Organic Chemistry,

9th Edition
L. G. Wade, Jr.

Chapter 2
Lecture
Acids and Bases;
Functional Groups

Chad Snyder, PhD

Grace College
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 Bond Dipole Moments

• Dipole moments are due to differences in electronegativity.

• They depend on the amount of charge and distance of
separation.
• They are measured in debyes (D).

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 Molecular Dipole Moment

• The molecular dipole moment is the vector sum of the bond

dipole moments.
• It depends on bond polarity and bond angles.
• Lone pairs of electrons contribute to the dipole moment.

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 Lone Pairs and Dipole
Moments

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 Intermolecular Forces

• Strength of attractions between molecules

influences the melting point (m. p.), boiling
point (b. p.), and solubility of compounds.
• Classification of attractive forces:
– Dipole–dipole forces
– London dispersions forces
– Hydrogen bonding in molecules with —OH
or —NH groups

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 Dipole–Dipole Forces
• Dipole–dipole interactions result from the approach
of two polar molecules.
• If their positive and negative ends approach, the
interaction is an attractive one.
• If two negative ends or two positive ends approach,
the interaction is repulsive.
• In a liquid or a solid, the molecules are mostly
oriented with the positive and negative ends
together, and the net force is attractive.

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 Dipole–Dipole Interaction

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 London Dispersion Forces
• One of the Van der Waal forces
• A temporary dipole moment in a molecule can
induce a temporary dipole moment in a nearby
molecule.
• An attractive dipole–dipole interaction results for a
fraction of a second.
• Main force in nonpolar molecules
• Larger atoms are more polarizable.

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 Dispersions

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 Effect of Branching on
Boiling Point

• The long-chain isomer (n-pentane) has the greatest

surface area and the highest boiling point.
• As the amount of chain branching increases, the
molecule becomes more spherical and its surface area
decreases.
• The most highly branched isomer (neopentane) has
the smallest surface area and the lowest boiling point.
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 Hydrogen Bonding
• Strong dipole–dipole attraction
• Organic molecules must have N—H or O—H to be
able to form a hydrogen bond.
• The hydrogen from one molecule is strongly
attracted to a lone pair of electrons on the oxygen
of another molecule.
• O—H is more polar than N—H, so alcohols have
stronger hydrogen bonding.

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 Hydrogen Bonds

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 Boiling Points and
Intermolecular Forces
CH 3 CH 2 OH CH 3 O CH3

ethanol, b. p. = 78 °C dimethyl ether, b. p. = –25 °C

Hydrogen bonding increases the b. p. of the molecule.

CH 3 CH 2 OH CH 3 CH 2 NH 2

ethanol, b. p. = 78 °C ethyl amine, b. p. 17 °C

O—H is more polar than N—H, so alcohols have stronger
hydrogen bonding and, therefore, higher boiling points.
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 Polarity Effects on Solubility

• Like dissolves like.

• Polar solutes dissolve in polar solvents.
• Nonpolar solutes dissolve in nonpolar
solvents.
• Molecules with similar intermolecular forces
will mix freely.

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 Polar Solute in Polar Solvent

A polar solute dissolves in a polar solvent.

Hydration releases energy; entropy increases.
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 Polar Solute in Nonpolar
Solvent

The solvent cannot break apart the intermolecular interaction

of the solute, so the polar solid will not dissolve in the
nonpolar solvent.
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 Nonpolar Solute in
Nonpolar Solvent

The weak intermolecular attractions of a nonpolar

substance are overcome by the weak attractions for a
nonpolar solvent. The nonpolar substance dissolves.

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 Nonpolar Solute with Polar
Solvent

If a nonpolar molecule were to dissolve in water, it would

break up the hydrogen bonds between the water molecules.
Therefore, nonpolar substances do not dissolve in water.
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 Classes of Compounds

• Classifications are based on

functional group.
• Three broad classes:
– Hydrocarbons: Compounds composed of only
carbon and hydrogen
– Compounds containing oxygen
– Compounds containing nitrogen

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 Hydrophobic and Hydrophilic

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 Arrhenius Acids
• Arrhenius acids are substances that
dissociate in water to give H3O+ ions.

• Stronger acids dissociate to a greater

degree than weaker acids.
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 Arrhenius Bases
• Arrhenius bases are substances that
dissociate in water to give hydroxide ions.

• Stronger bases (NaOH) dissociate more

than weaker bases (Mg(OH)2).

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 Brønsted–Lowry Acids
and Bases
Brønsted–Lowry acids are any species that donate a proton.
Brønsted–Lowry bases are any species that can accept a proton.

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 Conjugate Acids and Bases

• Conjugate acid: When a base accepts a proton, it

becomes an acid capable of returning that proton.
• Conjugate base: When an acid donates its proton,
it becomes capable of accepting that proton back.
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 Acid Strength

• an acid’s strength is expressed in its extent of

ionization in water

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 Base Strength

• The strength of an acid is inversely related to the

strength of its conjugate base.

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 Equilibrium Positions
of Acid–Base Reactions

1. The acid–base equilibrium favors formation of the

weaker acid and the weaker base.
2. The weaker acid has the larger pKa. The weaker base
has the larger pKb.
3. The weaker acid and the weaker base are always on the
same side of the equation. Both of them are reactants, or
both of them are products.
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 Equilibrium Positions of
Acid–Base Reactions

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 Solvent Effects on Acidity
and Basicity

• Water is amphoteric; it can react with an acid

or a base.
• Its conjugate acid is the hydronium ion, and
its conjugate base is the hydroxide ion.
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 Effect of Electronegativity
on pKa

• A more electronegative element bears a negative

charge more easily, giving a more stable conjugate
base and a stronger acid.
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 Effect of Size on pKa

• The negative charge of an anion is more stable if it is

spread over a larger region of space.
• Within a column of the periodic table, acidity increases
down the column.
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 Inductive Effects on Acidity

• Electron-withdrawing atoms and groups can stabilize

a conjugate base through the sigma bonds of the
molecule.
• The magnitude of this inductive effect depends on the
number of bonds between the electronegative
element and the site of the negative charge.
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 Inductive Effects on Acidity

• Stronger electron-withdrawing groups stabilize the

anion of the conjugate base more than weaker
groups do.
• Multiple electron-withdrawing groups stabilize the
conjugate base and increase the acidity more than a
single group does.
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 Hybridization Effects on Acidity

• The different hybridization states strongly

influence acidity.
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 Hybridization Effects on Acidity

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 Effect of Resonance on pKa

• If the negative charge on an atom can be delocalized over two or

more atoms, the acidity of that compound will be greater than when
the negative charge cannot be delocalized.
• The ethoxide anion is less acidic than the acetate ion simply
because the acetate ion can delocalize the negative charge.
• Methanesulfonic acid can delocalize the charge in three different
resonance forms, making it more acidic than the acetate ion.
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 Lewis Acids and Lewis Bases
• Lewis bases (called nucleophiles) are
species with available electrons than can be
donated to form a new bond.
• Lewis acids are species that can accept
these electrons to form new bonds.
• Since a Lewis acid accepts a pair of
electrons, it is called an electrophile.

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 Nucleophiles and Electrophiles
• Nucleophile: Donates electrons to a nucleus
with an empty orbital
• Electrophile: Accepts a pair of electrons
• When forming a bond, the nucleophile
attacks the electrophile, so the arrow goes
from negative to positive.
• When breaking a bond, the more
electronegative atom receives the electrons.

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 Hydrocarbons
• Alkanes: Single bonds between the carbons; all
carbons are sp3.
• Cycloalkanes: sp3 carbons form a ring.
• Alkenes: Double bonds are present in the
molecule; sp2 carbons.
• Cycloalkenes: Double bond in a ring
• Alkynes: Triple bonds are present; sp carbons.
• Aromatic: Contain a benzene ring

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 Alkane Naming

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 Cycloalkanes

• Cycloalkanes are a special class of alkanes

in the form of a ring.
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 Alkenes

• Alkenes are hydrocarbons that contain carbon–carbon

double bonds.
• Alkene names end in the –ene suffix.
• If the double bond might be in more than one position, then
the chain is numbered and the lower number of the two
double-bonded carbons is added to the name to indicate the
position of the double bond.
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 Alkenes

• Alkynes are hydrocarbons that contains

carbon–carbon triple bonds.
• Alkyne names end in the –yne suffix.

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 Aromatic Hydrocarbons

• Aromatic hydrocarbons (also called arenes)

are all derivatives of benzene.
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 Compounds Containing Oxygen

• Alcohols: Contain the hydroxyl group as the

main functional group
• Ethers: Contain two alkyl groups bonded to
an oxygen
• Aldehydes and ketones: Contain the
carbonyl group, C═O
• Carboxylic acids: Contain the carboxyl
group, —COOH

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 Alcohols

• Alcohols are organic compounds that

contain the hydroxyl group (—OH).

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 Ethers

• Ethers are composed of two alkyl groups

bonded to an oxygen atom.

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 Aldehydes and Ketones

• The carbonyl group, C═O, is the functional group for

both aldehydes and ketones.
• A ketone has two alkyl groups bonded to the carbonyl
group; an aldehyde has one alkyl group and a
hydrogen atom bonded to the carbonyl group.
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 Carboxylic Acids

• Carboxylic acids contain the carboxyl

group, —COOH, as their functional group.
• The carboxyl group is a combination of a
carbonyl group and a hydroxyl group.
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 Carboxylic Acid Derivatives

• Carboxylic acids are easily converted to a variety of acid

derivatives.
• Each derivative contains the carbonyl group bonded to an
oxygen or another electron-withdrawing element.
• These derivatives include acid chlorides, esters, and
amides.
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 Compounds Containing
Nitrogen

• Amines: Alkylated derivatives of ammonia

• Amides: Carboxylic acid derivative with a
nitrogen attached to the carbonyl group
• Nitriles: Contain the cyano group

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 Amines

• Amines are alkylated derivatives of

ammonia.

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 Amides

• Amides are derivatives that result from a

combination of an acid with ammonia or
an amine.
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 Nitriles

• A nitrile is a compound containing the

cyano group.

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