Acid-Base Chemistry
There are a couple of ways to
define acids and bases
Brønsted-Lowry acids and bases
Acid:H+ ion donor
Base: H+ ion acceptor
Lewis acids and bases
Acid: electron pair acceptor
Base: electron pair donor
Brønsted-Lowry Acids & Bases
Brønsted-Lowry Acids & Bases
Brønsted-Lowry Acids & Bases
In most acid-base systems, water may play a
role as either an acid (H+ donor) or a base (H+
acceptor)
Water as an acid
H2O(l) + B(aq) OH-(aq) + HB+(aq)
Water as a base
H2O(l) + HA(aq) H3O+(aq) + A-(aq)
Conjugate Acids & Bases
Acids react with bases and vice versa
All acids and bases come with a
conjugate pair—a base or acid,
respectively, that is formed in
conjunction with the original species
Examples
HCl(aq) + H2O(l) H3O+(aq) + Cl-(aq)
acid base conjugat conjugate
e acid base
Conjugate Acids & Bases
Examples
NaOH(aq) + H2O(l) OH-(aq) + H2O(l) + Na+(aq)
base acid conjugate conjugate
base acid
CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq)
acid base conjugate conjugate
base acid
Strengths of Acids and Bases
Strong acids donate H+ ions more easily
The stronger the acid, the weaker the
conjugate base associated with that acid
Strong bases accept H+ ions more easily
The stronger the base, the weaker the
conjugate acid associated with that base
Strengths of Acids and Bases
Stronger acids will always react to form weaker
conjugate bases
Stronger bases will always react to form weaker
conjugate acids
Example
H2SO4(aq) + NaOH(aq) + H2O(l) ???
sulfuric acid can react with either OH- or
H2O—which would it prefer? -
H2SO4(aq) + OH (aq) HSO4 (aq) + H2O(l)
- preferred
reaction
H2SO4(aq) + H2O(l) HSO4-(aq) + H3O+(aq)
Autoionization of Water
Water always undergoes some degree
of dissociation to form H3O+ ions and
OH- ions
2 H2O(l) H3O+(aq) + OH-(aq)
The equilibrium constant for this
process at 25 oC is:
Kw = [H3O+][OH-] = 1.0 x 10-14
In pure water
[H3O+] = [OH-] = 1.0 x 10-7 M
Autoionization of Water
Kw is temperature dependent—it
increases with increasing
temperature
Autoionization of Water
Example
Determine [H3O+] in a 0.053 M NaOH solution Step 1:
since NaOH is a strong base,
dissociation is complete
[OH-] = 0.053 M
Step 2: Use Kw to calculate [H3O+]
Kw [H
3
O
][OH -
] 1.0 x 10 -14
K
[H3 O ] -
w 1.0 x 10
-14
[OH ] 0.053
1.9 x 10-13 M
The pH Scale
pH is a measure of the hydronium ion
content of a solution
pH is defined as:
pH = -log[H3O+]
log is log base 10, not ln (natural log)
[H3O+] is given in molar units (M)
pH of pure water ([H3O+] = 1.0 x 10-7
M): pH = -log(1.0x10-7) = 7.0
pH of last example ([H3O+] = 1.9 x 10-13
M): pH = -log(1.9x10-13) = 12.7
The pH Scale
Neutral is defined as the pH of
pure water: pH = 7
Acidic solutions have pH
lower than 7: pH < 7 acidic
Basic solutions have pH
larger than 7: pH > 7 basic
The pH Scale
We can also use pOH to describe a solution
pOH is defined as: pOH = -log[OH-]
The sum of pH and pOH must equal 14 pH +
pOH = 14
assuming room temperature (25 oC)
The pH Scale
Example
Find [H3O+] of a solution that has pOH = 9.37
Method 1: Calculate pH, then [H3O+]
Step 1: Determine pH
pH = 14 – pOH = 14.00 – 9.37 = 4.63
Step 2: Determine [H3O+]
[H3O+] = 10-pH = 10-4.63 = 2.34 x 10-5 M
The pH Scale
Example
Find [H3O+] of a solution that has pOH = 9.37
Method 1: Calculate pH, then [H3O+]
Step 1: Determine pH
pH = 14 – pOH = 14.00 – 9.37 = 4.63
Step 2: Determine [H3O+]
[H3O+] = 10-pH = 10-4.63 = 2.34 x 10-5 M
Ionization Constants
The extent of dissociation of an acid or base in H2O
can be quantified using its ionization constant
Acids:
HA(aq) + H2O(l) H3O+(aq) + A-(aq)
acid base c. acid c. base
-
[H
O ][A ] [H O ][conjugate base]
K 3
3 a
[HA] [acid]
[HA] = undissociated acid in solution
Ionization Constants
Ka is a specific equilibrium constant
Acids:
HA(aq) + H2O(l) H3O+(aq) + A-(aq)
acid base c. acid c. base
-
[H
a 3
O ][A
] [H O ][conjugate base]
K [HA] 3
[acid]
[HA] = undissociated acid in solution
Ionization Constants
Example:
Acetic acid has a Ka = 1.8 x 10-5
Determine the pH of a 0.2 M acetic acid
solution
CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq)
We can approach this like any equilibrium
problem from Chap. 15
CH3COOH CH3COO- H3O+
initial 0.2 0 0
x x x x
-x
equil .2 – x
Ionization Constants
Example (con’t.):
pH = -log[H3O+] = -log(.0019) = 2.7
Ionization Constants
Kb is a specific equilibrium constant for bases
Bases:
B(aq) + H2O(l) HB+(aq) + OH-(aq)
baseacid c. acid c. base
- -
[HB ][OH
Kb [B] ] [OH ][conjugate acid]
[base]
[B] = undissociated base in solution
Ionization Constants
Example:
Determine [B] in a 1.82 x 10-3 M solution of NH3
NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)
NH3 NH4 + OH-
initial 1.82x10-3 0 0
-x x x
equil 1.82x10-3 – x x x
Ionization Constants
Example:
NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)
[NH
K 1.8x10 b
-5 ][OH
4
-
] x 2
[NH 3] 1.82x103 - x
x = 1.72 x 10-4 M = [NH4+] = [OH-]
[NH3] = 1.82 x 10-3 M – 1.72 x 10-4 M
= 1.65 x 10-3 M
Polyprotic Acids
Some acids contain more than one hydrogen
atom that may be donated to form H+ ion
These are called polyprotic acids
Examples include:
H2SO4 sulfuric acid (2 H+ ions)
H3PO4 phosphoric acid (3 H+ ions)
H2CO3 carbonic acid (2 H+ ions)
Polyprotic Acids
Each H atom has a unique Ka associated with its
release to form H+ ion
Consider phosphoric acid:
H3PO4(aq) + H2O(l) H2PO4-(aq) + H3O+(aq) 1st
Ka1 = 7.5 x 10-3
H2PO4-(aq) + H2O(l) HPO42-(aq) + H3O+(aq) 2nd
Ka2 = 6.2 x 10-8
HPO42-(aq) + H2O(l) PO43-(aq) + H3O+(aq) 3rd
Ka3 = 3.6 x 10-13
The first H atom is easiest to pull off, so it has the higher Ka
value
Strengths of Acids
Acid strength is determined by a
combination of factors:
Bond polarity—the H-A bond must be polar in
order for the H atom to be transferred to water as
H+
The H atom in CH4 is non-acidic because the C-H
bond is not polar
The H-Cl bond in HCl is polar, and HCl is a
strong acid
Strengths of Acids
Acid strength is determined by a combination
of factors:
Bond polarity—the H-A bond must be polar in order
for the H atom to be transferred to water as H+
The H atom in CH4 is non-acidic because the C-H
bond is not polar
The H-Cl bond in HCl is polar, and HCl is a
strong acid
Strengths of Acids
Acid strength is determined by a combination
of factors:
Bond polarity—the H-A bond must be polar in order
for the H atom to be transferred to water as H+
The H atom in CH4 is non-acidic because the C-H
bond is not polar
The H-Cl bond in HCl is polar, and HCl is a
strong acid
Strengths of Acids
Oxoacids are those with a H-O-Z linkage
The more O atoms attached to Z, the stronger the acid
Acid O atoms Ka
HOCl 1 3.5 x 10-8
HOClO 2 1.1 x 10-2
HOClO2 3 ~103
HOClO3 4 ~108
Relationship Between Ka and Kb
The Ka of an acid and the Kb of its conjugate base
are related:
HA(aq) + H2O(l) A-(aq) + H3O+(aq)
acid c. base
[A- ][H3O ]
Ka [HA]
A-(aq) + H2O(l) HA(aq) + OH-(aq)
base c. acid
[HA][OH ]
Kb
[A- ]
Relationship Between Ka and Kb
The Ka of an acid and the Kb of its conjugate base
are related:
The product Ka x Kb = Kw
-
Ka K [A ][H3 O ] [HA][OH ]
b
[HA] [A ]
[H3O ][OH ] K
w
-
This is true of any conjugate pair of acid and base
Salts of Acids and Bases
When an acid and a base undergo an exchange
reaction, the result is a salt and water:
HX(aq) + MOH(aq) MX(aq) + H2O
acid base salt
If a strong base is neutralized with a strong
acid, the resulting solution contains only the salt
HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)
Salts of Acids and Bases
Determine the pH of 0.284 M solution of sodium acetate,
NaCH3COO
NaCH3COO(aq) + H2O
Na+(aq) + CH3COOH(aq) + OH-(aq)
Complete ionic equation:
Na+(aq) + CH3COO-(aq) + H2O
Na+(aq) + CH3COOH(aq) + OH-(aq)
-
[CH COOH][OH ] Kw
K 5.56 x 10-10
3 -
[CH 3COO ] Ka
