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Chem 210

Training Set I

Organic Chemistry: Chem 210

Training Set I
The questions are arranged approximately in the order of the coverage of material in the lecture. This set covers the material of the first exam.

1. A bond is made by the overlap of an sp2 hybrid with an s orbital as shown below. What is the best graphical representation of the bond that forms at the same time?

* bond

a)

b)

c)

d)

e)

f)

2. Which of the following compounds has the shortest C-H bond?


a) H3 C CH3 b) H2 C CH2 c) HC CH d)

3. Which of the following statements about sp2 hybrid orbitals is not true? a) they are always present as a set of three sp2 orbitals b) they are usually used to form bonds (sometimes lone pairs) c) they are 33% s d) the ideal angle between two sp2 orbitals is 120 4. In a hypothetical molecule, a four-bonded carbon atom uses one sp and two sp5 hybrids to make three of its bonds. What is the remaining orbital that is used to make the fourth bond? a) pure s e) sp3 b) pure p f) sp4 c) sp g) sp5 d) sp2 h) sp6

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Chem 210

Training Set I

5. What are the hybridizations of the two oxygens in the acetate anion (CH3CO2)? a) both sp3 b) both sp2 c) both sp2.5 d) one sp2 and one sp3

6. Ammonia undergoes a rapid flip, wherein the hydrogens move from one side of the nitrogen atom to the other (like an umbrella in the wind), as shown in the diagram below. At the lowest energy points, the lone electron pair on nitrogen resides in an sp2.1 hybrid, but during the flip the hybridization of nitrogen changes continuously to finally reach the hybridization of the starting point again. What is the orbital that the lone pair resides in at the highest energy point during that transformation?

H H Energy N H (all atoms are in one plane)

H H H b) p f) sp4 N
c) sp g) sp5 d) sp h)
2

H N H H

a) s e) sp3

7. Lets assume that the H-P-H bond angle in PH3 is 90o (it really is 92o). What is the nature of the orbital holding the lone electron pair? a) sp3 hybrid b) sp2 hybrid c) sp hybrid d) pure s e) pure p f) intermediate between sp3 and sp2

8. Which of the following molecules have at least one sp hybridized carbon atom?

O I

CO II

CH3CN III

CO2 IV V

OH VI d) III, IV, VI

a) I, II, IV, VI

b) II, III, IV, VI

c) III, V, VI

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Chem 210

Training Set I

9. Which molecules have at least one atom that is sp2 hybridized? A: +CH2CH3 B: CH3OCH3 C: CH2CCH2 D: CH3CCH E: CH2CHCH3 F: CO G: OCHCH3 H: CH3CN I: CH3NH2

a) A and C b) F and H c) B and I d) A, G, and I

e) B, D, and H f) B, C, F, and G g) C, D, F, and H h) A, C, E, and G

10. In the methyl anion (CH3), the H-C-H bond angle is 106.6o (1/cos(106.6o) = 3.5). What is the hybridization index of the orbital holding the lone electron pair?

a) 3.0

b) 2.7

c) 2.3

d) 2.0

e) 1.8

11. In 1-bromo-3-chloro-1,2-propadiene (BrHC=C=CHCl) each terminal carbon is bonded to halogen and hydrogen atoms. Excluding the central carbon, what is the relative position of the terminal Br-C-H and Cl-C-H groups?

a) They are all in the same plane. b) They are in two planes 60o to each other. c) They are in two planes 90o to each other. d) They are in two planes 107o to each other. e) They are in two planes 109.5o to each other. f) They are in two planes 120o to each other. g) They are in two planes that freely rotate versus each other.
12. Assuming that oxygen and sulfur do not form double bonds in SO42, determine the formal charges for this anion (S is the central atom).

Atom: a) b) c) d) e) f) g) h)

O (all equivalent) +1 +1 +1/2 +1/4 -1 -1 -1/2 -1/4

S -4 -2 -2 -2 +4 +2 +2 +2
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Chem 210

Training Set I

13. What is the formal charge on nitrogen in the following species?

a) 1

b) 0

c) +1

d) +2

14. Which of the following compounds has the highest dipole moment?

15. Here is a comparison of and bonds. Which statement is false?

a) bonds are formed only by head-to-head overlap of atomic orbitals, while bonds are formed by head-to-head or lateral overlap. b) bonds have increased electron density on the bond axis, while bonds have no electron density on that axis. c) bonds are usually lower energy than bonds. d) A rotation around bonds does not change the overlap, while rotation around bonds leads to the diminished overlap. e) Only one bond, but one or two bonds can exist between two atoms.
16. Examine only the shortest CC bond in each of the following molecules. Arrange the molecules in order of increasing bond lengths of their shortest CC bond. (Hint: Think about how hybridization affects bond lengths.)

H2CCHCHCH2 A
a) b) c) d)
A<C<D<B C<D<A<B D<C<A<B D<B<C<A

[H2CCHCH2] B
e) f) g) h)

H2CCCH2 C

HCCH D

B<A<D<C B<C<D<A D<A<C<B B<D<C<A

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Chem 210

Training Set I

17. Compare the structure of CO2 and SO2. Which of them has a greater dipole moment and why? a) CO2 has a greater dipole because the electronegativity difference between carbon and oxygen is greater than that between sulfur and oxygen. b) CO2 has a greater dipole because the carbon is sp hybridized, and it forms shorter bonds with more negative charge on oxygens. c) SO2 has a greater dipole because the bond dipoles do not cancel in that molecule. d) SO2 has a greater dipole because one can write several resonance forms that show charge separation. e) Neither molecule has a dipole moment.

18. Which of the following is not a resonance structure of the other three?

19. Some resonance structures of diazomethane are shown below. Which statement about these structures is correct? H2C N N A H2C N N B H2C N N C H2C N N D

a) The central nitrogen atom is sp hybridized in A and B, but sp2 hybridized in C and D. b) Structure D contributes more to the description of the molecule than structure C. c) All structures satisfy the octet rule for all atoms. d) The equilibrium between A and B will be shifted to the left, because the negative charge is more stable on nitrogen than on carbon. e) All structures contribute equally to the description of the molecule. f) None of the statements is correct.

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Chem 210

Training Set I

20. Consider the allyl anion. Which orbital diagram represents the LUMO?

21-22. Consider the system of 1,3,5-hexatriene (see below). The molecular orbitals are shown schematically in a random order.

a)

b)

c)

d)

e)

f)

21. Which orbital corresponds to the HOMO of this hexatriene? 22. Which orbital corresponds to the LUMO of this hexatriene?

23. Below are the four lowest energy molecular orbitals of the pentadienyl cation (the highest energy is omitted). Which corresponds to the LUMO?

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Chem 210

Training Set I

24-27. The seven lowest molecular orbitals of formaldehyde (H2CO) are arranged according to their energy, from the lowest at the bottom (g) to the highest at the top (a). 24. Which orbital will interact the strongest with the empty s orbital of H+ in the protonation reaction? 25. Which orbital will interact the strongest in the reaction of formaldehyde with the hydride (H)? 26. Which is the C-O orbital? 27. Which orbital can be characterized as mainly C-O?

28. Consider the energy diagram (MO theory) of O2. Which orbital is the LUMO? a) the orbital built mainly of s atomic orbitals b) one of the two orbitals (same energy) c) the orbital built mainly of p atomic orbitals d) one of the two degenerate orbitals

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Chem 210

Training Set I

29. Which of the following best describes the lowest energy molecular orbital of an imine?

30. Which of the following molecules contain two conjugated bonds?

31. Which statement about the reaction of the methyl cation (CH3+) with the methyl anion (CH3) is incorrect? a) This is a Lewis acid Lewis base reaction. b) The HOMO controlling this reaction is the sp3-type orbital on the anion. c) The LUMO controlling this reaction is the sp3-type orbital on the cation. d) Ethane is the product of this reaction. e) There is some change of hybridization of both carbon atoms as the two ions combine. f) The HOMO-LUMO mixing of the two ions will produce two new molecular orbitals in the product, corresponding to the carbon-carbon and * bonds.

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Chem 210

Training Set I

32. Which of the following is not a good Lewis base? a) CH3SCH3 b) H2O c) CH3NH2 d) CH3CH3

33. What are the orbitals of the reactants which interact in the Lewis acid-base reaction between BH3 and H2O? a) an empty p orbital on boron and a non-bonding lone pair on oxygen b) an empty sp3 orbital on boron and a non-bonding long pair on oxygen c) a filled orbital on boron and an empty * orbital on oxygen. d) an empty s orbital on the hydrogen and a filled orbital on boron. 34. The HOMO- LUMO interactions between pairs of Lewis acids and bases are shown on the common energy scale below. The diagram accounts for orbital energies and overlaps. Which diagram represents the strongest interaction?
a) b) c) d)

35. For the following two acid base reactions, which statement is true?

a) I is favored to the right, II is favored to the left b) I is favored to the left, II is favored to the right c) I is favored to the right, II is favored to the right d) I is favored to the left, II is favored to the left

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Chem 210

Training Set I

36. Consider the following reaction involving two acids shown below: formic acid and HF. Which of the following statements about this reaction are true? A) B) C) D) E) F) G) H) Formic acid is the strongest Brnsted acid in the reaction. HF is the strongest Brnsted acid in the reaction. KF is the strongest Brnsted base in the reaction. KO2CH is the strongest Brnsted base in the reaction. The equilibrium favors the reactants. The equilibrium favors the products. Formic acid has a weaker conjugate base. HF has a weaker conjugate base.

O K+F+ H OH H

O O -K + + HF pKa = 3.2

pKa = 3.8

a) only A and D b) only B and F c) only C and H d) only D and G e) A, D, and F

f) B, D, and H g) A, C, and H h) B, D, E, and H i) A, D, F, and H j) B, C, D, and F

37. How many constitutional isomers of C4H10O contain alcohols (OH groups)? a) 1 b) 2 c) 3 d) 4 e) 5 f) 6

38. There are nine constitutional isomers with a formula C7H16. How many of these isomers have no secondary hydrogens? a) none b) one c) two d) three e) four f) five

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Chem 210

Training Set I

39. According to the IUPAC rules, what is the best name for the following compound?

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

3-ethyl-4,7-dimethylnonane 3,6-diethylisononane 3,6-diethylisodecane 3,6-diethyl-7-ethylnonane 1,1-diethyl-2,5-dimethylheptane 3,6-diethyl-7-(methylethyl)octane 3-ethyl-4,7-dimethylninenane

40. What is the correct IUPAC name for the following molecule?

a) 4-ethyl-2,5-dimethylnonane b) 5,7-dimethyl-6-ethylnonane c) 3-isobutyl-4-methyloctane d) 4-hexyl-2-methylhexane 41. Which of the following compounds contains at least one secondary alcohol?

a) I, II, IV, VI

b) I, III

c) I, II, III, V

d) I, III, V

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Chem 210

Training Set I

42-47. Fill in the missing words in the passage below with words from the provided list to best preserve the meaning of the paragraph. Some words may be used more than once. The (42) conformation of ethane is 12 kJ/mol more stable than the (43) conformation because of (44) strain. In general, any alkane is most stable when its bonds are (45) . In cycloalkanes three kinds of strain contribute to the overall energy: (1) torsional strain due to bond eclipsing, (2) (46) strain that is the result of repulsive van der Waals interactions, and (3) (47) strain attributable to angle distortions. a) torsional b) rotational c) conformational d) angle e) steric f) hysteric g) eclipsed h) staggered i) repulsive j) aligned

48. Which is the lowest energy conformation of butane?

49. What is the energy difference between the following conformational isomers?

a) 3.6 kcal/mol

b) 4.5 kcal/mol

c) 2.7 kcal/mol

d) 1.8 kcal/mol

50. Which equilibrium is not rapid at room temperature?

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Chem 210

Training Set I

51. What energy diagram would you expect for rotation about the central bond of 2methylbutane?
H 3C CH3 H H
6

H CH 3

conformation at dihedral angle of 0o energy scale in kcal/mol

a)

b)

0 -180

-120

-60

60

120

180

0 -180

-120

-60

60

120

180

c)

d)

0 -180

-120

-60

60

120

180

0 -180

-120

-60

60

120

180

52. Which of the following molecules have dipole moments? A: gauche conformation of 1,2-dibromoethane B: anti conformation of 1,2-dibromoethane C: trans-1,4-dibromocyclohexane D: cis-1,4-dibromocyclohexane E: tetrabromomethane F: dibromomethane a) A and B e) A, D, and F b) A and D f) A, C and E c) B and E g) B, C and E d) C and F h) B, D and E

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Chem 210

Training Set I

53. The carbon atoms of cyclopropane have been described as having sp3 hybridization, but with bent bonds. What is true about the valence-bond picture of cyclopropane? a) The hybrids making the C-C bonds have increased s character as compared to those of ethane. b) The hybrids making the C-C bonds have increased p character as compared to those of ethane. c) The bend C-C bonds have increased electron density above and below the plane of carbon ring (like bonds). d) The hybrids making the C-C bonds have more s character than the hybrids making the C-H bond in this compound. e) All the strain of cyclopropane is due to the angle strain. 54. Which of the two molecules can exist in a more stable form? a) trans-1,4-dimethylcyclohexane b) cis-1,4-dimethylcyclohexane 55. What is the energy difference between the two structures (the negative value means that the structure on the right is more stable)?

a) 1.15 kcal/mol

b) 1.15 kcal/mol

c) 2.3 kcal/mol

d) 2.3 kcal/mol

56. One of the two chair conformations of cis-1-chloro-3-methylcyclohexane is more stable than the other by 15.2 kJ/mol. What is the energy cost (in kJ/mol) of a 1,3diaxial interaction between a chlorine and a methyl group?. a) 2.5 b) 3.7 c) 5.8 d) 7.9 e) 10.4 f) 13.5

57. Which of the following chair cyclohexane structures has the lowest energy?

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Chem 210

Training Set I

58. Which is the most stable form of 1-ethyl-4-methylcyclohexane? Note: Me = -CH3, Et = -CH2CH3
a)
H Me H H H H H Et

b)
H Et

H H H

Me

c)
Me H

H H Et

d)
Et H

H Me H

e)
Et H

H H H

f)

H H

H Et H

Me

Me

59. What is the correct order of stabilities of the following isomeric structures, starting with one with the lowest energy?
A O O CH3 CH 3 H3 C B O O CH 3 C O O CH 3

CH3

a) A < B < C d) A < C < B

b) B < A < C e) B < C < A

c) C < A < B f) C < B < A

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Chem 210

Training Set I

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Chem 210

Training Set I

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

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Chem 210

Training Set I

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Chem 210

Training Set I

Answer key: Set I

1. D 2. C 3. A 4. G 5. B 6. B 7. D 8. B 9. H 10. D 11. C 12. F 13. C 14. B 15. A 16. C 17. C 18. D 19. F 20. A 21. E 22. A 23. A 24. B 25. A 26. C 27. G 28. C 29. B 30. C 31. C 32. D 33. A 34. A 35. A 36. H 37. D 38. B 39. A 40. A 41. D 42. H 43. G

44. A 45. H 46. E 47. D 48. C 49. C 50. B 51. A 52. E 53. B 54. A 55. D 56. E 57. D 58. C 59. E

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