Lecture 0: Acid-Base Chemistry

Reading: Zumdahl Chapters 7 and 8

Outline
Definition of Acids and Bases
Equilibrium Chemistry and Acids/Bases
Titrations
Brnsted-Lowry Acid-Base Definition
An acid is a proton donor, any species that donates an H
+
ion.
An acid must contain H in its formula (HNO
3
and H
2
PO
4
-
are two
examples).
A base is a proton acceptor, or any species that accepts an H
+
ion.
A base must contain a lone pair of electrons to bind the H
+
ion.
a few examples are NH
3
, CO
3
2-
, F
-
, as well as OH
-
.
Therefore in the Brnsted-Lowry picture, acids donate
protons and bases accept protons.
K
a
: the Acid Dissociation Constant
For the ionization of an acid, HA, in water:
The equilibrium constant for this reaction is referred to as K
a
:
The stronger the acid, the higher the [H
3
O
+
] at
equilibrium, and the larger K
a
:
Stronger acid higher [H
3
O
+
] larger K
a

HA(aq) + H
2
O(aq)
! " !
# ! !
H
3
O
+
(aq) + A
$
aq
( )

K
a
=
H
3
O
+
[ ]
A
!
[ ]
HA
[ ]
Strong acid undergoes
complete dissociation.
Weak acid undergoes
partial dissociation.
Note: H
+
= H
3
O
+
[H
3
O
+
] and pH
The hydronium ion concentration is generally expressed in
terms of pH.

pH = !log H
3
O
+
[ ]
The lower the pH, the greater the hydronium ion concentration.
Example: If the pH of a solution is 3.4, what is the hydronium ion
concentration?

H
3
O
+
[ ]
=10
! pH
=10
!3.4
= 3.98x10
!4
M
Determining Concentrations from K
a
and Initial [HA]
Problem: What is the pH of a 0.125 M HClO (hypochlorous acid)
solution? K
a
= 3.5 x 10
-8
Plan: We need to find [H
3
O
+
]. First, write the balanced equation and
the expression for K
a
and solve for the hydronium ion concentration.
Solution:
K
a
= = 3.5 x 10
-8

[H
3
O
+
] [ClO
-
]
[HClO]

HClO(aq) + H
2
O(aq)
! " !
# ! !
ClO
$
(aq) + H
3
O
+
(aq)
Concentration (M) HClO H
2
O H
3
O
+
ClO
-
Initial 0.125 ---- 0 0
Change -x ---- +x +x
Equilibrium 0.125 - x ---- x x
K
a
= = 3.5 x 10
-8

(x)(x)
0.125-x
assume 0.125 - x = 0.125
x
2
= 4.38 x 10
-9
x = [H
3
O
+
] = 6.61 x 10
-5

HClO(aq) + H
2
O(aq)
! " !
# ! !
ClO
$
(aq) + H
3
O
+
(aq)
Example (continued)

pH = !log H
3
O
+
[ ]
= !log 6.61x10
!5
( )
= 4.2
Autoionization of Water
K
w
= 1.0 x 10
-14
(at 25C)
For pure water the concentration of hydroxyl and hydronium ions
must be equal:
[H
3
O
+
] = [OH
-
] = 1.0 x 10
-14
= 1.0 x 10
-7
M (at 25C)
The molarity of pure water is: = 55.4M
1000g/L
18.02 g/mol

2H
2
O(aq)
! " !
# ! !
H
3
O
+
(aq) + OH
$
(aq)

K
w
= H
3
O
+
[ ]
OH
!
[ ]
Summary: Titration Curve Calculations
Stoichiometry: Add a strong base (acid) to a weak acid (base), and
determine the extent of neutralization using stoichiometric concepts.
Equilibrium: The concentration of weak base/acid conjugate
species is determined, and the equilibrium expression used to
determine [H
3
O
+
], or pH.
Acid/Base Titration Problems
Problems are a mix of stoichiometry and equilibrium.
Weak Acid Titration
Midpoint (Buffer)
Initial
Calculating the pH During a
Weak Acid-Strong Base Titration
Problem: Calculate the pH during the titration of 20.00 mL of
0.250 M nitrous acid (HNO
2
; K
a
= 4.5 x 10
-4
) after adding the
following volumes of 0.250 M NaOH : (a) 0.00 mL (b) 8.00 mL
(c) 10.00 mL (d) 20.00 mL.
Plan: (a) Just calculate the pH of a weak acid.
(b)-(d) Calculate the amounts of acid remaining after the
reaction with the base in addition to the conjugate base
concentration, and plug these into the equilibrium
expression.
HNO
2
(aq) + H
2
O(l) H
3
O
+
(aq) + NO
2
-
(aq)
K
a
= = = 4.5 x 10
-4
[H
3
O
+
] [NO
2
-
]
[HNO
2
]
x (x)
0.250 M
x
2
= 1.125 x 10
-4
x = 1.061 x 10
-2
pH = -log(1.061 x 10
-2
) = 1.97
Initial pH
Before addition of base, problem is exactly like a weak-acid
equilibrium problem.
Init 0.25 0 0
Change -x x x
Eq. 0.25-x x x
After 8 ml Addition of NaOH: Stoichiometry
OH
-
converts HNO
2
to NO
2
-
.
8.00 mL x 0.250 mmol/mL = 2.00 mmol OH
-
which will
convert (neutralize) 2.00 mmol of HNO
2.
Initially 20 mL x 0.250 mmol/ml = 5.00 mmol HNO
2
.
Therefore, 5.00 mmol - 2.00 mmol = 3.00 mmol of HNO
2
left,
and

2.00 mmol of NO
2
-
are produced.
HNO
2
(aq) + OH
-
(l) H
2
O(l) + NO
2
-
(aq)
HNO
2 (aq)
+ H
2
O
(l)
H
3
O
+
(aq)
+ NO
2
-
(aq)
Concentration (M)
Initial 0.107 0 0.071
Change -x x x
Equilibrium 0.107 - x x 0.071 + x
After 8 ml Addition of NaOH: Equilibrium
Need concentrations: mmol/total mL. Total ml = 28 ml

K
a
=
H
3
O
+
[ ]
NO
2
!
[ ]
HNO
2
[ ]
" H
3
O
+
[ ]
= K
a
HNO
2
[ ]
NO
2
!
[ ]
= 4.5x10
!4
( )
0.107
( )
0.071
( )
= 6.8x10
!4
pH = 3.17
After 10 ml Addition of NaOH: Stoichiometry
OH
-
converts HNO
2
to NO
2
-
.
10.00 mL x 0.250 mmol/mL = 2.5 mmol OH
-
which will
convert (neutralize) 2.5 mmol of HNO
2.
Initially 20 mL x 0.250 mmol/ml = 5 mmol HNO
2
.
Therefore, 5mmol - 2. 5 mmol = 2.5 mmol of HNO
2
left,
and

2.5 mmol of NO
2
-
are produced.
HNO
2
(aq) + OH
-
(l) H
2
O(l) + NO
2
-
(aq)
HNO
2 (aq)
+ H
2
O
(l)
H
3
O
+
(aq)
+ NO
2
-
(aq)
Concentration (M)
Initial 0.083 0 0.083
Change -x x x
Equilibrium 0.083 - x x 0.083 + x
After 10 ml Addition of NaOH: Equilibrium
Need concentrations, given by mmol/total mL. Total ml = 30 ml

K
a
=
H
3
O
+
[ ]
NO
2
!
[ ]
HNO
2
[ ]
" H
3
O
+
[ ]
= K
a
HNO
2
[ ]
NO
2
!
[ ]
= 4.5x10
!4
( )
0.083
( )
0.083
( )
= 4.5x10
!4
pH = 3.35
20 ml of NaOH: Equivalence
20.00 mL x 0.250 mmol/mL = 5 mmol OH
-
which will
convert (neutralize) 5 mmol of HNO
2.
Initially 20 mL x 0.250 mmol/ml = 5 mmol HNO
2
.
Therefore, all of the HNO
2
is converted to NO
2
-
!
pH is determined by NO
2
-
equilibrium:
HNO
2
(aq) + OH
-
(l) H
2
O(l) + NO
2
-
(aq)
NO
2
-

(aq) + H
2
O(l) OH
-
(aq) + HNO
2
(aq)

K
b
=
K
w
K
a
= 2.2x10
!11
=
OH
!
[ ]
HNO
2
[ ]
NO
2
!
[ ]
=
x
2
0.125
x = OH
!
[ ]
=1.65x10
!6
M
Initial [NO
2
-
] = 5mmol/40 ml = 0.125M
NO
2
-

(aq) + H
2
O(l) OH
-
(aq) + HNO
2
(aq)
Initial 0.125 0 0
Change -x x x
Equilibrium 0.125 - x x x

pOH = !log OH
!
[ ]
= 5.78

pH =14 ! pOH = 8.22
Equivalence (cont.)
Generic Titration Curves
: Initial
: Midpoint Buffer
: Equivalence
For 0.10 M HA