IChO 2003 · Theory problem 22

Face-centred cubic silver

Silver metal exists as a face-centered cubic (fcc) packed solid.

a) Draw an fcc unit cell.

Figure 1

b) How many atoms are present in the fcc unit cell?

c) The density of silver has been determined to be \(10.5\ \mathrm{g\,cm^{-3}}\). What is the length of each edge of the unit cell?

d) What is the atomic radius of the silver atoms in the crystal?

Official English text of the problem.

Answers

  • a) A cube with atoms centered at all eight corners and at the centers of all six faces.
  • b) \(4\) atoms per unit cell.
  • c) \(a=4.09\times10^{-8}\ \mathrm{cm}=409\ \mathrm{pm}\).
  • d) \(r=1.44\times10^{-8}\ \mathrm{cm}=144\ \mathrm{pm}\).

Solution

a) Draw a cube and place an atom at each of its eight vertices and at the center of each of its six faces, including the hidden faces. There is no atom at the body center. Neighboring atoms touch along the face diagonals.

b) Each corner atom is shared by eight unit cells, so it contributes \(1/8\) atom to the cell. Each face-centered atom is shared by two cells, contributing \(1/2\) atom. Therefore,

\[ Z=8\left(\frac18\right)+6\left(\frac12\right) =\boxed{4\text{ atoms per unit cell}}. \]

c) Use the standard molar mass \(M(\ce{Ag})=107.87\ \mathrm{g\,mol^{-1}}\) and Avogadro constant \(N_{\mathrm A}=6.02214076\times10^{23}\ \mathrm{mol^{-1}}\).

The mass of one unit cell is

\[ m_{\text{cell}}=\frac{ZM}{N_{\mathrm A}} =\frac{4(107.87\ \mathrm{g\,mol^{-1}})} {6.02214076\times10^{23}\ \mathrm{mol^{-1}}} =7.16489\times10^{-22}\ \mathrm g. \]

For a cube of edge length \(a\), the volume is \(a^3\). Hence,

\[ \rho=\frac{m_{\text{cell}}}{a^3}, \qquad a=\left(\frac{ZM}{\rho N_{\mathrm A}}\right)^{1/3}. \]

Substituting,

\[ a= \left[ \frac{4(107.87)} {(10.5)(6.02214076\times10^{23})} \ \mathrm{cm^3} \right]^{1/3} =4.08639\times10^{-8}\ \mathrm{cm}. \]

To three significant figures,

\[ \boxed{a=4.09\times10^{-8}\ \mathrm{cm} =0.409\ \mathrm{nm}=409\ \mathrm{pm}}. \]

d) Along a face diagonal, a corner atom touches the face-centered atom, which touches the opposite corner atom. The two center-to-center distances are each \(2r\), so the diagonal has length \(4r\). Geometrically, the face diagonal is \(a\sqrt2\). Thus,

\[ 4r=a\sqrt2, \qquad r=\frac{a}{2\sqrt2}. \]

Using the unrounded edge length,

\[ r=\frac{408.639\ \mathrm{pm}}{2\sqrt2} =144.476\ \mathrm{pm}. \]

To three significant figures,

\[ \boxed{r=144\ \mathrm{pm} =0.144\ \mathrm{nm} =1.44\times10^{-8}\ \mathrm{cm}}. \]

The answers were checked against the official answers published by the organisers.