Question

In: Chemistry

1. Assign oxidation numbers to the Iron atoms of Magnetite. Recall Magnetite's chemical formula Fe3O4 is...

1. Assign oxidation numbers to the Iron atoms of Magnetite. Recall Magnetite's chemical formula Fe3O4 is better written as FeOFe2O3.

2. Sketch electron filling of the d-orbitals for the Fe3+, Fe2+, Gd3+ and Y3+ ions. Rank them according to increasing paramagnetism.

3. Hessonite (Cinnamon Stone) is a variety of Grossular which is a Calcium-Aluminum rich garnet gemstone with a formula of Ca3Al2(SiO4)3.Would you expect this garnet to be magnetic? Explain.

Solutions

Expert Solution

1) Magnetite or Fe3O4 or FeO.Fe2O3 is a mixed oxide of iron and is said to be available in Inverse Spinel. Spinel is nothing but the site preferences of respective ions.

There are two available oxidation states of Fe here, i.e., +2 and +3. The site preferences in which these ion can arrange themselves are either in tetrahedral or octahedral voids.

Since every ion wants to attain higher stability, one of the Fe+3 is present in the octahedral voids (since it has more crystal field stabilization than tetrahedral and provides more stability to the ion).

Thus the overall arrangement is Fe+3O(Fe+2Fe+3)O3.

2) Fe+3- 3d5

all five unpaired electron, highly paramagnetic.

Fe+2- 3d6

four unpaired electrons, less paramagnetic that Fe+3

Gd+3- 4f7 5d0

No electrons in d orbital but all 7 electrons in f orbitals are unpaired. more paramagnetic than Fe+3.

Y+3- 4p65s04d0

no electrons in d orbital. all other orbitals are fully filled so no unpaired electrons. Y+3 is diamagnetic.

order of paramagnetism : Gd+3 > Fe+3 > Fe+2 > Y+3.

3) Generally aluminium silicates as compared to Iron silicates show very minimal or negligible magnetism. For example, in andradite, i.e., Ca3Fe+3(SiO4)3, due to the presence of a magnetic ion, the magnetic properties are prominent unlike in Hessonite where due to absence of any magnetic ion it lacks magnetic behaviour.


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