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12.2.3: Aluminum

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    373076
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    Aluminum is easily oxidized, and so its ore, Al2O3, is difficult to reduce. In fact water is reduced rather than Al3+(aq), and so electrolysis must be carried out in a molten salt. Even this is difficult because the melting point of Al2O3 is above 2000°C—a temperature which is very difficult to maintain.

    The first successful method for reducing Al2O3 is the one still used today. It was developed in the United States in 1886 by Charles Hall (1863 to 1914), who was then 23 years old and fresh out of Oberlin College. Hall realized that if Al2O3 were dissolved in another molten salt, the melting point of the mixture would be lower than for either pure substance. The substance Hall used was cryolite, Na3AlF6, in which the Al2O3 can be dissolved at just over 1000°C.

    Electrolytic_Cell_Used_in_Hall_Process.jpg
    Figure \(\PageIndex{1}\): The Hall process.

    The electrolytic cell used for the Hall process. (Figure \(\PageIndex{1}\)) consists of a steel box lined with graphite. This contains the molten Na3AlF6 and Al2O3 and also serves as the cathode. The anode is a large cylinder of carbon. Passage of electrical current maintains the high temperature of the cell and causes the following half-equations to occur:

    \[\text{Al}^{3+} + \text{3}e^{-} \rightarrow \text{Al}(l) \label{1} \]

    \[\text{2O}^{2-} + \text{C}(s) \rightarrow \text{CO}_2(g) + \text{4}e^{-}\label{2} \]

    Since the carbon anode is consumed by the oxidation half-equation, it must be replaced periodically. The video below shows the process

    Aluminum production requires vast quantities of electrical energy, both to maintain the high temperature and to cause half-equations \(\ref{1}\) and \(\ref{2}\) to occur. Currently about 5 percent of the total electrical energy produced in the United States goes into the Hall process. Much of this energy comes from combustion of fossil fuels and hence consumes a valuable, nonrenewable resource. Since Al is protected from oxidation back to Al2O3 by a surface coating of oxide, it is a prime candidate for recycling, as well as for applications such as house siding, where it is expected to remain for a long time. Throwing away aluminum beverage cans, on the other hand, is a tremendous waste of energy.

    Several other easily oxidized metals are currently produced by electrolysis, but not in such large quantities as Al. Mg is obtained by electrolyzing molten MgCl2 which is derived from seawater, and Na and Ca are produced together from a molten mixture of NaCl and CaCl2.

    Contributions and Attributions

    This page is licensed under a CC BY-NC-SA 4.0 license and was authored, remixed, and/or curated by Ed Vitz, John W. Moore, Justin Shorb, Xavier Prat-Resina, Tim Wendorff, & Adam Hahn. A detailed versioning history of the edits to source content is available upon request.


    12.2.3: Aluminum is shared under a not declared license and was authored, remixed, and/or curated by LibreTexts.

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