Acids and Bases

Chapter 15
 Some Properties of Acids
 Produce H+ (as H3O+) ions in water (the hydronium ion is a
hydrogen ion attached to a water molecule)
 Taste sour
 Corrode metals
 Electrolytes
 React with bases to form a salt and water
 pH is less than 7
 Turns blue litmus paper to red “Blue to Red A-CID”
 Some Properties of Bases
 Produce OH- ions in water

 Taste bitter, chalky

 Are electrolytes

 Feel soapy, slippery

 React with acids to form salts and water

 pH greater than 7

 Turns red litmus paper to blue “Basic Blue”

 Acid Nomenclature Review
Anion
Ending Acid Name
No Oxygen -ide hydro-(stem)-ic acid

-ate (stem)-ic acid

w/Oxygen
-ite (stem)-ous acid
An easy way to remember which goes with which…
“In the cafeteria, you ATE something ICky”
 Acid/Base definitions
Definition 1: Arrhenius

Arrhenius acid is a substance that produces H+ (H3O+) in water

Arrhenius base is a substance that produces OH- in water

4.3
 Acid/Base Definitions
• Definition #2: Brønsted – Lowry

Acids – proton donor

Bases – proton acceptor

A “proton” is really just a hydrogen

atom that has lost it’s electron!
 A Brønsted-Lowry acid is a proton donor
A Brønsted-Lowry base is a proton acceptor

conjugate conjugate
base acid
acid base
 ACID-BASE
ACID-BASE THEORIES
THEORIES
The Brønsted definition means NH3 is a BASE in
water — and water is itself an ACID
++ --
NH
NH33 ++ HH22O
O NH +
NH44 + OHOH
Base
Base Acid
Acid Acid
Acid Base
Base
Conjugate Pairs
 Learning Check!

Label the acid, base, conjugate acid, and

conjugate base in each reaction:
HCl
HCl ++ OH     Cl
OH--  Cl-- ++ H
H22O
O
Acid
Acid Base
Base Conj.
Conj. Conj.
Conj.
Base
Base Acid
Acid

H O + H SO    HSO --
+ H O
H22 O + H22 SO44    HSO44 + H33 O ++

Conj.
Conj. Conj.
Conj.
Base
Base Acid
Acid Base Acid
Base Acid
 Acids & Base Definitions
Definition #3 – Lewis

Lewis acid - a substance that

accepts an electron pair

Lewis base - a substance

that donates an electron
pair
 Lewis Acids & Bases
Formation of hydronium ion is also an
excellent example.
••
•• O—H ••
+ H O—H
H
H
H
ACID BASE

•Electron pair of the new O-H bond

originates on the Lewis base.
Lewis Acid/Base Reaction
The pH scale is a way of
expressing the strength of
acids and bases. Instead of
using very small numbers,
we just use the NEGATIVE
power of 10 on the Molarity
of the H+ (or OH-) ion.

Under 7 = acid
7 = neutral
Over 7 = base
 Calculating the pH
pH = - log [H+]
(Remember that the [ ] mean Molarity)

Example: If [H+] = 1 X 10-10

pH = - log 1 X 10-10
pH = - (- 10)
pH = 10
Example: If [H+] = 1.8 X 10-5
pH = - log 1.8 X 10-5
pH = - (- 4.74)
pH = 4.74
 Try These!
pH = - log [H+]
Find the pH of these:
pH = - log 0.15
1) A 0.15 M solution of
pH = - (- 0.82)
Hydrochloric acid
pH = 0.82

pH = - log 3 X 10-7
2) A 3.00 X 10-7 M pH = - (- 6.52)
solution of Nitric pH = 6.52
acid
 pH
pH calculations
calculations –– Solving
Solving for
for H+
H+
If the pH of Coke is 3.12, [H+] = ???
Because pH = - log [H+] then
- pH = log [H+]
Take antilog (10x) of both
sides and get
10-pH = [H+]
[H+] = 10-3.12 = 7.6 x 10-4 M
*** to find antilog on your calculator, look for “Shift”
or “2nd function” and then the log button
 More About Water
H2O can function as both an ACID and a BASE.
In pure water there can be AUTOIONIZATION

Equilibrium constant for water = Kw

Kw = [H3O+] [OH-] = 1.00 x 10-14 at 25 oC
 More About Water
Autoionization OH
OH
--

++
H O
H33O

Kw = [H3O+] [OH-] = 1.00 x 10-14 at 25 oC

In a neutral solution [H3O+] = [OH-]
and so [H3O+] = [OH-] = 1.00 x 10-7 M
 pOH
• Since acids and bases are
opposites, pH and pOH are
opposites!
• pOH does not really exist, but it is
useful for changing bases to pH.
• pOH looks at the perspective of a
base
pOH = - log [OH-]
Since pH and pOH are on opposite
ends,
pH + pOH = 14
pH [H++] [OH--] pOH
 [H3O ], [OH ] and pH
+ -

What is the pH of the 0.0010 M NaOH solution?

[OH-] = 0.0010 (or 1.0 X 10-3 M)
pOH = - log 0.0010
pOH = 3
pH = 14 – 3 = 11

OR Kw = [H3O+] [OH-]
[H3O+] = 1.0 x 10-11 M
pH = - log (1.0 x 10-11) = 11.00
 What is the pH of a 2 x 10-3 M HNO3 solution?
HNO3 is a strong acid – 100% dissociation.
Start 0.002 M 0.0 M 0.0 M
HNO3 (aq) + H2O (l) H3O+ (aq) + NO3- (aq)
End 0.0 M 0.002 M 0.002 M

pH = -log [H+] = -log [H3O+] = -log(0.002) = 2.7

What is the pH of a 1.8 x 10-2 M Ba(OH)2 solution?

Ba(OH)2 is a strong base – 100% dissociation.
Start 0.018 M 0.0 M 0.0 M
Ba(OH)2 (s) Ba2+ (aq) + 2OH- (aq)
End 0.0 M 0.018 M 0.036 M
pH = 14.00 – pOH = 14.00 + log(0.036) = 12.56
15.4
 Strong and Weak Acids/Bases
The strength of an acid (or base) is
determined by the amount of
IONIZATION.

HNO3, HCl, HBr, HI, H2SO4 and HClO4 are

the strong acids.
Strong and Weak Acids/Bases
• Generally divide acids and bases into STRONG or
WEAK ones.
STRONG ACID: HNO3 (aq) + H2O (l) 
H3O+ (aq) + NO3- (aq)
HNO3 is about 100% dissociated in water.
 Strong and Weak Acids/Bases
• Weak acids are much less than 100% ionized in
water.
*One of the best known is acetic acid = CH3CO2H
 Strong and Weak Acids/Bases

• Strong Base: 100% dissociated in water.

NaOH (aq)  Na+ (aq) + OH- (aq)
Other common strong
bases include KOH and
Ca(OH)2.
CaO (lime) + H2O -->
Ca(OH)2 (slaked lime)
Strong bases are the group I hydroxides
CaO Calcium, strontium, and barium hydroxides are
strong, but only soluble in water to 0.01 M
 Strong
Strong and
and Weak
Weak Acids/Bases
Acids/Bases
• Weak base: less than 100% ionized in water

One of the best known weak bases is ammonia

NH3 (aq) + H2O (l) ↔ NH4+ (aq) + OH- (aq)
Weak Bases
 Equilibria Involving
Weak Acids and Bases
Consider acetic acid, HC2H3O2 (HOAc)
HC2H3O2 + H2O ↔ H3O+ + C2H3O2 -
Acid Conj. base
++ --
[H
[H3 O
O ][OAc
][OAc ]] -5
Kaa 
K 3  1.8 10 -5
1.8 xx 10
[HOAc]
[HOAc]

(K is designated Ka for ACID)

K gives the ratio of ions (split up) to molecules (don’t split up)
 Ionization Constants for Acids/Bases

Acids Conjugate
Bases
Increase
strength

Increase
strength
 Equilibrium
Equilibrium Constants
Constants
for
for Weak
Weak Acids
Acids

Weak acid has Ka < 1

Leads to small [H3O+] and a pH of 2 - 7
Equilibria
Equilibria Involving
Involving A
A Weak
Weak Acid
Acid
You have 1.00 M HOAc. Calc. the
equilibrium concs. of HOAc, H3O+, OAc-,
and the pH.
Step 1. Define equilibrium concs. in ICE
table.
[HOAc] [H3O+] [OAc-]
initial 1.00
1.00 00 00

change -x
-x +x
+x +x
+x
1.00-x
1.00-x xx xx
equilib
 Equilibria
Equilibria Involving
Involving A
A Weak
Weak Acid
Acid
You have 1.00 M HOAc. Calc. the equilibrium concs.
of HOAc, H3O+, OAc-, and the pH.

Step 2. Write Ka expression

++ -- 22
-5
-5 [H O ][OAc
[H33O ][OAc ] ] x
x
KKa 1.8 x 10 =  1.00 - x
a 1.8 x 10 = [HOAc]
[HOAc] 1.00 - x

This is a quadratic. Solve using quadratic

formula.

or
or you
you can
can make
make an
an approximation
approximation if if xx is
is very
very
small!
small! (Rule
(Rule of
of thumb:
thumb: 10
10-5-5 or
or smaller
smaller isis ok)
ok)
Equilibria
Equilibria Involving
Involving A
A Weak
Weak Acid
Acid
You have 1.00 M HOAc. Calc. the equilibrium concs.
of HOAc, H3O+, OAc-, and the pH.

Step 3. Solve Ka expression

[H O ++][OAc--] x 22
KKa 1.8 x 10 -5
-5 == [H33O ][OAc ] x
a 1.8 x 10 [HOAc] 1.00
[HOAc] 1.00 -- xx
First assume x is very small because
Ka is so small.
22
-5 x
-5 = x
KKa 1.8 x 10
a 1.8 x 10 =1.00
1.00
Now we can more easily solve this
approximate expression.
 Equilibria
Equilibria Involving
Involving A
A Weak
Weak Acid
Acid
You have 1.00 M HOAc. Calc. the equilibrium concs.
of HOAc, H3O+, OAc-, and the pH.

Step 3. Solve Ka approximate expression

x 22
-5
-5 = x
KKa 1.8 x 10
a 1.8 x 10 =1.00
1.00

x = [H3O+] = [OAc-] = 4.2 x 10-3 M

pH = - log [H3O+] = -log (4.2 x 10-3) = 2.37
Equilibria
Equilibria Involving
Involving A
A Weak
Weak Acid
Acid
Calculate the pH of a 0.0010 M solution of formic
acid, HCO2H.
HCO2H + H2O ↔ HCO2- + H3O+
Ka = 1.8 x 10-4
Approximate solution
[H3O+] = 4.2 x 10-4 M, pH = 3.37
Exact Solution
[H3O+] = [HCO2-] = 3.4 x 10-4 M
[HCO2H] = 0.0010 - 3.4 x 10-4 = 0.0007 M
pH = 3.47
 Equilibrium
Equilibrium Constants
Constants
for
for Weak
Weak Bases
Bases

Weak base has Kb < 1

Leads to small [OH-] and a pH of 12 - 7
Relation
of Ka,
Kb,
[H3O+]
and pH
Equilibria Involving A Weak Base
You have 0.010 M NH3. Calc. the pH.
NH3 + H2O ↔ NH4+ + OH-
Kb = 1.8 x 10-5
Step 1. Define equilibrium concs. in ICE table
[NH3] [NH4+] [OH-]

initial 0.010
0.010 00 00
-x
-x +x
+x +x
+x
change
0.010
0.010 -- xx xx xx
equilib
Equilibria Involving A Weak Base
You have 0.010 M NH3. Calc. the pH.
NH3 + H2O  NH4+ + OH-
Kb = 1.8 x 10-5
Step 2. Solve the equilibrium expression
[NH ++][OH--] x 22
-5
-5 [NH44 ][OH ] = x
KKb  1.8 x 10
1.8 x 10 =
= = 0.010 - x
b [NH ]
[NH33 ] 0.010 - x

Assume x is small, so
x = [OH-] = [NH4+] = 4.2 x 10-4 M
and [NH3] = 0.010 - 4.2 x 10-4 ≈ 0.010 M
The approximation is valid !
 Equilibria Involving A Weak Base
You have 0.010 M NH3. Calc. the pH.
NH3 + H2O  NH4+ + OH-
Kb = 1.8 x 10-5
Step 3. Calculate pH
[OH-] = 4.2 x 10-4 M
so pOH = - log [OH-] = 3.37
Because pH + pOH = 14,
pH = 10.63
Types of Acid/Base Reactions:
Summary
Weak Bases are weak electrolytes

F- (aq) + H2O (l) OH- (aq) + HF (aq)

NO2- (aq) + H2O (l) OH- (aq) + HNO2 (aq)

Conjugate acid-base pairs:

• The conjugate base of a strong acid has no measurable
strength.
• H3O+ is the strongest acid that can exist in aqueous
solution.
• The OH- ion is the strongest base that can exist in aqueous
solution.

15.4
15.4
Strong Acid Weak Acid

15.4
 Ionized acid concentration at equilibrium
percent ionization = x 100%
Initial concentration of acid

For a monoprotic acid HA

[H+]
Percent ionization = x 100% [HA]0 = initial concentration
[HA]0

15.5
Ionization Constants of Conjugate Acid-Base Pairs

HA (aq) H+ (aq) + A- (aq) Ka

A- (aq) + H2O (l) OH- (aq) + HA (aq) Kb

H2O (l) H+ (aq) + OH- (aq) Kw

KaKb = Kw

Weak Acid and Its Conjugate Base

Kw Kw
Ka = Kb =
Kb Ka

15.7
 Molecular Structure and Acid Strength
H X H+ + X-
• Bond strength

The stronger The weaker • Polarity

the bond the acid

HF << HCl < HBr < HI

15.9
 Molecular Structure and Acid Strength
- +
Z O H Z O - + H+

The O-H bond will be more polar and easier to break if:
• Z is very electronegative or
• Z is in a high oxidation state

15.9
 Molecular Structure and Acid Strength

1. Oxoacids having different central atoms (Z) that are from

the same group and that have the same oxidation number.

Acid strength increases with increasing electronegativity of Z

•• ••
O O
••
••

••
••
•• •• •• ••
H O Cl O H O Br O
••

••
•• •• •• •• •• ••

Cl is more electronegative than Br

HClO3 > HBrO3

15.9
 Molecular Structure and Acid Strength

2. Oxoacids having the same central atom (Z) but different

numbers of attached groups.

Acid strength increases as the oxidation number of Z increases.

HClO4 > HClO3 > HClO2 > HClO

15.9
 Acid-Base Properties of Salts
Neutral Solutions:
Salts containing an alkali metal or alkaline earth metal
ion (except Be2+) and the conjugate base of a strong
acid (e.g. Cl-, Br-, and NO3-).
H 2O
NaCl (s) Na+ (aq) + Cl- (aq)

Basic Solutions:
Salts derived from a strong base and a weak acid.
H 2O
NaCH3COO (s) Na+ (aq) + CH3COO- (aq)

CH3COO- (aq) + H2O (l) CH3COOH (aq) + OH- (aq)

15.10
 Acid-Base Properties of Salts
Acid Solutions:
Salts derived from a strong acid and a weak base.

H 2O
NH4Cl (s) NH4+ (aq) + Cl- (aq)

NH4+ (aq) NH3 (aq) + H+ (aq)

Salts with small, highly charged metal cations (e.g. Al3+,

Cr3+, and Be2+) and the conjugate base of a strong acid.

Al(H2O)3+
6 (aq) Al(OH)(H2O)2+
5 (aq) + H (aq)
+

15.10
 Acid-Base Properties of Salts
Solutions in which both the cation and the anion hydrolyze:

• Kb for the anion > Ka for the cation, solution will be basic

• Kb for the anion < Ka for the cation, solution will be acidic

• Kb for the anion  Ka for the cation, solution will be neutral

15.10