Chem 210

Practice Exam 1C

Organic Chemistry: Chem 210

Practice Exam 1C
There are 33 questions on this exam. Check that you have done all of the problems and filled in the first 33 bubbles on the scantron. Most questions are worth 4 points; there are several two-point questions clearly labeled in the text. The maximum score on this exam is 100 points. Instructions Answer sheet 1) On the scantron, you need to clearly fill: your name and your student number, section number: test form (white = test form A; yellow = test form B). 2) Use a #2 pencil Exam policy 1) No electronic devices of any kind, such as calculators, cell phones, or even more advanced digital watches, are allowed. Possession of such devices during the exam, whether in use or not, is grounds for awarding a zero on the exam. 2) Molecular models are allowed (no instruction pages are permitted, however). 3) There are some blank pages at the end of the test that can be used as scratch paper. 4) Relevant tables, including the periodic table, are attached at the end of this exam. 5) Numerical values given in one question apply only to that question, and should not be used in other questions, unless there is a specific instruction to do so. If necessary, the values from the provided tables should be used, even if they differ from values that you may remember from different sources. 6) The exam results are based strictly on scantrons marks. No extraneous information is used to adjust the scores. Mark your choices with extra care. 7) Feel free to take this copy of the exam with you. The answer key will be posted on the web after the exam (under "News"). Hints 1) As you read the question, underline or circle key words to highlight them for yourself. 2) Questions have only one correct answer, unless indicated otherwise. No partial credit will be given. 3) There is no penalty for guessing.

All right reserved: P. Maslak, 2013

Page 1 of 11

Chem 210

Practice Exam 1C

1. (4 pts) Cycloalkanes with the formula of C6H12 have 12 different constitutional isomers. What is the maximum number of tertiary carbons possible in any of them? a) 1 b) 2 c) 3 d) 4 e) 5

2. (4 pts) Dipole moments usually are measured on collections of molecules, and represent average values for all conformations present. Which of the following collections of molecules will show a dipole moment (lone pairs are not shown explicitly)? A: ClH2CCH2Cl a) A and C e) A, B, and D B: NH3 b) A and E f) A, C, and E C: BF3 D: H3COCH3 c) B and C g) B, C, and E E: (CCl3)2 d) B and E

3-5. Consider all equivalent resonance structures for the cyclopentadienyl cation shown below.

3. (2 pts) What is the formal charge on carbon 1? a) 0 b) +1/5 c) +1/3 d) +1/2 e) +1

4. (2 pts) What is the bond order between carbons 1 and 2? a) 1 b) 7/5 c) 3/2 d) 5/3 e) 2

5. (4 pts) This cyclic carbocation has two sets of degenerate molecular orbitals. What is the correct ordering of energies of the MOs for this system?

a) b) c) d) e)

E=A<D<C=B E<D=B<A=C C=B<A=D<E C=D<B<A=E E<A=D<B=C

Page 2 of 11

All right reserved: P. Maslak, 2013

Chem 210

Practice Exam 1C

6. (4 pts) Taking into account hybridization and resonance effects, rank the following C-C bonds in order of decreasing length.

a) b) c) d) e)

A>C>D>B D>B>C>A C>A>D>B A>C>B>D B>D>C>A

7. (4 pts) Which one of the following isomeric structures has the lowest energy?

a)
Br OH Br

b)
HO Br

c)
HO

d)
Br OH

e)
Br

OH

8. (4 pts) Which statement about the following equilibrium is true?

O O

O + O H2O O pKa = 16 I II

O + O HO

pKa = 13 III IV

a) b) c) d) e)

The equilibrium favors III and IV. I and III are resonance structures. III is 3 times more acidic than II. II is the conjugate acid of I. IV is the strongest base in the system.

9. (2 pts) The torsional strain of a pair of eclipsing C-C bonds in cyclopentane is the same as the torsional strain of a pair of eclipsing C-H bonds. How much strain (in kJ/mol) is relieved on ring puckering from the flat cyclopentane to the envelope conformation, if the angle strain for both conformations is negligible? a) 7 b) 11 c) 21 d) 33 e) 45 f) 52
Page 3 of 11

All right reserved: P. Maslak, 2013

Chem 210

Practice Exam 1C

10. (4 pts) In the methyl anion (H3C) the H-C-H bond angles are ca. 107. On the other hand, in the allyl anion (H2C=CH-CH2) the H-C-H bond angles on the terminal carbons are ca. 120. Which statement accounts for this difference? a) The structures are not really different. In both species the lone pair is in an sp3 hybridized orbital, but with a different s character b) In the allyl anion the structure is stabilized by resonance, and in the methyl anion the charge is stabilized by increasing s-character in the orbital with the lone pair. c) A lone pair of electrons is always more stable in a p-type orbital than in an sp3 type orbitals. d) The HOMO of the allyl systems has orbital lobes on all carbons, but the HOMO of the methyl anion is localized mainly on hydrogens. 11. (4 pts) What is the name of the following hydrocarbon according to the IUPAC rules?

a) b) c) d) e) f) g)

3,3-dimethyl-5-propylhexane 6,6-dimethyl-4-propyloctane 3,3-diethyl-5-propyloctane 5,5-dimethyl-3-butyloctane 6,6-diethyl-4-propyllheptane 3,3-dimethyl-5-propyloctane 5,5-diethyl-3-butylheptane

12-13. Imagine a molecule of a flat (all carbons in one plane) cyclobutane with C-C bonds made of pure p orbitals. Lets call it A. 12. (2 pts) What is the H-C-H angle in A? a) 60o b) 90o c) 109.5o d) 120o e) 180o

13. (2 pts) Compare A to another flat cyclobutane, B, where the C-C bonds are made of hybrids with a large p character (and are bent like in cyclopropane), and to the real cyclobutane, C. Assuming that all structures have the same C-C bond lengths, arrange these molecules according to the diminishing torsional strain. a) A > B > C d) B > C > A b) A > C > B e) C > A > B c) B > A > C f) C > B > A

All right reserved: P. Maslak, 2013

Page 4 of 11

Chem 210

Practice Exam 1C

14. (4 pts) Which of the following molecules would have the following potential energy diagram for rotation about its central bond? Note: The 0o angle conformation was selected arbitrarily.

21 20 Energy kJ/mol 15 10 5 3.8 o 180 120o 7.6 o 60

21 18

3.8 0 o o 60 o 120

3.8 o 180

torsion angle

a) butane

b) 2-methylbutane

c) 2,3-dimethylbutane d) 2,2,3-trimethylbutane

15. (4 pts) Which statement about strain is incorrect? a) Strain energy is caused by imperfect bond lengths or angles. b) Perfectly staggered bonds do not contribute to the torsional strain. c) Cycloalkanes are puckered (except for cyclopropane) to minimize their torsional strain. d) Strained compounds release less energy during combustion than their strain-free isomers. e) Steric strain is defined as the repulsion that occurs when atoms are forced closer together than their van der Waals contact distance. 16. (4 pts) What is the energy difference (in kcal/mol) between the two compounds shown below? The negative sign indicates that the compound on the right is more stable.
Cl

Cl

a) 2.20

b) 1.55

c) 0.7

d) 1.55

e) 2.20

17. (4 pts) A carbon atom with a formal charge of +1 is bonded to three different substituents. The carbon uses one sp hybrid and one sp3 hybrid to make two of the bonds. What orbital is used to make the third bond? a) sp b) sp1.5 c) sp2 d) sp3 e) sp4 f) sp5
Page 5 of 11

All right reserved: P. Maslak, 2013

Chem 210

Practice Exam 1C

18-20. Consider the following reaction of benzoic acid and titanium tetrachloride. The lone pairs are not shown explicitly here.
O OH + TiCl4 product

18. (2 pts) Which of the following statements about this reaction is false? a) TiCl4 has low energy empty orbital available. b) Benzoic acid is the Brnsted base in this reaction. c) This is a Lewis acid-base reaction. d) Benzoic acid is the Lewis base in this reaction. 19. (2 pts) Which Lewis base MO is involved in product formation? a) nonbonding electron pair orbital on carbonyl oxygen (C=O) b) nonbonding electron pair on hydroxyl oxygen (OH) c) nonbonding electron pair on chlorine (not shown) d) lone pair in a d orbital on Ti (not shown explicitly here) e) orbital of benzene moiety 20. (2 pts) Which of the following is the main product of this reaction? (Lone electron pairs are not shown explicitly).
a) TiCl4 O OH b) TiCl4 OH c) O O H TiCl4 d) O O H TiCl4

21. (4 pts) Which one of the following structures is not a resonance form of the others?
a) b) c) d) e)

All right reserved: P. Maslak, 2013

Page 6 of 11

Chem 210

Practice Exam 1C

22. (4 pts) One chair conformation of cis-1,3-dimethylcyclohexane is 23.0 kJ/mol less stable than the other chair conformation. What is the strain energy difference (in kJ/mol) of the two chair conformations of 1,1,3-trimethylcyclohexane? (a) 8.3 b) 12.0 c) 15.4 d) 17.8 e) 20.0

23-28. The MOs of methylene, :CH2, in which all electrons are paired, are shown on the left. They are arranged according to their increasing energy from the bottom to the top, with (f) having the lowest energy and (a) having the highest. Answer the following questions by selecting the appropriate orbital. 23. (2 pts) Which orbital is the HOMO? 24. (2 pts) Which orbital is the LUMO? 25. (2 pts) Which orbital will be the most important in reaction of methylene with the hydride ion? 26. (2 pts) Which orbital corresponds to the lone electron pair? 27. (2 pts) If methylene were to be protonated, which orbital would be involved in the reaction? 28. (2 pts) All orbitals shown are combinations of atomic orbitals, except one. Which one?

29. (4 pts) Methylene, :CH2, with all its electrons paired (see questions 23- 28) reacts with H+ to give a new product. Which of the following reactions will yield the same product? a) removal of a proton from methane b) removal of a hydrogen atom from methane c) removal of a hydride from methane d) removal of two hydrogen atoms from methane e) removal of a hydride and a proton from methane

All right reserved: P. Maslak, 2013

Page 7 of 11

Chem 210

Practice Exam 1C

30-31. Consider the following compounds (Lone pairs are not explicitly shown).
a) O OH OH N HO CF3 N H b) c) d) e)

30. (2 pts) Which of the compounds is the strongest Brnsted acid? 31. (2 pts) Which of the compounds is the strongest Lewis base? 32. (4 pts) Which of the underlined atoms (in the molecules shown below) are of the sp3-hybridization type? Lone electrons pairs are not shown explicitly. A: (CH3)2O a) A and B B: (CH3)3N b) C and D c) A and C C: (CH3O)3B d) B, C, and D D: (CH2=CH)3C e) A, C, and D

33. (4 pts) The H-N-H bond angle in ammonia (:NH3) is 107o. Compared to ammonia, what would be the expectation for H-P-H bond angle in phosphine (:PH3)? a) The bond angles will be essentially the same because phosphorus is in the same column of the periodic table as nitrogen. b) The bond angle would be larger because phosphorus needs more p-character in its hybrids to form its longer bonds to hydrogen atoms. c) The bond angle would be larger because phosphorous is bigger and needs more space for its bonds. d) The bond angle would be smaller because phosphorous forms stronger bonds with hydrogen atoms. e) The bond angle would be smaller because phosphorus is less electronegative and needs more scharacter in its lone-pair hybrid.

------------------------------------------------------------------------------------------------------------------------------

End of the exam

All right reserved: P. Maslak, 2013

Page 8 of 11

Chem 210

Practice Exam 1C

Total Strain Energies in Cycloalkanes ring size kJ/mol kcal/mol 115 27.6 3 110 26.4 4 27 6.5 5 0 0 6 26 6.3 7 40 8.6 8

Energy Costs for Interactions in Alkane Conformers Interaction kJ/mole kcal/mole H-H eclipsed 4.0 1.0 H-CH3 eclipsed 6.0 1.4 CH3-CH3 eclipsed 11.0 2.6 CH3-CH3 gauche 3.8 0.9

All right reserved: P. Maslak, 2013

Page 9 of 11

Chem 210

Practice Exam 1C

All right reserved: P. Maslak, 2013

Page 10 of 11

Chem 210

Practice Exam 1C

Practice Exam 1C Answer key 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. C E B B E A A E D B F E A B D A D 18. 19. 20. 21. 22. 23. 24. 25. 26. 27. 28. 29. 30. 31. 32. 33. B A B C C D C C D D C C A E A E

All right reserved: P. Maslak, 2013

Page 11 of 11