Molecular Shapes, Symmetry and Molecular Orbital Theory

1. Draw Lewis structures for the following species: BF3 H2O2 PCl5 CO2 SO2 SO3 OF2 N2H4 N2F2 NO O3 FCO2 NO2 NO2+ NO2 2. Using the VSEPR rules describe and justify the molecular structures adopted by each of the following: ClF2ICl4 OCF2 N2O ClF2+ SF4 PCl2F3 O3 ClO2 BrF5 SO3 POCl3 IF7 SO32-

3. For each of the molecular structures in question 2) use a sketch to identify the symmetry elements present. Hence identify the point group of each molecule. 4. a) Account for the N-O bond lengths and the O-N-O bond angles in the following species: r(N-O)/pm O-N-O angle () NO2 119 134 NO2 124 115 NO2+ 115 180 b) What bond angle would you expect in O3 ? Give your reasons. c) Comment on the observation that NO2 is in equilibrium with a dimer whereas CO2 is monomeric at all temperatures. 5. What is a molecular orbital ? Briefly describe how molecular orbitals can be formed by the interaction of atomic orbitals. How can molecular orbitals be used to explain the formation of chemical bonds ? 6. a) Draw and label a molecular orbital energy level diagram for dinitrogen, N2. Annotate it with pictorial representations of the molecular orbitals involved. b) What is the bond order of N2? How is this reflected in the reactivity and physical properties of N2 molecules? c) Draw a molecular orbital energy level diagram for CO. How does it differ from that for N2? d) What is the bond order of CO? Draw a valence-bond (Lewis) representation of the CO molecule. What is the direction of the dipole in CO? Explain your answer. The bond dissociation enthalpy of N2 is 942 kJ mol-1 and that for CO is 1072 kJmol-1. Explain this observation. e) What properties in contrast to those of CO do you predict for NO from its electronic configuration and molecular orbital energy level diagram?

7. a) Construct a molecular orbital energy level diagram for HF. Show clearly, with suitable sketches, the principal linear combinations of atomic orbitals being used. Label the molecular orbitals appropriately. Use the diagram to explain what is meant by i) a non-bonding orbital ii) bond polarity b) Account for the trend in bond dissociation energies (D) given below. Diatomic molecule O2 N2 F2 Cl2 D/ kJ mol-1 495 945 155 242

c) Account for the oxygen to oxygen distances in the following species: O2+ 112 pm O2 121 pm O2- 133 pm O22- 149 pm

Which, if any, of these four species contains unpaired electrons ? 8. Give a simple description of the bonding in AH3 molecules where A is an element from group 15. What H-A-H bond angle do you expect if the bonding orbitals are constructed (a) from pure p orbitals or (b) from sp3 hybrid orbitals on A ? Comment on the following experimental bond angles: NH3 106 PH3 94 AsH3 92