The Structure and Bonding of Solids
The Structure and Bonding of Solids
Structural Chemistry of Materials, Politecnico di Milano, AY 2017/18.
1. Cu and Zn form two alloys, called α‐brass and β‐brass. Discuss their structures. Predict the density
of β‐brass, from the knowledge of the atomic radii of Cu (128 pm) and Zn (134 pm).
2. Define the lattice enthalpy for an ionic compound. Discuss how this could be measured
experimentally and calculated theoretically. Place the following compounds in order of increasing
lattice enthalpy (justify your answer!): CaF2, SrCl2, SrF2, PbO2.
3. What are the “thermochemical radii” of polyatomic ions? What are they useful for?
4. At room temperature, Fe has a BCC structure ( phase or Ferrite). Describe this structure and
derive the atomic radius of Fe from its experimental density (7.784 g/cm3). Can you identify the
likely site(s) for the insertion of impurity atoms (e.g. C)? What is their geometry and approximate
radius?
5. Draw and discuss the crystal structures of the ZnS polymorphs.
6. Can ZnS be truly described as an ionic compound, or should one expect some deviations from the
ionic model? Why?
7. Recently, compounds such as (CH3NH3)PbI3 have emerged as very promising materials in solar cells.
Their structure is analogous to that of other compounds with the general formula ABX3 (where
CH3NH3+ corresponds to a single, polyatomic ion). What is the name of this family of compounds?
Can you describe their structure?
8. Define the lattice enthalpy of ionic solids, and say how it may be calculated. Afterwards, consider
these compounds, all having the rock‐salt structure: LiF(c=1029,e=1030), LiI(c=834,e=853),
AgF(c=920,e=953), AgI(c=777,e=882). The numbers in parentheses are the calculated and
experimental values, in kJ/mol. Discuss the trends in these values, and the reasons for the
differences between “c” and “e”.
9. Briefly discuss the principles at the basis of the structure of silicon‐oxygen compounds.
10. C60 (the “buckyball” molecule) adopts a CCP structure in the crystalline state. Describe this
structure. Calculate an approximate radius for C60, from the knowledge of the crystal density (1.65
g/cm3). Calculate the radius of the cavity inside one molecule (use the van der Waals radius of C =
0.170 nm) and compare it with that of the octahedral and tetrahedral cavities between the
molecules.
11. To what structural type does SrTiO3 belong? Draw and describe its crystal structure, highlighting
the coordination of all atoms/ions. Estimate its density (in g/cm3), knowing that its unit cell has a=
3.905 Å.
12. Explain how ionic radii are defined and measured. Discuss, using binary AX compounds as a specific
case, how they can be used to rationalize ionic crystal structures and evaluate lattice energies.
13. Write an equation for the decomposition reaction of 2nd group carbonates. Describe and justify the
trend(s) in their thermal stability (decomposition temperatures), on the basis of the lattice energies
of the carbonates and their decomposition product(s).
14. Sketch the Born‐Haber cycle and calculate the lattice enthalpy of MgBr2 from the appropriate data
in the “Resources” and the following standard enthalpies (note: 1.0 eV=96.49 kJ/mol):
sublimation of Mg(s): +148 kJ/mol vaporization of Br2(l): +31 kJ/mol
dissociation of Br2(g): +193 kJ/mol formation of MgBr2(s): ‐524 kJ/mol
Would you expect the lattice enthalpies of MgCl2 and NaBr to be larger or smaller, and why?