Chapter 2 - Polar Covalent Bonds, Resonance and Acids/Bases

Goals
• To understand dipole moments and polarity.
• To understand how to draw “good” Lewis dot structures.
• To be able to draw resonance structures, and the rules involved.
• To understand acids and bases.
• To understand intermolecular interactions.
• To get acquainted with molecular models. Both the plastic and digital version.

Why?
Dipole moments and polarity play a big role in organic reactions, so having a fundamental
understanding of these is critical for subsequent chapters. Intermolecular interactions will also
play a role in understanding reactivity and solvent effects. Of course without a good Lewis dot
structure the reactivity of any given substrate may be misunderstood, thus this is also very
important. Acids and bases are part of understanding reactivity, and reactivity can sometimes be
understood better from molecular models, which I always encourage using in this course.

Additional Resources
Practice Problems on Florida Online.

Prerequisites
• Understanding Lewis Dot and Kekule Structures.
• Understanding electronegativity trends of the periodic table.

Terms
Dipole moments, intermolecular and intramolecular interactions, formal charge, Lewis and
Bronstead Acids and Bases, resonance.

Polar Bonds and Dipole Moments

1. Use electronegativity trends to predict the direction of the dipole moments of the
following bonds.

a. C—Cl

b. N—Cl

c. N—O

d. N—B

e. C—S

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 f. B—Cl

g. N—S

h. C—B

2. Determine the polarity (and overall dipole moment) of the following molecules.

a. CF4

b. CHF3

c. NH3

d. NH4+

e. BF3

f. CH3CHO

g. COS

Formal Charges – Part I

3. Determine the formal charge in the following: H3O+

Step 1: Draw a Lewis dot structure.

Step 2: Determine the formal charge as discussed today and in a previous lecture.

Step 3: Make sure all formal charges add up to the overall charge in the molecular
formula.

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Formal Charges – Part II

4. Determine the formal charges and any overall charge in the following:

a. Nitrate

b. Nitrite

c. Sulfite

d. Sulfate

e. Methyl cation

f. Methyl anion

g. NH3BH3

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 Resonance − Part I

Rules for resonance:

1. All the resonance structures must be valid Lewis structures for the compound.
2. Only the placement of electrons may be shifted from one structure to another
(electrons from π bonds or lone pairs may be shifted) Shift these electrons using a
full arrow in the direction of movement)
3. The number of unpaired electrons (if any) must remain the same. Most stable
compounds have no unpaired electrons, and tall the electrons must remain
unpaired in all resonance structures.
4. The major resonance contributor is the one with the lowest energy. Good
contributors generally have all octets satisfied, as many bonds as possible, and as
little charge separation as possible. Negative charges are more stable on more
electronegative elements such as O, N, and S.
5. Resonance stabilization is most important when it serves to delocalize a charge
over two or m ore atoms.

5. Draw the Lewis dot structure for the carbonate ion and any resonance forms that may
exist. Show arrow notation for the direction in which the electrons move, or the “flow of
electrons”.

Do the same for the acetate ion.

Do the same for nitromethane, CH3NO2.

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Resonance − Part II

6. Draw resonance forms for the following:

O
O

H
N

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INTRODUCTION TO ACID/BASE CHEMISTRY

Brønsted-Lowry Definition of Acids and Bases:

Acid: a substance that can donate a proton. Base: a substance that can accept a proton

Lewis Definition of Acids and Bases:

Lewis Acid: electron pair acceptor. Lewis Base: electron pair donor

Lewis Acids Commonly Used in this Course:

AlCl3, BF3, TiCl4, FeCl3, Li+, Mg2+, compounds containing an acidic proton.

Lewis Bases:
Any functional group containing O, N, or S and a lone pair of electrons.

Organic Chemistry Terms for Lewis Acids and Bases

Electrophiles (“electron-loving” reagents ): seek electrons to obtain a stable valence shell of
electrons. Thus, they are typicall electron-deficient themselves.

Nucleophiles (“nucleus-loving” reagents): seek a proton or some other positively charged center.

1. Identify each as either a Bronsted acid or base and either a Lewis acid or base.

a. Explain how ammonia can act as both an acid and a base. Which of these roles does it
commonly fill in aqueous solutions?

b. Show how water can serve as an acid or base.

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 c. Show how methanol can act as an acid or base. Write an equation for the reaction of
methanol and sulfuric acid.

2. Show arrow notation to indicate bond breaking/making in each example listed in 1a-1c.
Which is the nucleophile and which the electrophile?

a.

b.

c.

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Strengths of Acids and Bases
Ka and pKa

Acetic acid is a relatively weak acid and a 0.1M solution is only able to protonate water to the
extent of about 1%.

The equilibrium equation for this reaction is:

or

In organic chemistry we typically look at pKa:

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 3. Rank the following substances in order of increasing acidity.
OH

O O O
O

OH

pKa = 19.3 pKa = 9 pKa = 4.76

pKa = 9.9

Predicting Acid Base Reactions

An acid will donate a proton to a conjugate base of any acid that has a higher pKa, and the
conjugate base of an acid will remove a proton from any acid that has a lower pKa.

Ammonia has a pKa of 36, and acetone a pKa of 19. Will the following reaction take place?

+ NaNH2

INTERMOLECULAR FORCES

The strength of intermolecular forces (forces between molecules) determines the physical
properties (i.e. melting point, boiling point and solubility) of a compound.

Stronger intermolecular forces result in high melting points and boiling points.

More energy must be expended to overcome very strong forces between molecules.

The type of intermolecular forces important for a molecule are determined by its structure.

Dispersion Forces (Or London Forces, Van der Waal forces)

Dispersion forces result when a temporary dipole in a molecule caused by a momentary

shifting of electrons induces an opposite and also temporary dipole in an adjacent molecule.

These temporary opposite dipoles cause a weak attraction between the two molecules.
Molecules which rely only on disperson forces generally have low melting points and boiling
points

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 1. Of the molecules or atoms listed, which have dispersion forces?

a. O2

b. CH2Cl2

c. Ar

d. CH4

e. N2O

f. SCl2

g. Cl2

h. NCl3

i. O3

j. H2S

2. For some chlorine molecules, show the dispersion forces.

Step 1: Draw the Lewis dot structure for one molecule

Step 2: Draw multiple molecules in the structural form.

Step 3: (On your picture above), for one molecule show a temporary induced dipole.

Step 4: (On your picture above), on the same molecule, show how this affects the
distribution of electron density. (include partial charges)

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 Step 5: (On your picture above), on the neighboring molecules, show how this affects
(induces a dipole) on these molecules.

Are chlorine molecules polar?

If not, why can they temporarily have a dipole?

Polar or Nonpolar

1. Identify the molecules as polar or nonpolar.

a. O2

b. CH2Cl2

c. CHCl3

d. CH4

e. N2O

f. N2

g. NCl3

Dipole Forces − Part I

Dipole-dipole forces are between molecules with permanent dipoles.

There is an interaction between δ+ and δ - areas in each molecule; these are much weaker
than ion-ion forces.

Molecules align to maximize attraction of δ + and δ - parts of molecules.

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 2. Of the molecules or atoms listed, which have dipole forces?

a. COS

b. O2

c. CH2Cl2

d. CHCl3

e. Ar

f. CH4

g. N2O

h. SCl2

i. Cl2

j. NCl3

k. O3

l. H2S

Dipole Forces − Part II

3. Consider the data below. Identify the difference between the two sets of substances.
Boiling Point, K Boiling Point, K
H2 2 HCl 188
N2 77 HBr 206
O2 90 HI 238
What trend do you identify with regards to relative boiling point and total number of
electrons?

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 If you were asked to predict the relative boiling point of hydrogen fluoride, what would
you predict?

The boiling point of HF is 19°C. Does this fit with the trend?

What does this tell us about the forces between the molecules of HF?

Hydrogen Bonding Intermolecular Forces

Hydrogen bonds are a special case of dipole-dipole forces, thus they are places in their own
category.

There is an interaction between hydrogens bonded to strongly electronegative atoms (O, N or F)

and nonbonding electron pairs on other strongly electronegative atoms (O, N or F).

4. What are the criteria for a molecular substance to have hydrogen bonding?

5. Of the molecules listed below, which have hydrogen bonding? (You may get assistance
with the structures of some of the molecules)

a. H2O

b. HCl

c. CH4

d. CH2O

e. NH3

f. NF3

g. HF

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 h. CH3OCH3

i. CH3COOH

j. CH3CH2OH

k. CH3COCH3

6. Show the hydrogen bonding intermolecular interactions between at least three molecules
of water.

Assigning Intermolecular Forces and Assigning Relative Boiling Points

7. Determine the intermolecular forces for the sets of molecules and then select the
molecule which would have the highest boiling point (relative to the other molecule).

a. CO and O2

Highest Boiling Point:____________

b. SO2 and CO2

Highest Boiling Point:____________

8. Under standard conditions, the diatomic elements, H2, O2, N2, F2, and Cl2 are gases, Br2 is
a liquid, and I2 is a solid. Is this consistent with what you just learned?

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 9. Look at the following table of organic compounds. Does the data follow what we have
learned?

Molecular Models

This will be shown in class on how to access “virtual” models.

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