Chem/Chen/Mats 4214 Problem Set #1 Due in class, Wednesday, January 25

Spring 2012

1. Hydrogenation of polybutadiene converts both cis and trans isomers to the same linear structure, and vinyl groups to ethyl branches. A polybutadiene sample of molecular weight 168,000 was found by infrared spectroscopy to contain double bonds consisting of 47.2% cis, 44.9% trans, and 7.9% vinyl. After hydrogenation, what is the average number of backbone carbon atoms between ethyl side chains? 2. The following is a MALDI-TOF spectrum of an anionically prepared homopolymer. (a) Estimate Mw, Mn, and the polydispersity index;

(b) Propose a candidate repeat unit structure; (c) What, if anything, can you say about the end group structure based on these data? 3. R.E. Cohen and A. R. Ramos (Macromolecules 12, 131 (1979)) describe phase equilibrium studies of block copolymers of butadiene (B) and isoprene (I). One such polymer is described as having a 2:1 molar ratio of B to I with the following microstructure: B 45% cis-1,4; 45% trans-1,4; 10% vinyl. I over 92% cis-1,4. Draw the structure of a portion of this polymer consisting of about 15 repeat units, and having approximately the composition of this polymer.

4. Proton NMR spectroscopy is used to attempt to quantify the molecular weight of a poly(ethylene oxide) molecule with methyoxy end groups at each terminus. If the integration of the methyl protons relative to the methylene protons gave a ratio of 1:20, what can you say about the molecular weight? 5. The composition of the US Electoral College is shown in the accompanying table (Washington DC omitted). (a) Plot the electoral votes as a distribution, and locate the number and weight averages. What is the polydispersity index of the impact of the individual states in the presidential election? (b) What kind of average impact does a state have in a vote in the US House of Representatives? (c) What kind of average impact does a state have in a vote in the US Senate?
State Alabama Alaska Arizona Arkansas California Colorado Connecticut Delaware Florida Georgia Hawaii Idaho Illinois EV 9 3 10 6 55 9 7 3 27 15 4 4 21 State Indiana Iowa Kansas Kentucky Louisiana Maine Maryland Massachusetts Michigan Minnesota Mississippi Missouri Montana EV 11 7 6 8 9 4 10 12 17 10 6 11 3 State Nebraska Nevada New Hampshire New Jersey New Mexico New York North Carolina North Dakota Ohio Oklahoma Oregon Pennsylvania Rhode Island EV 5 5 4 15 5 31 15 3 20 7 7 21 4 State South Carolina South Dakota Tennessee Texas Utah Vermont Virginia Washington West Virginia Wisconsin Wyoming Total electors EV 8 3 11 34 5 3 13 11 5 10 3 535