LECTURE 8

Buffer solutions
Buffer pH range
Buffer capacity
Change of pH
Calculations

By the end of this lecture you should

http://www.wewwchemistry.com/2012/12/how-do-buffers-work.html

Be able to define a buffer solution

Be able to calculate the buffer pH from
Henderson-Hasselbalch equation
Understand how buffers work
Understand and quantify the buffer
pH range and capacity
Calculate the changes in pH in buffer
solutions
Understand the role of buffer in
biochemical processes

Reading for this lecture

Chapters
15.2

Pages
572-578

Chapters
18.2

Pages
711-717

Buffer Solutions
!! Buffer solution (or buffer) is a solution that resist the change of pH
(upon dilution, addition of H+/OH-)
Buffer is a solution containing a mixture of a
weak acid and its conjugate base (CH3COOH + CH3COO-)
weak base and its conjugate acid (NH3 + NH4+)
Buffer is prepared by
mixing a weak acid with a salt of this acid and a strong base
(CH3COOH + CH3COONa)
mixing a weak base and a salt of this base and a strong acid
(NH3 + NH4Cl)
partial neutralization of a weak acid with strong base
(x CH3COOH + NaOH x CH3COONa + (1-x) CH3COOH + H2O
partial neutralization of a weak base with strong acid
(x NH3 + HCl x NH4Cl + (1-x) NH3 + H2O)

Example
Which of the following combinations will result in a buffer solution?

50 mL of 0.1 M acetic acid AND 25 mL of 0.1 M NaOH

50 103 0.1 5mmol of acid AND 25 103 0.1 2.5mmol of base
2.5mmol of salt AND 2.5mmol of acid

25 mL of 0.1 M acetic acid AND 50 mL of 0.1 NaOH

25 103 0.1 2.5mmol of acid AND 50 10 3 0.1 5mmol of base
2.5mmol of salt AND 2.5mmol of base

50 mL of 0.1 M acetic acid AND 15 mL of 0.2 M KOH

50 103 0.1 5mmol of acid AND 15 103 0.2 3mmol of base
3mmol of salt AND 2mmol of acid

50 mL of 0.1 M acetic acid AND 35 mL of 0.2 M KOH

50 103 0.1 5mmol of acid AND 35 103 0.2 7mmol of base
5mmol of salt AND 2mmol of base

Example
Which of the following combinations will result in a buffer solution?

50 mL of 0.1 M acetic acid AND 25 mL of 0.1 M NaOH

50 103 0.1 5mmol of acid AND 25 103 0.1 2.5mmol of base
2.5mmol of salt AND 2.5mmol of acid

25 mL of 0.1 M acetic acid AND 50 mL of 0.1 NaOH

25 103 0.1 2.5mmol of acid AND 50 10 3 0.1 5mmol of base
2.5mmol of salt AND 2.5mmol of base

50 mL of 0.1 M acetic acid AND 15 mL of 0.2 M KOH

50 103 0.1 5mmol of acid AND 15 103 0.2 3mmol of base
3mmol of salt AND 2mmol of acid

50 mL of 0.1 M acetic acid AND 35 mL of 0.2 M KOH

50 103 0.1 5mmol of acid AND 35 103 0.2 7mmol of base Cant base & salt
5mmol of salt AND 2mmol of base

also make a
buffer?

The pH of a buffer
7.2

CH 3COONa CH 3COO Na
CH 3COO H 2O

6.7

CH 3COOH OH

{SB1} Na cS
{SB 2} CH 3COO CH 3COOH cS cA

{EN } Na H CH 3COO OH
CH 3COO H
Ka
CH 3COOH
K w H OH

6.2

pH

5.7
5.2
4.7
1.E-09

H cS K a H cA K a K w H K a K w 0
3

1.E-07

1.E-05

cbuffer

Acetic acid buffer

pK a 4.8

pH=f (Ka, cA, cS)

Too complex for
practical use

1.E-03

cS
1
cA

1.E-01

1.E+01

The pH of a buffer -- simplification

H cS K a H cA K a K w H K a K w 0
3

cS H cA K a H 0

CH 3COO H
Ka
CH 3COOH

c
H K a A
c
S

pH pK a log

CH 3COOH K cA
H K a
a
cS
CH 3COO

cS
cA

Henderson-Hasselbalch equation

pH pK a log

cconj. base
cacid

pH pK a log

cS
cA

The pH of a buffer depends on

the ratio of base/acid only

7.2
6.7

pH

6.2
5.7
5.2
4.7
1.E-09

1.E-07

1.E-05

1.E-03

1.E-01

cbuffer

Henderson-Hasselbalch equation

pH pK a log

cconj. base
cacid

The pH of a buffer depends on

the ratio of base/acid only

1.E+01

7.2
6.7

pH

6.2
5.7
5.2
4.7
0.0

0.5

1.0

1.5

cbuffer

Henderson-Hasselbalch equation

pH pK a log

cconj. base
cacid

The pH of a buffer depends on

the ratio of base/acid only

2.0

Mechanism of buffering
If acid is added to the buffer it reacts with the conjugate base
H 3O CH 3COO

CH3COOH

CH 3COOH H 2O

CH 3COOH cA x

CH 3COO cS x

CH3COO- CH3COOH

CH3COO- CH3COOH

H+

If base is added to the buffer it reacts with the conjugate acid

OH CH 3COOH

CH3COO-

CH 3COO H 2O

CH 3COOH cA y

CH 3COO cS y
CH3COOH CH3COO-

Adding H+ is equivalent to
withdrawing OHy = -x

OH-

CH3COOH

CH3COO-

Mechanism of buffering

pH pK a log

cS x
cA x

9
8
7
pH

6
5
4
3
2
1

OH- added

H+ added

Mechanism of buffering

pH pK a log

cS x
cA x

14
12

pH

10
8

6
4
2
0

OH- added

H+ added

pH range and buffer capacity

are the two important buffer characteristics.
The pH range of a buffer is the range of pH where the buffer acts effectively.
The ratio of salt and acid concentrations extends the range around pKa,
typically by 1pH unit.

The buffer capacity is the amount of acid or base that can be added to the buffer
before the pH begins to change rapidly.
Buffers have optimum capacity when cS 1
cA

The higher the concentrations (cS, cA) the higher the buffer capacity

pH range and buffer capacity

8
7

buffer capacity

pH range

pH

4
3
2

OH- added

H+ added

Buffer capacity comparison of different base/acid ratios

Acetic Acid/Sodium Acetate Buffer

6.0

5.5
cS/cA=1/1
cS/cA=1/2

5.0

pH

cS/cA=2/1
cS/cA=1/10

4.5

cS/cA=10/1

4.0

3.5

OH- added

H+ added

Example
Will the following combinations result in a buffer solution?

50 mL of 0.1 M acetic acid AND 50 mL of 0.1 M NaOH

50 103 0.1 5mmol of acid AND 50 103 0.1 5mmol of base
5mmol of salt AND 0mmol of acid

H cS K a H cA K a K w H K a K w 0
3

buffer

salt of a weak acid and a strong base

H cS K a H K w H K a K w 0
3

However, a salt is fully dissociated

CH 3COONa CH 3COO Na

and anions will react with water

CH 3COO H 2O

CH 3COOH OH

In principle, it is a buffer
but with a very narrow pH range
and a very low buffer capacity

Buffers prepared from a weak base and a corresponding salt (weak base+strong acid)

NH 3 H 2O

NH 4 OH

NH 4 OH
Kb
NH 3

NH 3 K cB
OH K b
b
cS
NH 4
pOH pK b log

cS
cB

Comparison
Henderson-Hasselbalch
CH 3COOH

CH 3COO H

CH 3COO
pH pK a log
CH 3COOH

Heylman
NH 3 H 2O

NH 4 H 3O

NH 4
pOH pK b log
NH 3
NH 4
14 pH 14 pK a log
NH 3
pH pK a log

Heylman Equation

conj. base

pH pK a log
conj. acid

NH 3
NH 4

Calculations
A buffer solution is prepared by dissolving 12g of formic acid and 23g of sodium formate
in 1L of solution. Calculate the pH of the buffer.
K a , HCOOH 1.7 104
M HCOOH 46g/mol

M HCOONa 68g/mol

pK a log K a log1.7 104 3.77

nHCOOH

mHCOOH 12

0.261mol
M HCOOH 46

23
0.338mol
68
n
0.261
c A HCOOH
0.261mol/L
V
1
n
0.338
cS HCOONa
0.338mol/L
V
1
c
pH pKa log S
cA
nHCOONa

pH 3.77 log

0.338
3.88
0.261

Calculations
Caculate the pH of a buffer solution from previous example upon addition of
a) 0.1mol HCl
b) 0.1mol NaOH.
H HCOO HCOOH

OH HCOOH HCOO +H 2O

addition of x HCl will

addition of x NaOH will

decrease cS cS cSo x

increase cS cS cSo x

increase c A c A c Ao x

decrease c A c A c Ao x

pH pK a log

cS
cA

pH pK a log

cS
cA

cSo x
pH pK a log o
cA x

cSo x
pH pK a log o
cA x

0.338 0.1
pH 3.77 log
0.261 0.1
pH 3.60

pH 3.77 log
pH 4.20

0.338 0.1
0.261 0.1

Calculations
Calculate a capacity of a buffer from previous example for a pH range 3-4.6
pH pK a log

cS
cA

pH pK a log

cS
cA

cSo x
pH pK a log o
cA x

cSo x
pH pK a log o
cA x

0.338 x
0.261 x
0.338 x
0.83 log
0.261 x
0.338 x
100.83
0.261 x
0.338 x
6.761
0.261 x
6.761 0.261 x 0.338 x

0.338 x
0.261 x
0.338 x
0.77 log
0.261 x
0.338 x
100.77
0.261 x
0.338 x
0.17
0.261 x
0.17 0.261 x 0.338 x

1.765 6.761x 0.338 x

0.0444 0.17 x 0.338 x

1.427 7.761x

1.17 x 0.294

x 0.184mol OH

x 0.251mol H

4.6 3.77 log

3 3.77 log

Calculations
Calculate a capacity of a buffer from previous example for a pH range 3-4.6
pH pK a log

cS
cA

pH pK a log

cSo x
pH pK a log o
cA x

cSo x
pH pK a log o
cA x 6

0.338 x5
0.261 x4
0.338 x
0.83 log
3
0.261 x
0.338 x
100.83
2
0.261 x
0.338 x
1
6.761
0.261 x
-0.3
6.761 0.261 x 0.338 x

0.338 x
0.261 x
0.338 x
0.77 log
0.261 x
0.338 x
100.77
0.261 x
0.338 x
0.17
0.261 x
0.3
0.17 0.261 x 0.338 x
3 3.77 log

pH

4.6 3.77 log

1.765 6.761x 0.338 x

cS
cA

-0.2

-0.1

0.1

H+ added / mol

0.2

0.0444 0.17 x 0.338 x

1.427 7.761x

1.17 x 0.294

x 0.184mol OH

x 0.251mol H

Buffers in living organisms

Living cells make use of buffers to maintain the acid-base homeostasis
regulation of acidity/alkalinity maintaining the stability of the body's internal
environment in response to changes in external conditions.
Human blood
Is an intricate slightly basic buffer that maintains pH in the range 7.35-7.45

Carbonic acid/bicarbonate buffer

H (aq ) HCO3 (aq )

pH pK a , H 2CO3

H 2CO3 (aq )

H 2O (l ) CO2 ( g )

HCO3
log
H 2CO3

pK a , H 2CO3 6.37

HgbH O2

HgbO2 H