BUFFER

SOLUTION
 WHAT IS A BUFFER SOLUTION?

A buffer solution is solution that can resist drastic
changes in pH upon the addition of small amount of
strong acid or strong base.

 Sometimes it is important in chemical and biological

systems that pH remains nearly constant

This can be achieved by using BUFFERS –

solutions that resist drastic changes in pH
 Two types of buffer solutions:
Acidic buffer solution and Basic buffer solution

How to prepare buffer solutions

 Acidic buffer
A mixture of a weak acid + soluble ionic salt of
the weak acid.
Example: A mixture of CH3CO2H/NaCH3CO2
Basic buffer
A mixture of a weak base + soluble ionic salt of
the weak base

Example: NH3/NH4Cl
 Which of the following are buffer systems? (a) KF/HF
(b) KCl/HCl, (c) Na2CO3/H2 CO3

(a) HF is a weak acid and KF is its salt that contain

conjugate base F- - buffer solution

(b) HCl is a strong acid

not a buffer solution
(c) H2CO32- is a weak acid and Na2CO3- is its salt that contains
conjugate base CO32- buffer solution

16.3
Chemistry In Action: Maintaining the pH of Blood

16.3
A buffer solution is a solution of:
1. A weak acid or a weak base and
2. The salt of the weak acid or weak base
Both must be present!

A buffer solution has the ability to resist changes in pH upon

the addition of small amounts of either acid or base.

Consider an equal molar mixture of CH3COOH and CH3COONa

CH3COOH (aq) H+ (aq) + CH3COO- (aq)

Adding more acid creates a shift left IF

enough acetate ions are present
16.3
Notice how the solutions are made up:

- they contain a conjugate acid-base pair

The common ion effect is the shift in equilibrium caused by the
addition of a compound having an ion in common with the
dissolved substance.

Consider mixture of CH3COONa (strong electrolyte) and

CH3COOH (weak acid).

CH3COONa (s) Na+ (aq) + CH3COO- (aq)

common
ion
CH3COOH (aq) H+ (aq) + CH3COO- (aq)

16.2
If a small amount of OH- or H3O+ is added to

a buffer it will react with the basic or acidic

component of the buffer respectively
 Consider the acetic-acid/sodium acetate buffer

CH3COONa(aq)  CH3COO-(aq) + Na+(aq) (1)

CH3COOH(aq) + H2O(l)
CH3COO-(aq) + H3O+(aq) (2)
 Sodium acetate dissolves completely to produce

a high concentration of acetate ions

 Adding a strong acid means H3O+ is added

Equilibrium (2) shifts to the left. This reaction

occurs to a great extent
- +
CH3COO (aq) + H3O (aq)
CH3COOH(aq) + H2O(l)
 Use the Henderson-Hasselbach equation

pH = pKa + log [conjugate base]

[acid]

[salt]
pH = pKa + log
[acid]
 OR…… Use the Henderson-Hasselbach equation
Consider mixture of salt NaA and weak acid HA.
NaA (s) Na+ (aq) + A- (aq) [H+][A-]
Ka = pKa = -log Ka
HA (aq) H+ (aq) + A- (aq) [HA]

Ka [HA]
[H ] =
+
[A-] Henderson-Hasselbach
[HA] equation
-log [H+] = -log Ka - log
[A-] [conjugate base]
- pH = pKa + log
-log [H ] = -log Ka + log
+ [A ] [acid]
[HA]
-
pH = pKa + log [A ]
[HA]

16.2
 What is the pH of a solution containing 0.30 M HCOOH
and 0.52 M HCOOK?

Mixture of weak acid and conjugate base!

HCOOH (aq) H+ (aq) + HCOO- (aq)

Initial (M) 0.30 0.00 0.52
Change (M) -x +x +x
Equilibrium (M) 0.30 - x x 0.52 + x
-
Common ion effect pH = pKa + log [HCOO ]
[HCOOH]
0.30 – x  0.30
[0.52]
0.52 + x  0.52 pH = 3.77 + log = 4.01
[0.30]
HCOOH pKa = 3.77
16.2
 What is the pH of a solution containing 0.30 M HCOOH
and 0.52 M HCOOK?

Mixture of weak acid and conjugate base!

HCOOH (aq) H+ (aq) + HCOO- (aq)

Initial (M) 0.30 0.00 0.52
Change (M) -x +x +x
Equilibrium (M) 0.30 - x x 0.52 + x

Ka for HCOOH = 1.8 x 10 -4

x = 1.038 X 10 -4
[H+] [HCOO-]
Ka = pH = 3.98
[HCOOH]
16.2
 HCl H+ + Cl-
HCl + CH3COO- CH3COOH + Cl-

16.3
 5 g of NH3NO3( MW 80) is disso
 Calculate the pH of the 0.30 M NH3/0.36 M NH4Cl buffer
system. What is the pH after the addition of 20.0 mL of
0.050 M NaOH to 80.0 mL of the buffer solution?
NH3 (aq) + H2O (l) NH4+ (aq) + OH- (aq)
[NH4+] [OH-]
Kb = = 1.8 X 10-5
[NH3]
Initial 0.30 0.36 0
Change -x +x +x
End 0.30 - x 0.36 + x x
(.36 + x)(x)
1.8 X 10-5 =
(.30 – x)
0.36x
1.8 X 10 
-5
x = 1.5 X 10-5 pOH = 4.82 pH= 9.18
0.30
16.3
 Calculate the pH of the 0.30 M NH3/0.36 M NH4Cl buffer
system. What is the pH after the addition of 20.0 mL of
0.050 M NaOH to 80.0 mL of the buffer solution?
final volume = 80.0 mL + 20.0 mL = 100 mL
NH4+ 0.36 M x 0.080 L = 0.029 mol / .1 L = 0.29 M
OH- 0.050 x 0.020 L = 0.001 mol / .1 L = 0.01M
NH3 0.30 M x 0.080 = 0.024 mol / .1 L = 0.24M
start (M) 0.29 0.01 0.24
NH4+ (aq) + OH- (aq) H2O (l) + NH3 (aq)
end (M) 0.28 0.0 0.25
[H+] [NH3]
Ka= = 5.6 X 10 -10
[NH4+] [H+] = 6.27 X 10 -10
[H+] 0.25 pH = 9.20
= 5.6 X 10 -10

0.28 16.3
 Calculate the pH of the 0.30 M NH3/0.36 M NH4Cl buffer
system. What is the pH after the addition of 20.0 mL of
0.050 M NaOH to 80.0 mL of the buffer solution?

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

[NH3] [0.30]
pH = pKa + log pKa = 9.25 pH = 9.25 + log = 9.17
[NH4+] [0.36]
final volume = 80.0 mL + 20.0 mL = 100 mL

start (M) 0.29 0.01 0.24

NH4+ (aq) + OH- (aq) H2O (l) + NH3 (aq)
end (M) 0.28 0.0 0.25

[0.25]
pH = 9.25 + log = 9.20
[0.28]
16.3
 Titrations
In a titration a solution of accurately known concentration is
added gradually added to another solution of unknown
concentration until the chemical reaction between the two
solutions is complete.

Equivalence point – the point at which the reaction is complete

Indicator – substance that changes color at the

endpoint (hopefully close to the equivalence point)

Slowly add base

to unknown acid
UNTIL
The indicator
changes color
(pink) 4.7
Strong Acid-Strong Base Titrations
100%
NaOH (aq) + HCl (aq) H2O (l) + NaCl (aq) ionization!
OH- (aq) + H+ (aq) H2O (l) No equilibrium

16.4
Weak Acid-Strong Base Titrations
CH3COOH (aq) + NaOH (aq) CH3COONa (aq) + H2O (l)
CH3COOH (aq) + OH- (aq) CH3COO- (aq) + H2O (l)
At equivalence point (pH > 7):
CH3COO- (aq) + H2O (l) OH- (aq) + CH3COOH (aq)

16.4
Strong Acid-Weak Base Titrations
HCl (aq) + NH3 (aq) NH4Cl (aq)
H+ (aq) + NH3 (aq) NH4Cl (aq)
At equivalence point (pH < 7):
NH4+ (aq) + H2O (l) NH3 (aq) + H+ (aq)

16.4
Acid-Base Indicators

16.5
The titration curve of a strong acid with a strong base.

16.5
 Which indicator(s) would you use for a titration of HNO2
with KOH ?

Weak acid titrated with strong base.

At equivalence point, will have conjugate base of weak acid.
At equivalence point, pH > 7
Use cresol red or phenolphthalein

16.5
 Exactly 100 mL of 0.10 M HNO2 are titrated with 100 mL of
a 0.10 M NaOH solution. What is the pH at the
equivalence point ?
start (moles) 0.01 0.01
HNO2 (aq) + OH- (aq) NO2- (aq) + H2O (l)
end (moles) 0.0 0.0 0.01
0.01
Final volume = 200 mL [NO2 ] = 0.200 = 0.05 M
-

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

Initial (M) 0.05 0.00 0.00
Change (M) -x +x +x
Equilibrium (M) 0.05 - x x x
[OH-][HNO2] x2
Kb = = = 2.2 x 10 -11 pOH = 5.98
[NO2-] 0.05-x
0.05 – x  0.05 x  1.05 x 10-6 = [OH-] pH = 14 – pOH = 8.02