemann. Vol. 1, pp. 1385.).

Ethanol ignites and explodes on contact with nitrosyl perchlorate (Hoffmak, K.A. et al. 1909. Berichte. 42:2031.).

Ethylene glycol is hypergolic with CrO3, KMnO4, and Na2O2 (Oouchi, H. et al. 1982. Chemical Abstracts 97:8605.).

Glycerol ignites on contact with KMnO4 (British Chemical Industrial Safety Council. 1974. Quarterly Safety Summary 45:11-122.).

Glycerol and chlorine can explode at slightly elevated temperatures (Statesir, W.A. 1973. Chemical Engineering Progress 69(4):54.).

Reaction of BrF5 and ethanol may cause fire or explosion (Mellor, J.W. 1956. Mellor's Comprehensive Treatise on Inorganic and Theoretical Chemistry. Vol. 2, Supp. 1. p. 172. Longmans, Green and Co Ltd.).

Ethanol ignites in contact with chromyl chloride (Mellor, J.W. 1943. Mellor's Comprehensive Treatise on Inorganic and Theoretical Chemistry. Vol. 11, p. 396. Longmans, Green and Co Ltd.).

Reaction of C1-C3 alcohols and barium perchlorate yield highly explosive alkyl perchlorates (Kirk-Othmer Encyclopedia of Chemical Technology. John Wiley & Sons, Inc. 1964. Volume 5. pp. 75.).

Alcohols can form explosive mixtures with H2O2 (MCA Safety Datasheet 53. Safety Datasheets, Manufacturing Chemists' Association, Washington. 1969.).

NaBrO3 and KBrO3 can produce explosive compounds with ethylene glycol (Oouchi, H. et al. 1982. Chemical Abstracts 97:8605.).

Methanol and lead perchlorate may form explosive methyl perchlorate (Willard, H.H. et al. 1930. Journal of the American Chemical Society 52:2396.).

Methanol can form explosive methyl hypochlorite in contact with sodium hypochlorite (Urben, P.G. 1995. Bretherick's Handbook of Reactive Chemical Hazards, 5th Edition. Oxford: Butterworth-Heinemann. pp. 1283.).

Ethanol can form explosive ethyl perchlorate with uranyl perchlorate (Eramesta, O. 1942. Suomen Kemist 15B:1.), KClO4 (Burton, H. et al. 1955. Analyst 80:16.), or magnesium perchlorate (Urben, P.G. 1995. Bretherick's Handbook of Reactive Chemical Hazards, 5th Edition. Oxford: Butterworth-Heinemann. pp. 1320.).

Reaction of ethanol with AgNO3 can form explosive silver fulminate and ethyl nitrate (Luchs, J.K. 1966. Photog. Sci. Eng. 10:334.).

Reaction of sodium hypochlorite and ethylene glycol can be violent after a short induction period (Bickerton, J. 1991. Chemistry in Britain 27(6):504.).

P4O6 reacts violently with methanol (Thorpe, T.E. et al. 1890. Journal of the Chemical Society 57:569-573.).

Disulfuryl difluoride and ethanol react violently (Hayek, E. 1951. Monatshefte f眉r Chemie. 82:942.).

Bromine and ethanol react vigorously with heat generation (Muir, G.D. 1972. Chemistry in Britain 8:6.).

Ethanol reacts with hypohalites to form haloforms, but is the only primary alcohol that can undergo this type of reaction (Logsdon, J.E. 2004. Ethanol. In Kirk-Othmer Encyclopedia of Chemical Technology. John Wiley & Sons, Inc. (Online)).

Methyl and ethyl alcohol may be oxidized to toxic and low-BP formaldehyde and acetaldehyde respectively by strong oxidizing agents such as K2Cr2O7 and KMnO4 (Morrison, R. T. and Boyd, R. N. Organic Chemistry, Allyn and Bacon, Inc, Boston: 1973, pp. 528).

Oxidation of methanol may proceed to CO2 (Rodd, E. H, ed. Chemistry of Carbon Compounds, Elsevier Publishing Company, Amsterdam, 1951, vol. 1a, pp. 298).

The reaction of ethyl alcohol and calcium hypochlorite yields chloroform, and by extension may also yield fluoroform with calcium hypofluorite (Rodd, E. H, ed. Chemistry of Carbon Compounds, Elsevier Publishing Company, Amsterdam, 1951, vol. 1a, pp. 304).

The reaction between the [ClO3]- ion and methanol may yield chlorine gas, carbon dioxide and chlorine dioxide gases (Masschelein, W. J. Chlorine Dioxide. Ann Arbor Science Publishers Inc, Ann Arbor, MI: 1979. pp. 120).

Potential Gas Byproducts

• Carbon Monoxide (CO)
• Carbon Dioxide (CO2)
• Hydrogen (H2)
• Hydrogen Halide (HX)
• Halogen Gas (X2)
• Halogen Oxides (XO2)