CHEM 203 HOMEWORK 2 Molecular properties

1. Determine the formal charge on each non-H atom in the following organic molecules:

(0)
H C H H C H H C H H C N O
H H H (0)
 oxidation
states: – 4 –3 –2 +2 –1 –2

CH3 CH3 CH3 CH3

HN N CH3 H3C Pb CH3 H2C As CH3 H3C I
CH3 CH3 CH3
CH3
all C's: –2 all C's: –4 all CH3's: –4 all C's: –2
N(–): –2 Pb: +4 CH2(–): –4 I: –3
N(+): –2 As(+): +5 (other answers
for I may be
acceptable)

2. Calculate the oxidation state of each non-H atom in the above molecules and that of the starred C atoms
in the following ones:

+2 –2 –1 +2 +1 0
H CH3 H3C * H3C * CH3 0
H * H *
C O *
H C OH H * C OH C O C O *
H C OH C O
HO H H H3C H CH3 H

3. Whereas methane, CH4, is combustible, carbon tetrachloride, CCl4, is not. Formulate an argument based on
electronic principles to account for this fact.
The combustion of a compound entails the transfer of electrons from that compound to dioxygen, resulting in
changes in the oxidation states of reacting atoms. For methane:
H
H C H + 2 O=O O=C=O + 2 H2O note: the ox. st. of H
remains +1 throughout
H
oxidn. state oxidn. state oxidn. state oxidn. state
of C = –4 of O = 0 of C = +4 of O = –2
oxidn. state
of O = –2
The C-atom in methane has an oxidation state of –4: it has formally acquired 4 electrons, and thus it is neon-like in
electron configuration, highly electron rich, and readily inclined to donate electrons. Its reaction with O2, an electron
acceptor (it advances from the oxidation state of 0 to that of –2, thereby acquiring electrons), occurs readily.
By contrast, the C-atom in CCl4 has an oxidation state of +4: it has formally lost 4 electrons, and thus it is helium-like
in electron configuration, highly electron deficient, and quite disinclined to donate electrons, even to potent acceptors
such as O2.
CHEM 203 HOMEWORK 2 p. 2

Electrons could be transferred to O2 from the Cl atoms (oxidation state = –1). However, Cl is a highly electronegative
element that does not readily give up electrons. Furthermore, such a process would yield rather endothermic chlorine
oxides; e.g.:

Cl
Cl C Cl + 2 O=O O=C=O + 2 Cl2O
Cl
oxidn. state oxidn. state oxidn. state oxidn. state
of C = +4 of O = 0 of C = +4 of O = –2
oxidn. state oxidn. state oxidn. state
of Cl = –1 of O = –2 of Cl = +1

Reaction with O2, i.e., combustion, is no longer feasible.

4. Complete the following mechanistic diagrams by drawing all required curved arrows and formal charges:
H3C Cl H3C Cl
a. CH–Cl Al CH–Cl Al Cl
H3C Cl Cl H3C Cl

H3C CH3
S
b. CH3-CH2-S
S–CH3 CH3-CH2-S–S–CH3 + H3C S CH3

c. H3C H OH CH4 + OH

H H
d. H3C C O H3C C O
H H

5. Estimate Keq and ΔG° for the following acid-base equilibria:

relevant pKa values (approximate)
–
a. H3 P + HBr H4P + Br NH4 ≈9 H–Br ≈ –8

b. NH4 + CH3COO NH3 + CH3COOH PH4 ≈–9 CH3COOH ≈5

c. CH3–OH + CF3COOH CH3–OH2 + CF3COO CH3–OH2 ≈ –3 CF3COOH ≈ 0.5

[H+] [A–]
reminder: for a generic acid H–A H+ + A – pKa = – log Ka, and Ka =
[A–] Ka [HA]
[HA] [H+]
Therefore, = and =
[HA] [H+] [A–] Ka
So:
CHEM 203 HOMEWORK 2 p. 3

–
a. H3 P + HBr H4P + Br
[PH4+] [Br–] [PH4+] [Br–] [H+] 108
pKa ≈ – 8 pKa ≈ – 9 Keq = = • = • = 10–1
[PH3] [HBr] [PH3] [HBr] 109 [H+]

ΔG° ≈ – nRT • ln 10–1 ; for n = 1 mol:

ΔG° ≈ – 1.98 x 10–3 x 298 x 2.303 x (–1) ≈ – 1.4 x (– 1) = + 1.4 kcal/mol (unfavorable)

b. NH4 + CH3COO NH3 + CH3COOH

pKa ≈ 9 pKa ≈ 5

[CH3COOH] [NH3] [NH3] [CH3COOH] 10–9 [H+]

Keq = = • = • = 10–4
[NH4 +] [CH3 COO–] [NH4 +] [CH3 COO–] [H+] 10–5

ΔG° ≈ – nRT • ln 10–4 ; for n = 1 mol:

ΔG° ≈ – 1.98 x 10–3 x 298 x 2.303 x (–4) ≈ – 1.4 x (– 4) = + 5.6 kcal/mol (unfavorable)

c. CH3–OH + CF3COOH CH3–OH2 + CF3COO

pKa ≈ 0.5 pKa ≈ – 3

[CH3OH2+] [CF3COO–] [CH3OH2+] [CF3COO–] 10–0.5 [H+]

Keq = = • = • = 10–3.5
[CH3OH] [CH3COOH] [CH3OH] [CH3COOH] [H +] 103

ΔG° ≈ – nRT • ln 10–3.5 ; for n = 1 mol:

ΔG° ≈ – 1.98 x 10–3 x 298 x 2.303 x (–3.5) ≈ – 1.4 x (– 3.5) = + 4.9 kcal/mol (unfavorable)

6. Predict the major product of each of the following reactions and write an accurate mechanism for its
formation:

H CH3 H CH3 H H
a. C C H3C C C H3C C C CH3
H3C H H H H I
H–I –
I

H–F
b. CH2 CH–CH2–CH3 NO REACTION !!!
CHEM 203 HOMEWORK 2 p. 4

H2 H2 H2
H2C C H2C C H2C C CH3
c. C CH2 C CH3 C
H2C C H2C C H2C C Br
H2 H2 H2
H–Br –
Br

H3C CH3 H CH3 H H

d. C C H3C C C H3C C C CH3
H H H H H Br
H–Br –
Br

H2 H2 H2
C C C
e. H2C CH H2C CH2 H2C CH2
H2C CH H2C C H2C C H
C H–I C H C
H2 H2 H2 I
–
I

H O-CH2–CH3 H H
f. H2C=CH–O-CH2–CH3 H C C H C C O-CH2–CH3
H H H Cl
H–Cl
–
Cl

because

H O-CH2–CH3 H O-CH2–CH3
H C C H C C
H H H H

H3C H3C H3C H

O-CH2–CH3
g. C=CH–O-CH2–CH3 H C C H C C O-CH2–CH3
H3C H3C H
H3C Cl
H–Cl –
Cl

because

H3C O-CH2–CH3 H3C O-CH2–CH3

H C C H C C
H3C H H3C H