Chapter 4: Acids and Bases

4.1: Arrhenius Acids and Bases

Arrhenius Definition:
An acid is a substance that dissolves in water to produce
A base is a substance that dissolves in water to produce

H
OH

ions.
-

ions.

A proton dissolved in aqueous solution will be represented by a hydronium ion

.

H aq H 2 O H 3 O aq

Hydration of the hydronium ion gives

H 3 O aq H 2 O l

H 5O 2

H 3O

(Monohydrated Form)

H 5 O 2 aq

(Dihydrated Form)

4.2: Bronsted-Lowry Acids and Bases

Bronsted-Lowry Acid: An acid is a proton donor.
Bronsted-Lowry Base: A base is a proton acceptor.
An acid-base reaction is a proton-transfer reaction.
Conjugate Acid-Base Pair: Any pair of molecules or ions that can be
interconverted by transfer of a proton.
Conjugate Base: The species formed when an acid transfers a proton to a base.
Conjugate Acid: The species formed when a base accepts a proton from an acid.

The members of a conjugate acid-base pair differ by a proton.

The Lewis structure is written for each reactant and product, showing all valence
electrons on reacting atoms. The use of a curved arrow can show the transfer of a
proton from an acid to a base. The tail is located at an electron pair (lone or
bonding) and the head of the arrow shows the new location of the electron pair.

The curved arrow indicates movement of electrons, not atoms.

Arrows should always point forward and not point backwards.

Bronsted-Lowry definitions do not require water as a reactant.

Example:

Lewis Structure

Guided Practice:
For each conjugate acid-base pair, identify the first species as an acid or base and
the second species as its conjugate base or conjugate acid. In addition, draw Lewis
structures for each species, showing all valence electrons and any formal charges.

(a)

(b)

(c)

CH 3 OH, CH 3 OH 2

H 2 CO 3 , HCO 3

CH 3 NH 2 , CH 3 NH 3

Independent Practice:
For each conjugate acid-base pair, identify the first species as an acid or base and
the second species as its conjugate acid or conjugate base. In addition, draw Lewis
structures for each species, showing all valence electrons and any formal charges.

(a)

(b)

(c)

H 2 SO 4 , HSO 4

NH 3 , NH 2

CH 3 OH, CH 3 O -

Guided Practice:
Write these reactions as proton-transfer reactions. Label which reactant is the acid
and which is the base, which product is the conjugate base of the original acid, and
which is the conjugate acid of the original base. In addition, write Lewis structures
for each reactant and product, and use curved arrows to show the flow of electrons
in each reaction.

(a)

H 2 O NH 4 H 3 O NH 3

Water is the base (proton acceptor), and ammonium ion is the acid (proton donor).

(b)

CH 3 CH 2 OH NH 2 CH 3 CH 2 O - NH 3

Ethanol is the acid (proton donor), and amide ion

acceptor).

Independent Practice:

NH 2

is the base (proton

Write these reactions as proton-transfer reactions. Label which reactant is the acid
and which is the base, which product is the conjugate base of the original acid, and
which is the conjugate acid of the original base. In addition, write Lewis structures
for each reactant and product, and use curved arrows to show the flow of electrons
in each reaction.

(a)

(b)

CH 3SH OH -

CH 2 O HCl

CH 3S - H 2 O

CH 2 OH Cl -

Bronsted-Lowry Bases With Two or More Receptor Sites

We will consider a carbonyl group that is bonded to either an oxygen or a nitrogen.
The more stable charged species is the one in which the charge is more delocalized.
Example:

Proton transfer to carbonyl oxygen yields cation A, and to hydroxyl oxygen gives
cation B.
Which is more stable? (Lower energy)
Two place the positive charge on oxygen, and one places it on carbon:

A-1 and A-3 make greater contributions to the hybrid, because all atoms have
complete octets.
A-2 makes the carbonyl carbon have an incomplete octet.
Protonation on hydroxyl oxygen gives cation B:

B-2 makes a minor contribution to hybrid because of adjacent positive charges.

Protonation of a carboxyl group is preferential on the carbonyl oxygen because this
cation has greater delocalization of the positive charge.
Guided Practice:
The functional group created when the

OH

of a carboxyl group is replaced by an

NH 2

group is called an amide. Draw the structural formula of acetamide, which is

derived from acetic acid, and determine if proton transfer to the amide group from

HCl

occurs preferentially on the amide oxygen or the amide nitrogen.

There are 2 possible protonated forms:

There are 3 contributing structures that can be drawn for cation A:

Structures A-1 and A-3 make the greater contributions to the hybrid because all
atoms in each have complete octets; A-3 makes a greater contribution than A-1
because it has the positive charge on the less electronegative atom.
There are 2 contributing structures that can be drawn for cation B:

B-2 makes little contribution to hybrid because it creates/separates unlike charges

and places positive charges on adjacent atoms. Cation B is localized on the amide
nitrogen.
We conclude that proton transfer to the carbonyl oxygen (Cation A) of the amide
group gives the more delocalized/stable cation.
Independent Practice:
Following is a structural formula for guanidine, the compound by which migratory
birds excrete excess metabolic nitrogen. The hydrochloride salt of this compound is
a white crystalline powder, freely soluble in water and ethanol.
(a) Write a Lewis structure for guanidine showing all valence electrons.
(b) Does proton transfer to guanidine occur preferentially to one of its
(cation A) or to its

NH

NH 2

groups

group (cation B)? Explain.

4.3 Acid Dissociation Constants,

Bases

pK a

, and the Relative Strengths of Acids &

The equilibrium expression for the dissociation of any uncharged acid:

1000 g/L
We can treat the concentration of water as a constant equal to

or

55.6 mol/L

K eq
. Combining the concentration of water and
constant

Ka

creates the acid dissociation

Because dissociation constants for most acids are numbers with negative exponent,
acid strengths are expressed as

The larger the value of

pK a

The smaller the value of

pK a

, the weaker the acid.

pK a

, the stronger the acid.

The weaker the acid, the stronger its conjugate base.

The stronger the acid, the weaker its conjugate base.