3.

091 Introduction to Solid-State Chemistry - Fall 2012 Problem Set 5 Problem set quiz scheduled for October 16th

1.

Butadiene (C4H6) reacts with itself to form a dimer with the formula C8H12. The reaction is second order in C4H6. The value of the rate constant is 7.7 x 10-3 M-1s-1. (a) What is the initial rate of reaction in a reactor filled with butadiene to a concentration of 3.091 M? Express your answer in M s-1. (b) In the reactor described in part (a) how long does it take for the concentration of butadiene to drop to 10% of its initial value?

2. (a) Create a graph of energy versus extent of reaction. On the figure label the following. Use the numbers provided. (1) energy state of the reactants; (2) energy state of the products; (3) energy change of the reaction; (4) activation energy of the reaction. (b) An inhibitor, acting in a manner opposite that of a catalyst, retards the rate of reaction. Draw on the figure from part a) the curve associated with the conduct of the same reaction in the presence of an inhibitor. 3. Administratium bromide (AdBr) decomposes readily at temperatures exceeding 37C. The figure below shows how the rate of reaction varies with the concentration of AdBr. The rate, r, is in units of M s-1 and the concentration of AdBr, c, is in units of M (mole L-1). The slope has a value of a 1.67 and the intercept has a value of 0.490. (a) What is the order of reaction? (b) Calculate the instant rate of decomposition of AdBr when its concentration is 0.03091 M. Express your answer in M s-1.

3.091 Intro. to Solid-State Chem.

PS 5

4. Azomethane (CH3N2CH3) decomposes at 600 K to C2H6 and N2. The decomposition is first order in azomethane. Calculate t1/2 from the data in the table. Time, s 0 2000 4000 PCH3N2CH3, atm 8.2 x 10-2 3.99 x 10-2 1.94 x 10-2

5. How long will it take for the decomposition in Problem 4 to be 99.9% complete?

6. Nitramide (O2NNH2) decomposes in aqueous solution to N2O and H2O. What is the experimental rate law, [N2O]/t, for the decomposition of nitramide if the mechanism for the decomposition is O2NNH2 O2NNH- + H+ (fast) O2NNHH+ + OHN2O + OH+ N2O (slow) (fast)

7. Draw schematically in two diagrams, the temperature dependence of electrical conductivity over the temperature range from 10K to 300K in a metal and in a semiconductor. (Rationalize the respective behavior.)

8. Will electro-magnetic radiation of = 5.00 x 10-7 m generate conduction electrons in intrinsic germanium (Ge)?

9. Determine if light of = 1.3 x 10-6 m incident on silicon can generate electrons in the conduction band. 10. You have two unidentified solids. One of these is known to have an energy band gap (Eg) of 0.7 eV, the other one of 1.9 eV. Describe how you can unambiguously differentiate the two from each other without complex instrumentation and explain the phenomenon which is the basis of your analysis.

3.091 Intro. to Solid-State Chem.

PS 5

11. A material exhibits an optical band edge (transition from absorption of light to transmission) at = 4.62 x 1014 s-1. (a) Draw a diagram which reflects the absorption behavior of this material.

12. a) A crystal of unknown origin and nature is found to be transparent to light of frequencies up to 4.84 x 1014 Hz. Draw a meaningful and informative energy band diagram for this crystal. b) Gallium nitride (GaN) is a semiconductor with a band gap, Eg, of 3.2 eV. Sketch the absorption spectrum of this material, i.e., plot % absorption versus wavelength, . On your plot indicate the value of the absorption edge of GaN.

13. Magnesium is a metal; germanium is a semiconductor. Making reference to energy-level diagrams, explain the electrical properties of each element.

14. Hydrogen and helium solids are stable at low temperatures and elevated pressures. Solid hydrogen (H) is metallic, while solid helium (He) is an insulator. Making reference to the energy level diagrams of each, explain the difference in the electrical properties of solid H and solid He.

3.091 Intro. to Solid-State Chem.

PS 5