Chemistry 4000Introduction to Inorganic Chemistry: The Different Perspectives of BondingProblem Set 3

Show your work for maximum credit.1. The following is the lattice of lithium bismuthide.

a. Show what holes are filled by Li+ with respect to Bi3-.

b. How many ions are in the lattices?

2. Compare and contrast the diamond lattice (Figure 6.20 b) and the β-cristobalite (Figure 6.20 c) lattice in terms of:

a. The unit cell lattice type

b. The number of atoms/ions in the unit cell

c. The coordination numbers

Bi3-

Li+

Li3Bi

3. The measured density of NaCl is 2.167 g cm-3. From your understanding of the relationships among density, volume, Avogadro’s number, and formula weight, calculate the volume of the unit cell and the length of the edge of the cell.

4. Using the Born-Haber cycle, calculate the heat of formation of potassium fluoride. You may have to look up some of the values that you need to perform this calculation. Please reference your source(s).

5. The crystal structure of LaF3 is different from those discussed. Assume it is unknown. Using the equation of Kapustinskii, estimate the lattice energy.

6. Consider three solids A, B, and C. The band structures for these solids are represented below, with the shaded areas indicating occupancy by electrons. (The corresponding gap for Si(s) is 2 x 10-19 J).

a. For each of the solids shown above, predict its electronic properties. That is, would it be a conductor, an insulator, or a semiconductor? Justify your answer.

CBA

2 x 10-19 J = 1.2 eV

b. How would your answer to part (a) change (if at all) if the energy gap between the bands increased by a factor of 10, to around 12 eV? Describe any changes you expect.

7. Describe three conditions that would enable an ionic compound to be a conductor?

8. a. Of the following doped semiconductors, which will be p-type or n-type?

i. arsenic in germanium

ii. germanium in silicon

iii. indium in germanium

b. For the case of indium in germanium, draw a detailed band gap diagram.

9. Show the reaction of the superbase 1,8-bis(dimethylamino)naphthalene leveling ammonia to its conjugate base form. Assume that the superbase can only accept one proton.

1,8-bis(dimethylamino)naphthalene

10. a. If you have a 10 mL saturated solution of Zn(CN)2 and 10 mL of 300 μM of an unspecified ligand that can form a tetrahedral Zn2+ complex with an extremely high stability constant as to result in 100% complexation, determine whether the Zn2+ or the unspecified ligand will be the limiting reagent. The Ksp of 8.0x10-12 for Zn(CN)2.

b. What is the theoretical yield of the tetrahedral Zn2+ complex in terms of moles?

c. Given the Ka of HCN (10-9.21), write the equilibrium expression for the protonation of CN- in water in terms of the change in initial concentration of CN-.

d. Is the protonation of CN- thermodynamically favorable? Why or why not?

11. Name the following compounds:

a. [Cu(NH3)4][PtBr4] 

b. [Co(en)2Cl(NO2)]Cl

c. Na3[Al(C2O4)3]

d. W(CO)5PMe3 

12. Draw the stereo isomers of:

a. [PdCl2F(PMe3)]- if square planar and tetrahedral geometries are possible

b. dibromotetracarbonyliron(II)

13. To which ligand will Ni2+ have a higher affinity and why: PhNH2 or PhSH.