CHEM 203 HOMEWORK 1 Review of Introductory Chemistry

1. Experiments indicate that the molecule of PCl3 has a dipole moment, µ, equal to ca. 1 D, but AlCl3 has very
nearly µ = 0 D. Propose a molecular geometry for PCl3 and AlCl3.

The P–Cl and the Al–Cl bonds are both polarized, because Cl is more electronegative
than either P or Al. Furthermore, the bond dipole is directed toward the more
electronegative Cl atom.

For PCl3 to have a permanent dipole moment, individual bond dipoles (vectors!) must
add up to a nonzero value.

For AlCl3 to have no net dipole moment, individual bond dipoles (vectors!) must cancel
out.

Because of the vector nature of bond dipoles, a nonzero overall molecular dipole for
PCl3 implies a TRIGONAL PYRAMIDAL geometry:

By the same logic, a zero overall molecular dipole for AlCl3 implies a TRIGONAL
PLANAR geometry:

2. Each atom in the following molecules has a full complement of valence electrons:

H H Cl
H H
O O C N O H Al H
H H H
2 H
1 3 4
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For each molecule:

a. Calculate the formal charge on each non-hydrogen atom and determine the total charge on the molecule.
b. Specify hybridization states of non-hydrogen atoms and propose a reasonable geometry for the molecule
on the basis of VSEPR (Valence Shell Electron Pair Repulsion).
c. Indicate whether individual bonds are σ-type or π-type.
d. Predict whether the molecule will exhibit a permanent dipole moment.
e. On the basis of what you know at this time, indicate whether the molecule may be regarded as a Lewis
acid, a Lewis base, or neither.
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3. Certain poisonous mushrooms contain a toxin that exhibits a structural motif termed a "pyridine N-oxide."
This subunit is variously represented as either structure A or B below. In your opinion, which structure, A or
B, best depicts pyridine N-oxide? Why?
H H
H C H H C H
C C C C
C N C N
H C O H C O
A H H B
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Structure A.
In structure B, the nitrogen atom accommodates 10 valence electrons. Thus, it violates
the octet rule, which is ALWAYS respected by atoms of the second row of the periodic
table (Li, Be, B, C, N, O, F).

4. Draw a complete (electron dots, formal charges, ...) Lewis structure of:
a. a molecule that is a Lewis base;

Any molecule containing atoms that possess a lone pair; e.g.:

O N
; H H ; etc.
H H
H

b. a molecule that is a Lewis acid;

Any molecule that has a vacant orbital capable of accepting an electron pair from a
suitable donor; e.g.:

vacant p-type orbital

H Cl
H B ; Cl Al ; etc.
H Cl

c. a molecule that is neither a Lewis acid nor a Lewis base;

Any molecule that has neither a vacant orbital capable of accepting an electron pair,
not heteroatom(s) with lone pair(s); e.g.:

H H
H C H ; H Si H ; etc.
H H

d. a molecule is both a Lewis acid and a Lewis base;

Any molecule that has both a vacant orbital capable of accepting an electron pair, and
heteroatom(s) with lone pair(s); e.g.:

vacant p-type orbital

F
lone F B
pairs
F
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e. a molecule that is a strong Bronsted acid;

e.g., the common mineral acids:

O
H–O S O–H ; H Cl ; etc.
O

f. a molecule that is a weak Bronsted acid;

e.g., the common organic acids, such as acetic acid, or perhaps HF:

H O
H C C O–H ; H F ; etc.
H

g. a Lewis acid that is not a Bronsted acid;

Any Lewis acid that cannot possibly donate protons; e.g.:

F Cl
F B ; Cl Al ; etc.
F Cl

h. a Bronsted acid that is also a Lewis base;

Any Bronsted acid that incorporates heteroatoms with lone pairs, e.g.:

O H O
H–O S O–H ; H Cl ; H C C O–H ; H F ; etc.
O H

i. an anion that is also a Bronsted acid;

An anion that can still donate a proton; e.g.:

O O O O
H–O S O ; O C C O–H ; H–O P O ; etc.
O O

j. an anion that is not a Bronsted acid.

An anion that cannot possibly donate a proton; e.g.:

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O H O
O S O ; H C C O ; Cl ; etc.
O H

5. The table below lists the standard bond dissociation enthalpies (ΔHo, kcal/mol) for all possible diatomic
molecules formed by univalent atoms A, B, C, and D.
A-A + 50 A-C + 85 B-B + 65 B-D + 90 C-D + 95
A-B + 100 A-D + 70 B-C + 80 C-C + 45 D-D + 105
a. Which molecule possesses the strongest bond? The weakest bond?

Molecule D–D has the strongest bond; molecule C–C has the weakest bond

b. Estimate ΔHo for the reactions shown below and state whether each reaction is enthalpically favorable or
unfavorable:
a. A–A + B–B 2 A–B c. A–D + C–D A–C + D–D

b. A–B + D–D A–D + B–D d. A–B + C–C A–C + B–C

A–A + B–B 2 A–B A–B + D–D A–D + B–D

bonds broken bonds formed bonds broken bonds formed

A–A + 50 2 A–B A–B + 100 A–D – 70

B–B + 65 2 x (– 100) D–D + 105 B–D – 90

total + 105 – 200 kcal / mol total + 205 – 160 kcal / mol

ΔH = + 105 – 200 = – 95 kcal / mol ΔH = + 205 – 160 = + 45 kcal / mol

enthalpically favorable enthalpically unfavorable

A–D + C–D A–C + D–D A–B + C–C A–C + B–C

bonds broken bonds formed bonds broken bonds formed

A–D + 70 A–C – 85 A–B + 100 A–C – 85

C–D + 95 D–D – 105 C–C + 45 B–C – 80

total + 165 – 190 kcal / mol total + 145 – 165 kcal / mol

ΔH = + 165 – 190 = – 25 kcal / mol ΔH = + 145 – 165 = – 20 kcal / mol

enthalpically favorable enthalpically favorable

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6. Rotation about the CH2–CH2 bond of the molecule of 1-propylamine, CH3–CH2–CH2–NH2, produces four
limiting conformers. One of these is particularly stable. The remaining three limiting conformers may be
estimated to contain 0.7, 3.0, and 5.0 kcal/mol more energy than the most stable conformer.

a. Define two reference atoms in the molecule of 1-propylamine.

The logical choice is: the N atom and the C atom of the CH3 group

b. Clearly label the dihedral angle, θ, between them.

H3C θ
NH2
H C
H C
H H

c. Draw a Newman projection of each limiting conformer and assign their relative energy content.

θ = 120° θ = 60° θ = 180°

θ = 0° H3C H3C
H3C H H H
H3C NH2 NH2 H

H H H H H
H H NH2
H H H H NH2
H
second more third more least energetic
most energetic energetic energetic conformer
conformer conformer conformer (staggered, anti )
(eclipsed, syn ) (eclipsed) (staggered, gauche ) E = 0.0 kcal/mol
E = 5.0 kcal/mol E = 3.0 kcal/mol E = 0.7 kcal/mol

d. Construct a conformational energy diagram of the molecule for 0 ≤ θ ≤ 180°.

energy
kcal/mol

5.0

3.0

0.7

0.0
60° 120° 180° θ, deg
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10

7. Draw a clear structure of:

a. A chiral, acyclic organic molecule, A, which contains two stereogenic carbons

OH
H
e.g.,
H
HO A

b. An achiral, acyclic organic molecule, B, which contains two stereogenic carbons

OH OH
e.g., H H

c. The enantiomer, C, of molecule A above

H
HO

OH
H
C

d. A diastereomer, D, of molecule B above

OH OH
H H

e. Fischer projections of molecules A – D

CH3 CH3
CH3 CH3
H OH HO H
HO H H OH
H H H H
H OH HO H
H OH H OH
CH2CH3 CH2CH3
CH3 CH3
A B C D