The Crystal Structures of Corundum and Hematite

Corundum model, side view.

Corundum, Al₂O₃ (aluminum = silver; oxygen = red). A hexagonal (rhombohedral) crystal system constructed of aluminum atoms that are each surrounded by six oxygen atoms. The oxygen atoms are not bonded at the corners of a regular octahedron.

Hematite model, side view.

Hematite, Fe₂O₃ (iron = orange; oxygen = red). A hexagonal (rhombohedral) crystal system constructed of iron atoms surrounded by six oxygen atoms not at the corners of a regular octahedron.

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In 1925 Linus Pauling and Sterling Hendricks published a paper detailing the crystal structures of corundum and hematite. It was the fifth crystal structure analysis that Pauling had undertaken. During the early years of his research, Pauling had a tendency to correct the work of others, and the determination of hematite and corundum’s crystal structures was not an exception.

In 1917 the British father and son duo of William Henry and William Lawrence Bragg had studied the structure of ruby using X-rays. Citing this data, they hypothesized in 1924 that each aluminum atom in ruby is equidistant from six oxygen atoms, and that each oxygen atom is equidistant from four aluminum atoms. The Bragg’s used this hypothesis in their later work on theories of birefringence (the refraction of a ray of light into two slightly different and unequal rays) and to explain the intensity of X-ray reflections, in terms of temperature variation, from the faces of ruby crystals.

Hendricks and Pauling were not certain of the Bragg’s methods, and wrote in their analysis of corundum, “an exact knowledge of the arrangement of the constituent atoms in ruby would make the arguments of these papers much more convincing.” (J. Am. Chem. Soc., 47 (1925), p. 781)

Corundum is a gemstone whose varieties include ruby and sapphire. It is an aluminum oxide, and the second hardest mineral known to science after diamond. This property is generally attributed to the strong and short bonds which pull oxygen and aluminum atoms close together, making the crystal unusually hard and very dense.

Corundum model, top view.

Hematite comes in many varieties, each having their own unique name and composition. Hematite is an iron oxide, and very important as an ore of iron. It is also used as a pigment and is collected as a mineral specimen. It is blood red in powdered form, but can be gray, black, red or brown in its solid form. It is also used in jewelry, either as a set stone, or as a piece itself.

Pauling and Hendricks used Laue and spectral photographs, as well as the theory of space groups, to analyze the crystal structures of hematite and corundum. They found that, contrary to the Braggs’ hypothesis, the spacing of atoms in corundum’s atomic structure was not equidistant. Though they confirmed the Braggs’ ratio of oxygen to aluminum atoms, they found that instead of forming the corners of a regular octahedron around aluminum atoms, three of the six oxygen atoms were closer to the aluminum atom than were the other three. Similarly they found that instead of forming the corners of a regular tetrahedron around oxygen atoms, two of the aluminum atoms surrounding each oxygen atom were closer than the other two.

Sir William Lawrence Bragg

Pauling and Hendricks disproved the Braggs’ hypothesis of a constant aluminum-oxygen distance, and found that the Braggs’ value for the distance between aluminum and oxygen was also incorrect. The publication of the Pauling-Hendricks findings and the professional implications of their critique were not missed by the Braggs. Pauling was later told that Lawrence Bragg resented his “intrusion” into the fields of crystallography and mineralogy, and that he considered Pauling to be a competitor. Consequently, many of Pauling’s initial publications, often critiques of the work that others had done, led to the start of what would become a long lasting rivalry between himself and the Braggs.

Pauling later claimed that his view of their relationship was very different, both at the beginning of his academic career and the end of it.   According to Pauling, the work that was initiated to correct the Braggs’ early hypotheses was done in order to strengthen the validity of their subsequent claims. In regards to the influence of atomic arrangements on birefringence, this work was successful.

Pauling had perceived the early relationship between himself and W. L. Bragg as that of professor and student, respecting the work that the Braggs had done, and acknowledging that it had enabled him to study crystallography and chemical bonds upon his entrance to Caltech. In reference to the rivalry perceived by the Braggs, Pauling wrote “I did not think of my own scientific work as being competitive; I found it engrossingly interesting for its own sake.” Overall it seems that Pauling and the Braggs were not merely separated by an ocean, but also by an unfortunate misunderstanding of motives.

Pauling research notebook entries on the structures of corundum and hematite.

More on Pauling and Hendricks’ determination of the structures of corundum and hematite can be found in Pauling’s Research Notebook 4.   The larger story of Pauling’s structural chemistry work, including his relationship with the Braggs, is told in Linus Pauling and the Nature of the Chemical Bond: A Documentary History.