Chemistry 140A Fall, 2004 NAME: Ima Key

First Midterm Exam-200 points 10/19/04

1. (10 points) Draw the Lewis dot structure for the nitro group (NO2-) Be sure to draw all valence electrons and indicate charges where appropriate. (Chapter 1; #28d)

(-)
O N O (10 pts)

(-) (+) (-)

O N O (8 pts)

2. (16 pts; 6 pts. each contributor) Draw two resonance structures for the following molecule. Label your resonance contributors "A" and "B". Indicate which of your resonance contributors is better and give one reason why it is better. N N C

(-) (-) (+)

B

(+)
A

(+)
N N C

(-) (+)
C N

(-)
C D

(+)

(-)

(2 points) Better resonance contributor: E>A>B>D>C (2 points) Reason: for E: charges properly located; minimize charge separation

3. (13 points) Draw all possible atomic energy orbital levels from 1s through and including 3d listing them from lowest energy to highest. Next, fill in the electrons for boron. Correct orbitals listed and correct # of each: 4 points Correct energy level positioning: 4 points Correct electron palcement for Boron: 5 points

3d 4s 3p 3s E 2p 2s 1s

Consider the following compounds in answering questions 4-7:

O

*
D C4H8

A C4H10

B C6H6O

C C4H8

*
O E C4H10 O F C4H10O OH G C6H6O

H C9H18 O

*
O

I C7H12O2 O

J C9H18 O

K C7H10O2 O

*
H L C4H8O M C4H8O N C7H12O2 O

4. (18 points) list all the pairs of constitutional isomers shown above (eg: N and M, etc.) 3 points each; minus 3 for any additional pairs listed or any wrong pairs listed

A and E B and G C and D

H and J I and N L and M

5. (10 points) Give the hybridization for the starred (*) carbon atom in: (2 points each) Molecule B: sp2 Molecule D: sp2 Molecule G: sp2 Molecule K: sp Molecule L: sp3 6. (4 points) For molecule K, give the total number of: (2 points each) Sigma bonds: 18 Pi bonds: 3 7. (20 points) Write the name of the functional groups present in: (4 points each) Molecule N: ESTER Molecule H: ALKENE Molecule M: ALDEHYDE Molecule K (2 functional groups): ALKYNE and ESTER

8. (10 points) Name the following molecules according to the IUPAC system of nomenclature: (minus 3 for incorrect alpha order of substituents; minus 3 for wrong numbering) H CH3 CH3 H3C C C C CH2CH2CH2CH2CH3 CH2 CH H3C (Chapter 2; # 28d) CH3

CH2 CH2 CH3 CH3

4-ethyl-3,4,5-trimethyl-5-(2-methylpropyl)decane or 5-isobutyl-4-ethyl-3,4,5-trimethyldecane

Consider the following two molecules, "A" and "B" shown as Newman projections:

tBu H H CH3 A H H H H

iPr H H tBu B

9. (5 points) When both molecules are in the staggered gauche conformation, which one has the higher energy?

10. (10 points) Draw the staggered gauche conformation for A in Newman projection format.

tBu H H H CH3 H or H3C H

tBu H H H

11. (10 points) Draw the bond line formula for B

12. (15 points) Provide the IUPAC name for A

2,2-dimethylpentane

13. (25 points) For the following reaction, draw a Reaction Coordinate-Potential Energy diagram in which step 1 is EXOTHERMIC and the overall conversion (from A+B to D) is ENDOTHERMIC. Be sure to draw dashed lines to clarify the energy levels of A+B; C and D. Also, label the energy levels that correspond to A+B, C and D by writing these letters at the appropriate place along the reaction coordinate.

A + B

step 1

step 2

E D A+B

RC 14. (5 points) Can the conversion of C to D as described in question #13 be exothermic assuming that step 1 is exothermic and the overall process is endothermic? (YES or NO)

NO
15. (5 points) Can the conversion of C to D as described in question #13 be endothermic assuming that step one is exothermic and the overall process is exothermic? (YES or NO)

YES
16. (4 points) For the first step described in #13 above, is the entropy positive or negative in value?

NEGATIVE

17. (10 points) Draw the major product of the free-radical chlorination of twistane, shown below. (Do not try to draw twistane, just add a chlorine to the appropriate position on the structure provided. (Chapter 3; #25c) MAJOR PRODUCT OF FREE RADICAL CHLORONATION of TWISTANE:

Cl

18. (10 points) Draw the product of the chlorination of twistane that would be EXPECTED to be the major product based on statistical analysis. (Do not try to draw twistane, just add a chlorine to the appropriate position on the structure provided.) EXPECTED MAJOR CHLORINATION PRODUCT OF TWISTANE BASED ON STATISTICS: most numerous proton is "Ha" Ha Hc Hb Hb Hc Ha Ha Ha Hc Ha Ha Ha Ha Hc Hb Hb

Four 3o Hc Four 2o Hb Eight 2o Ha Cl