QUÍMICA INORGANICA I

TALLER 2
1. (a) Write equations to show how you expect compounds 7.24 to 7.28 to dissociate in aqueous solution.
(b) Suggest how compound 7.29 will react with NaOH in aqueous solution. What salts would it be possible
to isolate? (c) While it is convenient to draw the structures of compounds 7.24 to 7.28 as shown below,
these suggest that the P and S atoms violate the octet rule. Redraw structures 7.24 and 7.25 so that the P
atoms obey the octet rule.

2. In the reaction of t-butyl bromide with Ba(NCS)2, the product is 91 per cent S-bound t-Bu-SCN. However,
if Ba(NCS)2 is impregnated into solid CaF2, the yield is higher and the product is 99 per cent t-Bu-NCS.
Discuss the effect of alkaline earth metal salt support on the hardness of the ambident nucleophile SCN–.
(See T. Kimura, M. Fujita, and T. Ando, J. Chem Soc., Chem. Commun., 1990, 1213.)
3. The hydroxoacid Si(OH)4 is weaker than H2CO3. Write balanced equations to show how dissolving a solid,
M2SiO4, can lead to a reduction in the pressure of CO2 over an aqueous solution. Explain why silicates in
ocean sediments might limit the increase of CO2 in the atmosphere.
4. In their paper “The strengths of the hydrohalic acids” (J. Chem.Educ., 2001, 78, 116), R. Schmid and A.
Miah discuss the validity of literature values of the pKas for HF, HCl, HBr, and HI. (a) On what basis have
the literature values been estimated? (b) To what is the low acid strength of HF relative to HCl usually
attributed? (c) What reason do the authors suggest for the high acid strength of HCl?
5. The complex anion [FeCl4]– is yellow whereas [Fe2Cl6] is reddish. Dissolution of 0.1 mol FeCl3(s) in 1 dm3
of either POCl3 or PO(OR)3 produces a reddish solution that turns yellow on dilution. Titration of red
solutions in POCl3 with Et4NCl solutions leads to a sharp colour change (from red to yellow) at a 1:1 mole
ratio of FeCl3/Et4NCl. Vibrational spectra suggest that oxochloride solvents form adducts with typical
Lewis acids by coordination of oxygen. Compare the following two sets of reactions as possible
explanations of the observations.
6. (a) Discuss the factors that contribute towards KCl being a readily soluble salt (35 g per 100 g H2O at 298
K). (b) Develop your answer to part (a) by using the following data: ΔhydH°(K+, g) = -330 kJ mol–1; ΔhydH°
(Cl–, g) = - 370 kJ mol–1; ΔlatticeH°(KCl, s) = -715 kJ mol–1.
7. Answer the following questions using the Frost diagram in Fig. 5.18. (a) What are the consequences of
dissolving Cl2 in aqueous basic solution? (b) What are the consequences of dissolving Cl2 in aqueous acid?
(c) Is the failure of HClO3 to disproportionate in aqueous solution a thermodynamic or a kinetic
phenomenon?.
8. Using the following Latimer diagram, which shows the standard potentials for sulfur species in acid
solution (pH =0), construct a Frost diagram and calculate the standard potential for HSO4–/S8 (s)
the couple.

9. (a) Explain why water with high concentrations of dissolved carbon dioxide and open to atmospheric
oxygen is very corrosive towards iron. (b) The ligand EDTA forms stable complexes with hard acid centres.
How will complexation with EDTA affect the reduction of M2+ to the metal in the 3d-series?
10. In each of the following reactions, relate starting materials and products by the processes of reduction,
oxidation, disproportionation or no redox change. In some reactions, more than one process is taking place.

11. The commercial purification of copper metal is carried out in electrolytic cells. The anode is composed of
impure (‘blister’) copper, and the electrolyte is a mixture of aqueous CuSO4 and H2SO4. During
purification, copper is effectively transferred from the anode to the cathode, and pure copper is thereby
produced. (a) How does an electrolytic cell differ from a galvanic cell? (b) Write half equations for the
cathode and anode reactions. (c) Is the overall cell reaction spontaneous? If not, how does it occur?
12. (a) In aqueous solution at pH 0, Mn3+ disproportionates to MnO2 and Mn2+. Write equations for the two half-
reactions involved in this process. (b) Use Fig. 8.2 to obtain values of E° for the half-equations in part (a).
(c) Determine E°cellcand a value of ΔG°(298 K) for the disproportionation of Mn3+(aq) at pH 0. Write an
equation to which this value of ΔG°(298 K) refers.