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Hazard Predictions

• Corrosive: Reaction products may be corrosive
• 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

The combination of active metals with acetals, hemiacetals, or ketals may result in reactions of the former with alcohols or ethers similar to the reactions described below:

ALCOHOLS:

Ethanol reacts with active metals to form the ethoxide ion and H2 gas (Logsdon, J.E. 2004. Ethanol. In Kirk-Othmer Encyclopedia of Chemical Technology. John Wiley & Sons, Inc. (Online)).

Isopropanol reacts with finely-divided aluminum to form H2 gas. The reaction is exothermic, and can be vigorous after an induction period (Logsdon, J.E., R.A. Loke. 1996. Isopropyl Alcohol. In Kirk-Othmer Encyclopedia of Chemical Technology. John Wiley & Sons, Inc. (Online); Wilds, A.L. 1944. Organic Reactions 2:198).

After an induction period, MeOH/CCl4 can dissolve active metals such as Al, Mg, and Zn, and the dissolution process is rapid and exothermic. Flammable H2 or CH4 gases may be produced. Methanol forms highly explosive mixtures with aluminum or magnesium, and the mixing process can be violent (Shidlovskii, A.A. 1947. Chemical Abstracts 41:1105d; Urben, P.G. 1995. Bretherick's Handbook of Reactive Chemical Hazards, 5th Edition. Oxford: Butterworth-Heinemann. pp. 1658; Kuppers, J.R. 1978. Journal of the Electrochemical Society 125:97-98).

Methanol releases toxic and flammable carbon monoxide gas when distilled over powdered zinc (Rodd, E. H, ed. Chemistry of Carbon Compounds, Elsevier Publishing Company, Amsterdam, 1951, vol. 1a, pp. 298)

ETHERS:

Dioxane reacts explosively with Raney Ni at 210C (Mozingo, R. 1955. Organic Synthetics 3:182).

Aluminum powder can abstract the oxygen atom from diethyl ether even at very low temperatures. Reactive hydrocarbon radicals may be produced during this process (Murdock, T. O., Ph.D. Thesis, Univ. N. Dakota, 1977).

Diethyl ether is used to dissolve magnesium metal for preparation of Grignard reagents. The lone pairs in ether stabilize the metal, and do not react with the atom (Loudon, Marc. 2002. Organic Chemistry. 4th ed. New York: Oxford University Press. p. 334-336).

Potential Gas Byproducts

• Hydrogen (H2)
• Hydrocarbons