Acids and Bases II

:
Acid-Base Equilbria
Acids and Bases: Chem 16
• Arrhenius Definition




( )
O H OH + H
l 2
-
(aq) (aq)
÷
÷
+

• ACIDS – donates H
+


• HNO
3,
H
3
PO
4,
H
2
SO
4,
HCl, HI, HBr,
CH
3
COOH, organic-COOH, H
2
SO
3


• BASES – donates OH
-



NaOH, KOH, LiOH, CsOH,
Mg(OH)
2
,Sr(OH)
2
,Ba(OH)
2
, Ca(OH)
2

Acids and Bases: Chem 16
• Bronsted-Lowry Definition

+
+ · +
4(aq)
-
(aq) 3(g) (l) 2
NH OH NH O H

• ACIDS – donates H
+

• (proton donor)

• HNO
3,
H
3
PO
4,
H
2
SO
4,
HCl, HI, HBr,
CH
3
COOH, organic-COOH, H
2
SO
3


• BASES – accepts H
+

• (proton acceptor)


• NH
3
, organic-NH
2
, NaOH, KOH, LiOH,
CsOH, Mg(OH)
2
,Sr(OH)
2
,Ba(OH)
2
, Ca(OH)
2

Acids and Bases: Chem 16
• Bronsted-Lowry Definition

Acids and Bases: Chem 16
• Amphoterism:
– Species that can behave as an acid or base are
called amphoteric.




– Proton transfer reactions in which a species
behaves as either an acid or base is called
amphiprotic
O H 2 ) Zn(NO HNO 2 Zn(OH)
2 2 3 3 2
+ ÷ +
- 2
4
-
2
Zn(OH) OH 2 Zn(OH) ÷ +
HPO
4
3-
+ H
2
O  H
2
PO
4
2-
+ OH
-

HPO
4
3-
+ H
2
O  PO
4
3-
+ H
3
O
+


Acids and Bases: Chem 16
• Lewis Definition


• ACIDS – electron-pair acceptor

• H
+
(∴ all molecules with H
+
)
• Electron deficient molecules
(below-octet atoms eg. Boron
cmpds)

• BASES – electron-pair donor


• OH
-
(∴ all molecules with OH
-
)
• Molecules with lone e
-
pairs
acid base
OH NH O H NH
-
4 2 3
÷ +
÷
+
+
base acid
BF Na BF NaF
-
4 3
+
÷
÷
+
+
Lewis
Brønsted-Lowry
Arrhenius
Hehehe...
Acids and Bases: Chem 16  17
• The Autoionization of water
÷ +
÷
+
+ -
(aq) (aq) 3 ) ( 2 ) ( 2
OH O H O H O H
 
Equilibrium-constant expression:
2
2
-
3
c
] O [H
] ][OH O H [
K
+
=
But concentration of water is
constant (and large) at 25
o
C,
therefore:
] ][OH O H [ K K
-
3 w c
+
= ¬
Experimental concentration H
+
is
determined to be 1.00x10
-7
at
25
o
C, therefore:
C 25 at 10 1.00x K
) 10 x 00 . 1 )( 10 (1.00x K
o 14 -
w
-7 -7
w
=
=
Acids and Bases: Chem 16  17
pH = -log [H
3
O
+
] or simply –log[H
+
]
pOH = -log[OH
-
]
K
w
= 1.00 x 10
-14
= [H
+
][OH
-
] at 25
o
C
∴ pOH + pH = 14.00


Proof:
-log K
w
= -log [1.00 x 10
-14
] = -log ([H
+
][OH
-
])
-log K
w
= 14.00 = -log[H
+
] + -log[OH]
-

14.00 = pH + pOH

Acids and Bases: Chem 16  17
• Calculate the [H
3
O
+
], pH, [OH
-
], and pOH for a 0.020 M HNO
3

solution.
– Is HNO
3
a weak or strong acid?
– What is the [H
3
O
+
] ?
| |
( )
70 . 1 pH
10 0 . 2 -log pH
10 0 . 2 O H
0.020 0.020 020 . 0
NO O H O H HNO
2
2
3
-
3 3
100%
2 3
=
× =
× =
+ ÷ ÷ ÷ ÷ +
÷
÷ +
+ ~
M
M
M M M
• What is pH of water at its normal boiling
point? Is it acidic or basic?
– Given:
∆H
f
o
H2O(l)
= -285.83 kJ/mol
∆H
f
o
OH-(aq)
= -230.0 kJ/mol
 When concentration of acid reaches 1.00 x 10
-5

and below, the [H
+
] of H
2
O should be added, where
[H
+
] = 1.00 x 10
-7
(only used at 25
o
C)

 Example: What is the pH of a solution prepared
by diluting 1.0 mL of 0.1 M HCl with 1000 liters
of water?

Acids and Bases: Chem 16
• Relative Strengths of Acids and Bases
Conjugate Acid-Base Pairs
 The weaker the acid or base, the stronger the conjugate partner.

 The stronger the acid or base, the weaker the conjugate partner.

2(g) (l) 2 (aq) 3 2 (aq) 3 (aq) 3 (aq) 3 2
(aq) 3 (aq) (aq) (aq) 3
CO O H CO H OO 2NaCH OOH CH 2 CO Na
COOH CH NaCl HCl OO NaCH
+ ¬ + ÷÷ ÷ +
+ ÷÷ ÷ +
STRONGER
ACID and BASE
WEAKER
ACID and BASE
Ionization Constants for Monoprotic
Weak Acids and Bases
• Consider an aqueous solution of acetic acid,
CH
3
COOH. What is the equilibrium constant
expression?

CH
3
COOH
(aq)
+ H
2
O
(l)
⇄ CH
3
COO
-
(aq)
+ H
3
O
+
(aq)

] O COOH][H [CH
] COO ][CH O H [
K
2 3
-
3 3
c
+
=
But [H
2
O] = 55.6 M, very high and almost constant, therefore
COOH] [CH
] COO ][CH O H [
K K
3
-
3 3
a c
+
= ~
• Because of its simplified form, we can write
the equation for dissociation as

CH
3
COOH
(aq)
⇄ CH
3
COO
-
(aq)
+ H
+
(aq)


COOH] [CH
] COO ][CH H [
K
3
-
3
a
+
=
COOH] [CH
] COO ][CH O H [
K K
3
-
3 3
a c
+
= ~
K
a
is the acid-dissociation constant


• For weak bases,
NH
3(aq)
+ H
2
O
(l)
⇄ NH
4
+
(aq)
+ OH
-
(aq)



O] ][H [NH
] ][NH OH [
K
2 3
4
c
+
÷
=
] [NH
] ][NH OH [
K
3
4
b
+
÷
=
K
b
is the base-dissociation constant. But why???
Does the base dissociate, like acids?
[acid]
] base e ][conjugat H [
K
a
+
=
[base]
] acid e ][conjugat OH [
K
b
÷
=
HA ⇄ H
+
+ A
-

B
-
+ H
2
O ⇄ OH
-
+ BH
 The ionization constant values for several acids are given
below.
◦ Which acid is the strongest?
Acid Formula K
a
value
Acetic CH
3
COOH 1.8 x 10
-5

Nitrous HNO
2
4.5 x 10
-4

Hydrofluoric HF 7.2 x 10
-4
Hypochlorous HClO 3.5 x 10
-8
Hydrocyanic HCN 4.0 x 10
-10
Ionization Constants for Monoprotic Weak Acids
and Bases
 The order of increasing acid strength for these weak
acids is:
HCN > HClO > COOH CH > HNO > HF
3 2
 Calculate the concentrations of the various species in
0.15 M acetic acid, CH
3
COOH, solution.

 ALWAYS write down the ionization reaction and
the ionization constant expression.
| || |
| |
5
3
-
3 3
a
-
3 3 2 3
10 8 . 1
COOH CH
COO CH O H
K
COO CH O H O H COOH CH
÷
+
+
× = =
÷ +
÷
+
Ionization Constants for Monoprotic
Weak Acids and Bases
xM xM -x)M . (
xM xM xM
M
+ +
+ +
÷ +
÷
+
+
15 0 ] [ m Equilibriu
- Change
0.15 ] [ Initial
COO CH O H O H COOH CH
-
3 3 2 3
• Short-cut: Use the simplfying assumption-
Since x << 0.15, assume that 0.15 – x ≈ 0.15
If K
a
/[ ]
initial
is < 1.0x10
-3
, the simplifying assumption is valid
Percent Ionization of Weak
Acids/Bases
 Calculate the percent ionization of 0.15 M acetic acid. The
percent ionization of acetic acid is
| | | |
| |
% 1 . 1 % 100
15 . 0
10 6 . 1
ionization %
% 100
COOH CH
H or COO CH
= ionization %
3
original
3
-
3
= ×
×
=
×
÷
+
M
M
equil
equil
Percent Ionization of Weak
Acids/Bases
• Calculate the percent ionization of 0.15 M
hydrocyanic acid, HCN. K
a
= 4.0 x 10
-10
– Compare the %ionization of HCN and HOAc.
 Note that the [H
+
] (or %ionization) in 0.15 M
acetic acid is 215 times greater than for
0.15 M HCN.
Solution K
a
[H
+
] pH % ionization
0.15 M
HOAc
1.8 x 10
-5
1.6 x 10
-3
2.80 1.1
0.15 M
HCN
4.0 x 10
-10
7.7 x 10
-6
5.11 0.0051
Solvolysis: Reaction of Acid/Base with
solvent
• Solvolysis is the reaction of a substance with
the solvent in which it is dissolved.

• Hydrolysis refers to the reaction of a
substance with water or its ions.

• Combination of the anion of a weak acid with
H
3
O
+
ions from water to form nonionized
weak acid molecules.
Solvolysis: Reaction of Acid/Base with
solvent
• Consider the acid HA


HA + H
2
O ⇄ A
-
+ H
3
O
+
K
a

Reverse form:
A
-
+ H
3
O
+
⇄ HA + H
2
O K
a

= 1/K
a


• Consider the conjugate base, A
-

A
-
+ H
2
O ⇄ HA + OH
-
K
b

Reverse form:
HA + OH
-
⇄ A
-
+ H
2
O K
b

= 1/K
b
Solvolysis: Reaction of Acid/Base with
solvent
• How is K
a
related to K
b
?
HA + H
2
O ⇄ A
-
+ H
3
O
+
K
a

A
-
+ H
2
O ⇄ HA + OH
-
K
b



H
2
O + H
2
O ⇄ H
3
O
+
+ OH
-
K
w

b a w
K x K K =
a
w
b
K
K
K =
b
w
a
K
K
K =
 The order of increasing acid strength for the weak
acids is:
HCN > HClO > COOH CH > HNO > HF
3 2
 The order of increasing base strength of the
anions (conjugate bases) of the same acids
is:
- - -
3
-
2
-
CN < ClO < COO CH < NO < F
1.8 x 10
-5
4.5 x 10
-4
7.2 x 10
-4
3.5 x 10
-8
4.0 x 10
-10
a
w
b
K
K
K =
5.6 x 10
-10
1.4 x 10
-11
2.2 x 10
-11
2.9 x 10
-7
2.5 x 10
-5
The stronger the acid/base, the weaker is its
conjugate
Strengths of Acids and Bases
 Strengths of BINARY Acids - acid strength increases with
decreasing H-X bond strength.

◦ VIIA hydrohalic acids
Bond strength has this periodic trend
HF >> HCl > HBr > HI
Acid strength has the reverse trend.
HF << HCl < HBr < HI
◦ VIA hydrides.
Bond strength has this trend.
H
2
O >> H
2
S > H
2
Se > H
2
Te
The acid strength is the reverse trend.
H
2
O << H
2
S < H
2
Se < H
2
Te

Strengths of Acids and Bases
• Down a group: size, energy to break H- bond
(electronegativity), acidity

Arrange in order of increasing acidity:
NH
3
, OH
2
, HF
 NH
3
< OH
2
< HF
(Electronegativity trend: NH
3
< OH
2
< HF)

• Across a period: electronegativity, acidity



Strengths of Acids and Bases
• TERNARY ACIDS - hydroxides of nonmetals
that produce H
3
O
+
in water.
– Consist of H, O, and a nonmetal.
HClO
4
H
3
PO
4


Strengths of Acids and Bases
• Acidity of ternary acids with same central
element increase with increasing oxidation
state of central element, and increasing O
atoms
HClO < HClO
2
< HClO
3
< HClO
4

weakest strongest

Cl oxidation states
+1 +3 +5 +7

Strengths of Acids and Bases
• ternary acids of the same group and same
number of O atoms increase in acidity with
increase electronegativity of central atom
H
2
SeO
4
< H
2
SO
4

HBrO
4
< HClO
4

HBrO
3
< HClO
3


However for
phosphorus ternary
acids:
H
3
PO
2
> H
3
PO
3
>
H
3
PO
4
– relative
position of H is
important (based on
structures only!)

Hard and Soft Acids and Bases
From previous discussion, the STRENGTH of an
acid or a base depends on the value of its
dissociation constant K
a
or K
b
, respectively

Hardness or Softness of an acid/base depends on
POLARIZABILITY of molecule
◦ Recall that “Polarizability“ is used in describing the
type of IMFA of molecules
◦ The concept of Hardness or Softness of acids/bases is
Lewis-structure dependent, therefore it is a concept
applied only in the LEWIS DEFINITION of acids/bases.
• More polarizable molecules (greater # of π e
-

or lone pairs) – SOFT Lewis acids/bases
• Less polarizable molecules – HARD Lewis
acids/bases
HARD acid-HARD base
SOFT acid-SOFT base
Dissociation
constant
In general, molecules that involve
HARD acid-SOFT base
SOFT acid-HARD base
Hard Lewis acid
Which is the Hardest Lewis base? Which is the softest?
- - -
3
-
2
-
CN ClO COO CH NO F
HARDEST
Lewis
base
SOFTEST
Lewis
base
• In a 0.12 M solution of a weak monoprotic acid, HY, the acid is
5.0% ionized. Calculate the dissociation constant for the weak
acid.
 The pH of a 0.10 M solution of a weak monoprotic
acid, HA, is found to be 2.97. What is the value of
its dissociation constant?
Polyprotic Acids/Bases
• Many weak acids contain two or more acidic hydrogens.
– Examples include H
3
PO
4
and H
3
AsO
4
.

• The calculation of equilibria for polyprotic acids is done in a stepwise
fashion.
– There is a dissociation constant for each step

• Consider arsenic acid, H
3
AsO
4
, which has three ionization constants.
1 K
a1
= 2.5 x 10
-4
2 K
a2
= 5.6 x 10
-8

3 K
a3
= 3.0 x 10
-13
• Calculate the concentration of all species in 0.100 M
arsenic acid, H
3
AsO
4
, solution.
You may apply the simplifying assumption in each step (1 ICE
table/ dissociation)
11 -
a2 (aq) 3
- 2
3(aq) (l) 2
-
3(aq)
-7
a1 (aq) 3
-
3(aq) (l) 2 3(aq) 2
10 x 4.7 K O H CO O H HCO
10 x 4 . 4 K O H + HCO O H CO H
= + ÷ +
= ÷ +
+
+
8 -
b2 (aq) 3(aq) 2 (l) 2
-
3(aq)
-4
b1 (aq)
-
3(aq) (l) 2
- 2
3(aq)
10 x 2.3 K HO CO H O H HCO
10 x 1 . 2 K HO + HCO O H CO
= + ÷ +
= ÷ +
÷
÷
b2 a2
w
b1 a1
K K
K
K K
K HO PO H O H PO H
K HO PO H O H HPO
K HO + HPO O H PO
b3 (aq) 4(aq) 3 (l) 2
-
4(aq) 2
b2 (aq)
-
4(aq) 2 (l) 2
- 2
4(aq)
b1 (aq)
- 2
4(aq) (l) 2
- 3
4(aq)
÷
÷
÷
+ ÷ +
+ ÷ +
÷ +
b3 a3
b2 w a2
b1 a1
K K
K K K
K K
13 -
a3 (aq) 3
- 3
4(aq) (l) 2
- 2
4(aq)
8 -
a2 (aq) 3
- 2
4(aq) (l) 2
-
4(aq) 2
-3
a1 (aq) 3
-
4(aq) 2 (l) 2 4(aq) 3
10 x 3.60 K O H PO O H HPO
10 x 6.20 K O H HPO O H PO H
10 x 50 . 7 K O H + PO H O H PO H
= + ÷ +
= + ÷ +
= ÷ +
+
+
+
• The behaviour of an amphiprotic species
(acting as base or acid) depends on its
dissociation constants
11 -
a2 (aq) 3
- 2
3(aq) (l) 2
-
3(aq)
-8
b2 (aq) 3(aq) 2 (l) 2
-
3(aq)
10 x 4.80 K O H CO O H HCO
10 x 2.38 K OH CO H O H HCO
= + ÷ +
= + ÷ +
+
÷
12 -
b3 (aq) 4(aq) 3 (l) 2
-
4(aq) 2
-8
a2 (aq) 3
- 2
4(aq) (l) 2
-
4(aq) 2
10 x 1.33 K OH PO H O H PO H
10 x 6.20 K O H HPO O H PO H
= + ÷ +
= + ÷ +
÷
+
7 -
b2 (aq)
-
4(aq) 2 (l) 2
- 2
4(aq)
-13
a3 (aq) 3
- 3
4(aq) (l) 2
- 2
4(aq)
10 x 1.61 K OH PO H O H HPO
10 x 3.6 K O H PO O H HPO
= + ÷ +
= + ÷ +
÷
+
• What is the pH of the resulting solution
obtained by dissolving 1.52 g of
NaH
2
PO
4
•2H
2
O in 50.00 mL water? If the salt
added was Na
2
HPO
4
•2H
2
O instead, will the
solution be basic or acidic?

• You accidentally spilled muratic acid (2.0 M
HCl) on the rubber slippers of your room
mate. To neutralize the acid, you looked for a
base in your dorm stock room, and you found
two salts – sodium bicarbonate and sodium
phosphate. Which of the two salts will you
use?
Inorganic Lewis Acids – Hydrolysis of
Metal Ions
Because metal ions are positively charged,
they attract the electrons of oxygen atoms in
water.
◦ Depending on the strength of electron interacting
with the cation, the water molecule can turn into
hydroxide anion and release H
+




◦ The acid strength of these ion-complexes acting as
Lewis acids depend on size and charge of cation
center

3 -
a (aq)
2
(aq) 5 2
3
) aq ( 6 2
10 x 2.0 K H (OH) O) Fe(H ) O Fe(H = +
÷
÷
+ + +
Na(NO
3
) Ca(NO
3
)
2
Zn(NO
3
)
2
Al(NO
3
)
3

7.0 6.9 5.5 3.5
Salts of acids and bases
 Aqueous solutions of salts of strong acids and strong bases
are neutral
Examples: NaCl (from HCl and NaOH)
K
2
SO
4
(from KOH and H
2
SO
4
)

 Aqueous solutions of salts of strong bases and weak acids
are basic
Examples: NaCN (from NaOH and HCN)
K
2
C
2
O
4
(from KOH and H
2
C
2
O
4
)

 Aqueous solutions of salts of weak bases and strong acids
are acidic
Examples: NH
4
Cl (from NH
3
and HCl)
(CH
3
)
3
NHBr ((CH
3
)N and HBr)

How about – KHC
2
O
4
? NaHSO
4
? LiHSO
3
?



Salts of acids and bases
• Aqueous solutions of salts of weak bases and
weak acids can be neutral, basic or acidic.
The values of K
a
and K
b
determine the pH.

NH
4
CH
3
COO?
Compare K
a
of NH
4
+
vs K
b
of OAc
-

MgNH
4
PO
4
?
Compare K
a
of NH
4
+
and Mg
2+
vs K
b
of OAc
-

NH
4
(HCO
3
)?
Compare K
a
of NH
4
+
vs K
b
/K
a
of amphiprotic HCO
3
-






Common Ion Effect
and
Buffers/Buffer Capacity
Common Ion Effect –
A special name for a Le Chatelier-based shift
• Consider a solution of 0.05 M acetic acid, CH
3
COOH (50.00
mL)

5 -
a (aq) 3 (aq) 3 ) l ( 2 (aq) 3
10 x 1.8 K O H COO CH O H COOH CH = +
÷
÷
+
+ ÷
O H COO CH O H COOH CH
(aq) 3 (aq) 3 ) l ( 2 (aq) 3
+ ÷
+ ÷÷ ÷ +
O H COO CH O H COOH CH
(aq) 3 (aq) 3 ) l ( 2 (aq) 3
+ ÷
+ ÷÷ ÷ +
• Describe the direction of equilibrium shift
After adding 10.00 mL of 0.5 M HCl



After adding 10.00 mL of 0.5 M NaCH
3
COO
In COMMON-ION effect, the direction of shift of equilibrium is always
towards the side that diminishes the added common/similar ion
Common Ion Effect –
A special name for a Le Chatelier-based shift
• Consider a solution of 0.05 M acetic acid,
CH
3
COOH (50.00 mL)

• Describe the pH of the final mixture
– After adding 10.00 mL of 0.5 M HCl


– After adding 10.00 mL of 0.5 M NaCH
3
COO



DECREASE pH, more ACIDIC
INCREASE pH, less ACIDIC
Buffers
• Solutions that contain BOTH acid component
and its conjugate base
– Conjugate base is directly added, not the one
calculated from equilibrium
– Examples :
• Acetic acid added with sodium acetate
• Ammonium chloride added with aqueous ammonia
solution

• Solutions that resist drastic pH changes

Henderson-Hasselbalch Equation
Simplified equation for pH calculation
involving buffers
Buffers
 What is pH of a buffer that is 0.12 M in lactic acid, HC
3
H
5
O
5
,
and 0.10 M in sodium lactate?
K
a
= 1.40 x 10
-4


The most important aspect of buffer solutions is that they resist
drastic changes of pH upon adding strong acids or bases!
O H COO O H C O H COOH O H C
(aq) 3 (aq) 3 4 4 ) l ( 2 (aq) 3 4 4
+ ÷
+
÷
÷
+
0.10 M 0.12 M
+ x + x - x
I
C
E
0.12 - x 0.10 + x x

(0.12)
(0.10)
pK pH
a
+ =
x) (0.12
x) (x)(0.10
K
a
÷
+
=
Common Ion Effect – Buffers
• Non-buffer Case - Consider the a solution of 50.00 mL of 0.05 M acetic
acid, CH
3
COOH. Calculate the pH of the final mixture after adding 10.00
mL of 0.05 M HCl.
O H COO CH O H COOH CH
(aq) 3 (aq) 3 ) l ( 2 (aq) 3
+ ÷
+
÷
÷
+
 Because HCl is a strong acid, it directly contributes to the initial
concentration of H
3
O
+
in the equilibrium calculation
 Set-up ICE table in MOLE basis, then convert to molarity when
calculating/equating to Ka.
(10.00 mL) •
(0.05 M)
(50.00 mL) •
(0.05 M)
+ x + x - x
I
C
Common Ion Effect – Buffers
• Buffer CASE - Consider a solution of 50.00 mL 0.05 M acetic acid
(CH
3
COOH) and 0.05 M sodium acetate (NaCH
3
COO). Calculate the pH of
the final mixture after adding 10.00 mL of 0.05 M HCl.
Step 1: STOICHIOMETRIC calculation
Which has the lowest change in pH (∆pH)?

 Try calculating the pH after adding 10.00 mL of 0.05 M NaOH (instead HCl)
for the 2 cases.
Step 2: EQUILIBRIUM calculation, HH

mL) 60.00 volume (total
M) mL)(0.05 (60.00
mL) 60.00 volume total (
M) mL)(0.05 00 . 40 (
log pK pH
a
(
¸
(

¸

=
(
¸
(

¸

=
+ =
Henderson-Hasselbalch Equation
HA + H
2
O ⇄ A
-
+ H
3
O
+

B + H
2
O ⇄ BH
+
+ HO
-

 HH equation only used when salt is present – that is, present
separately, not the [salt] from ICE calculation

 The salt-component must be added separately, or generated by
neutralizing the main component

 In calculations involving buffers, ICE table must be in terms of
MOLES especially if volumes are not same. However, equating with Ka
must be in MOLARITY.

 HH equation is allowed only when “simplifying assumptions” are
valid
Preparation of Buffers
Buffers can be prepared in three ways

◦ Adding a solid component to a liquid component
 Ex. NaCH
3
COO solid added to a solution of acetic acid (acetic-
acetate buffer)

◦ Neutralizing a liquid component with a strong opposite
component
 Ex. Aqueous ammonia added with liquid HCl (ammonia-
ammonium buffer)
Aqueous phosphoric acid added with solid NaOH
(phosphate buffer)

◦ Mixing two solid components in the same volume of
water
 Ex. Solid NaH
2
PO
4
•H
2
O and solid Na
2
HPO
4
•7H
2
O dissolved in
water (phosphate buffer)

Preparation of Buffers
• How many grams of NH
4
Cl must be added to
2.0 L of 0.10 M NH
3
to form a buffer of pH
9.00?
Kb NH
3
= 1.8 x 10
-5

 What volume of 0.5 M NaOH must be added
to 50 mL of 0.1 M benzoic acid (C
6
H
5
COOH)
to make 100.0 mL of 0.05 M benzoate buffer
that is pH 4.5?
Ka benzoic acid = 6.3 x 10
-5

Preparation of Buffers
• Prepare a 100.0 mL 0.1 M phosphate buffer, pH 8.00.
– Given:


H
3
PO
4

pKa1 = 2.12
pKa2 = 7.21
pKa3 = 12.38
Molarity H
3
PO
4
(liquid) = 14.85 M
Formula weight
NaH
2
PO
4
•H
2
O = 137.99 g/mole
Na
2
HPO
4
•7H
2
O = 268.07 g/mole
7.21 pK O H HPO O H PO H
a2 (aq) 3
- 2
4(aq) (l) 2
-
4(aq) 2
= + ÷ +
+

) PO H (moles
) HPO (moles
log pK pH
-
4 2
- 2
4
a2
+ =
components buffer moles total HPO moles PO H moles
- 2
4
-
4 2
= +
M) (0.1
)
L 1
mL 1000
(
mL) (100.0
HPO moles PO H moles
- 2
4
-
4 2
= +
Buffer Capacity
Amount of acid or base (usually in mL) needed to
change the pH of a buffer solution by 1 degree.

Compare the two buffers:
- 100 mL of 1.0 M NaCH
3
COO and 1.0 M CH
3
COOH
- 100 mL of 0.1 M NaCH
3
COO and 0.1 M CH
3
COOH

- Which has the highest buffer capacity relative to 1.0 M
NaOH?
Acid-Base Neutralizations:
Indicators, Titrations
and
pH curves
Acid-Base Indicators
• The point at which chemically equivalent amounts of acid and
base have reacted is called the equivalence point.

• The point at which a chemical indicator changes color is called
the end point.

2 color 1 color
O H In O H HIn
(aq) 3 (aq) ) l ( 2 (aq)
+ ÷
+
÷
÷
+
b color a color
OH HIn O H In
(aq) (aq) ) l ( 2 (aq)
÷ ÷
+
÷
÷
+
Acidic indicator
Basic indicator
Acid-Base Indicators
• The equilibrium constant expression for an indicator
would be expressed as:

[HIn]
] ][In O [H
K
-
3
a
+
=

[HIn]
] [In

] O [H
K
-
3
a
=
+
pH range when indicator
changes its color depends
largely on K
a
of the indicator
Acid-Base Indicators
Color change ranges of some acid-base indicators
Indicator
Color in
acidic
range pH range
Color in
basic range
Methyl violet Yellow 0 - 2 Purple
Methyl orange Pink 3.1 – 4.4 Yellow
Litmus Red 4.7 – 8.2 Blue
Phenolphthalein Colorless 8.3 – 10.0 Red
Titration Curves
Strong Acid titrated with Strong Base
Given: 25.00 mL of 0.5 M HClO
4
, calculate the pH of the
resulting solution after adding the following volumes of
0.5 M NaOH:

Volume of
0.5 M NaOH
(mL)
Mmoles
NaOH
Mmoles
HClO
4

remaining
Total
Volume
(mL)
[H
+
]
final
pH
0.00 0.0 12.5 25.0 0.5000 0.301
5.00 2.5 10.0 30.0 0.3333 0.477
10.00 5.0 7.5 35.0 0.2143 0.669
15.00 7.5 5.0 40.0 0.1250 0.903
20.00 10.0 2.5 45.0 0.0555 1.256
25.00 12.5 0 50.0 1x10
-7
7.000
30.00 15.0 0 55.0 2.2x10
-13
12.657
Methyl orange
Phenolphthalein
Litmus
Methyl violet
• Strong Acid/ Strong Base Titration Curve
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
0 5 10 15 20 25 30 35 40
pH
Volume Titrant (0.5 M NaOH)
SA-SB curve
Titration Curves
Weak Acid titrated with Strong Base
Given: 25.00 mL of 0.5 M CH
3
COOH, calculate the pH of
the resulting solution after adding the following volumes of
0.5 M NaOH:

Volume of
0.5 M
NaOH (mL)
Mmoles
NaOH
Mmoles
CH
3
COOH


remaining
Mmoles
CH
3
COO
-

produced
Total
Volume
(mL)
pH
0.00 0.0 12.5 0 25.0 0.301
5.00 2.5 10.0 2.5 30.0 4.143
10.00 5.0 7.5 5.0 35.0 4.569
15.00 7.5 5.0 7.5 40.0 4.921
20.00 10.0 2.5 10.0 45.0 5.348
25.00 12.5 0 12.5 50.0 9.071
30.00 15.0 0 12.5 55.0 12.658
Methyl orange
Phenolphthalein
Litmus
Methyl violet
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
0 5 10 15 20 25 30 35 40
pH
Titrant volume
WA-SB curve
WA vs SB Titration Curve Regions
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
0 5 10 15 20 25 30 35 40
pH
Titrant volume
WA-SB curve
Initial Region: Use ICE
and K
a

pH = ½ (pK
a
+ pC
HA
)
Buffer Region: HH Equation
pH = pK
a
+ log (moles A
-
/moles HA)
At half equivalence point:
pH = pK
a

Equivalence Region: Use ICE
and K
b

pOH =
½ (pK
b
+ p[moles HA/total
volume])
Excess base region:
pOH = -log (moles excess base/ total volume)
Buffer Region: HH Equation
pH = pK
a
+ log [moles titrant/(moles
analyte – moles titrant )]
Methyl orange
Phenolphthalein
Litmus
Methyl violet
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
0 5 10 15 20 25 30 35 40
acetic curve
lactic curve
HClO curve
Titration
Curve of
Different
Acids vs
Strong Base
• A 0.1044-g sample of an unknown monoprotic acid required
22.10 mL of 0.0500 M NaOH to reach the endpoint. (a) What
is the molecular weight of the acid? (b) As the acid is titrated,
the pH of the solution after the addition of 11.05 mL of the
base is 4.89. What is the K
a
of the acid?
 A biochemist needs 750 mL of an acetic acid-sodium acetate
buffer with pH 4.50. Solid sodium acetate, NaC
2
H
3
O
2
, and
glacial acetic acid, HC
2
H
3
O
2
, are available. Glacial acetic acid is
99% pure by mass and has a density of 1.05 g/mL. If the
buffer is to be 0.20 M in HC
2
H
3
O
2
, how many grams of the salt
and how many milliliters of glacial acetic acid must be used?
Titration Curves of Polyprotic Acids vs
SB
H
2
A + H
2
O ⇄ HA
-
+ H
3
O
+
K
a1
HA
-
+ H
2
O ⇄ A
2-
+ H
3
O
+
K
a2

pH Curve will show:
 2 Equivalence points
 Buffer region similar to weak monoprotic acid region
 Amphiprotic region
First Equivalence Point: H
2
A + NaOH ⇄ Na
+
+ HA
-
+ H
2
O
Second Equivalence Point: HA
-
+ NaOH ⇄ Na
+
+ A
2-
+ H
2
O
Amphiprotic region starts at the 1st equivalence point
region. The region between the 1st equivalence point and
2nd equivalence point is a buffer region composed of HA
-

and A
2-
. In this region, the buffer HA
-
and A
2-

predominates the amphiprotic species HA
-
. 
Weak H
2
A vs SB
Initial Region: Use ICE
pH = ½ (pK
a1
+ pC
H2A
)
Buffer Region: HH Equation
pH = pK
a1
+ log (moles HA
-

/moles H
2
A)
Amphiprotic Region
pH = ½ (pKa
1
+ pKa
2
)
Buffer Region: HH Equation
pH = pK
a2
+ log (moles A
2-

/moles HA
-
)
Equivalence Region: Use ICE and K
b1

pOH = ½ (pK
b1
+ p[moles H
2
A/total volume])
Excess base region:
pOH = -log (moles excess base/ total volume)
Weak H
3
A vs Strong Base Titration
Suppose you want to do a physiological
experiment that requires a pH 6.5 buffer. You find
that the organism with which you are working is
stable to a certain acid and its sodium salts (H
2
X:
Ka
1
= 2x10
-2
, Ka
2
= 5.0x10
-7
). You have available
1.0 M of this acid and 1.0 M NaOH in the lab.
How much of the NaOH should be added to 1.0 L
of the acid to make a buffer at pH 6.50?
 What is the pH of a solution made by mixing 0.30
mole NaOH, 0.25 mole Na
2
HPO
4
, and 0.20 mole
H
3
PO
4
with water and diluting with 1.00 L?
H
3
PO
4

pKa1 = 2.12
pKa2 = 7.21
pKa3 = 12.38