ALMUSTAQBAL UNIVERSITY COLLEGE

Biomedical Engineering Department

Stage : Second year students

Subject : Chemistry 1 - Lecture 10

Lecturer: Assistant professor Dr. SADIQ . J. BAQIR

Buffer solutions

The buffer is a mixture of a weak acid and its conjugate base (Salt) or a
weak base and its conjugate acid(Salt) , that resists change in pH of a
solution due to dilution or addition of a small amounts of strong acid or
base . Buffers are used to Maintain the pH of solutions at relatively
constant and predetermined level.
Usually, buffers have a useful pH range = pKa ± 1,

Calculation of the pH of different types of Buffer solutions

1. acidic buffers

Consists of weak acid (HA) and its salt (A-) .Typical example is (acetic
acid – acetate salt ( CH3COOH – CH3COO- )

HA + H2O ⇌ H3O⁺ + Aˉ ‫ ــــــــــــــــــــ‬1

[𝐻3 𝑂+ ][𝐴− ]
Ka =
[𝐻𝐴]

Aˉ + H2O ⇌ OHˉ + HA ‫ ــــــــــــــــــــ‬2

[𝑂𝐻][𝐻𝐴] 𝐾𝑤
Kb = =
[𝐴−] 𝐾𝑎
equilibrium① will decrease CHA by amount [H3O⁺] and equilibrium ② will
increase it by amount [OH-].

[HA]equil. = CHA – [H3O⁺] + [OHˉ ]

Similarly equilibrium ① will increase [Aˉ] by amount [H3O+]

while equilibrium ② will decrease [Aˉ] by amount [OHˉ] then

[Aˉ ]equil. = CA- + [H3O⁺] – [OHˉ ]

As we have acid then

[HA] = CHA – [H3O+]

[A-] = CA- + [H3O+]

And because we have weak acid then

[HA]  CHA

[Aˉ ]  CA-

[𝐻3 𝑂+ ][𝐴− ]
Ka =
[𝐻𝐴]

[𝐻𝐴]
[H3O⁺] = Ka
[𝐴− ]

𝐶𝐻𝐴
[H3O+] = Ka
𝐶𝐴−

𝐶𝐻𝐴
- log [H3O] = -log Ka - log
𝐶𝐴−
 𝐂𝐀
pH = pKa + log
𝐂𝐇𝐀

𝐂𝐬𝐚𝐥𝐭
** pH = pKa + log ( Henderson equation)
𝐂𝐚𝐜𝐢𝐝

Example: what is the pH of a solution that is (0.40 M) in formic acid

(Ka= 1.80 x 10-4 ) and (1.0 M) in sodium formate ?

Solution :

The pH of the solution will be effected by Ka of formic acid (HCOOH)

and Kb of formate ion (HCOO-)

HCOONa → HCOO- + Na+

HCOOH + H2O ⇌ HCOO- + H3O+ Ka = 1.77 x10ˉ⁴

𝑲𝒘
HCOO- + H2O ⇌ HCOOH + OH- Kb = = 5.65 x 10ˉ¹¹
𝑲𝒂

Since Ka of formic acid >> Kb for formate the solution will be acidic
and Ka will determine the H3O+ conc.

𝐂𝐬𝐚𝐥𝐭
pH = pKa + log
𝐂𝐚𝐜𝐢𝐝

pKa = - log Ka = - log (1.77 x 10-4) = 3.75

𝟏.𝟎
pH = 3.75 + log = 4.14
𝟎.𝟒

[H3O+]= 10-pH = 10- 4.14 = 7.2 x 10-5

 [H3O⁺]
Check if 𝑥 100 ‹ 10 % Then approximation is valid
[𝐻𝐶𝑂𝑂𝐻]

7.2 x10−5
𝑥 100 = 0.018 %
0.4

The approximation is valid:

B) basic Buffers

It is composed of a solution of a weak base (B) and it`s conjugate acid

(Salt) BH+ e.g : NH3-NH4Cl .

+ - [OH− ][BH+ ]
1) B + H2O ⇌ BH + OH Kb =
[B]

NH3 + H2O ⇌ NH4+ + OH-

Kw [H3 O+ ][B]
2) BH+ + H2O ⇌ H3O+ + B Ka = =
Kb [BH+ ]

NH4+ + H2O ⇌ H3O+ + NH3

[B] will decrease in equilibrium ①by amount [OH-] & increase in
equilibrium ②by [H3O+]
Then [B] = CB – [OH-] + [H3O+]
Similarly [BH+] will increase in equilibrium① By [OH-] and decrease
in equilibrium② by [H3O+].
Then [BH+] = CBH+ + [OH-] – [H3O+]
[B] ≡ CB and [BH+]≡CBH+ (by approximation)
[OH− ][BH+ ]
Kb =
[B]
 CB
[OH-]= Kb
CBH+

[BH+ ]
pOH= pKb + log [B]

Csalt
pOH = pKb + log (Henderson equation)
Cbase

In General:
𝐂𝐬𝐚𝐥𝐭
pH = pKa + 𝐥𝐨𝐠 (for acidic buffer)
𝐂𝐚𝐜𝐢𝐝

𝐂𝐬𝐚𝐥𝐭
pOH = pKb + 𝐥𝐨𝐠 (for basic buffer)
𝐂𝐛𝐚𝐬𝐞

pH = 14 – pOH
Example: calculate the pH of a solution that is 0.2 M in NH3 and 0.3 M
in NH4Cl ( Kb =1.75 x10-5) .
Solution:
NH4Cl → NH4+ + Cl-
Kw 10−14
+
NH4 + H2O ⇌ NH3 + H3O +
Ka = = = 5.7 x 10−10
Kb 1.75 x 10−5

NH3 + H2O ⇌ NH4+ + OH- Kb = 1.75x10−5

because Kb >> Ka the solution is assumed to be basic
𝐂𝐬𝐚𝐥𝐭
pOH = pKb + 𝐥𝐨𝐠 (for basic buffer)
𝐂𝐛𝐚𝐬𝐞

pKb = - log Kb = - log (1.75 x 10-5) = 4.75

𝟎.𝟑
pOH = 4.75 + 𝐥𝐨𝐠 = 4.93
𝟎.𝟐
To check the validity of approximation we calculate [OH-]
[OH-]= 10-pOH = 10- 4.93 = 1.17 x 10-5
[OH− ]
then Check if 𝑥 100 ‹ 10 % Then approximation is valid
[𝐵𝑎𝑠𝑒]

1.17 𝑥 10−5
Then x 100 = 5.85 x 10-3 (approximation is valid)
0.2

pH= 14 − 4.93 = 9.07

Properties of buffer solution:

① Effect of dilution:
The pH of the buffer solution remains independent of dilution until the
concentration of species it's contain are decreased to the point where the
approximation mentioned above become invalid .
Example: calculate the change in pH of a buffer containing (0.4M)
formic acid HCOOH (Ka=1.77x10-4) and (1M) sodium formate
HCOONa after dilution by a factor of 50 times .
Solution:
HCOONa → HCOO- + Na+

HCOOH + H2O ⇌ HCOO- + H3O+ Ka = 1.77 x10ˉ⁴

𝑲𝒘
HCOO- + H2O ⇌ HCOOH + OH- Kb = = 5.65 x 10ˉ¹¹
𝑲𝒂

Since Ka of formic acid >> Kb for formate the solution will be acidic.

[HCOONa]
pH = pKa + log [HCOOH]
pKa = - log(1.77x10-4) = 3.75
a. Before Dilution
1
pH = 3.75 + log = 4.15
0.4

[H3O+]= 10-pH = 10- 4.15 = 7.2 x 10-5

[H3O⁺]
Check if 𝑥 100 ‹ 10 % Then approximation is valid
[𝐻𝐶𝑂𝑂𝐻]
7.1 x10−5
𝑥 100 = 0.0177 %
0.4

The approximation is valid.

b. After dilution with 50 times .
M1V1 = M2V2

for [HCOOH]
0.4 x1 = M2 x 50
0.4
[HCOOH] = = 8 x 10−3 M
50

For [HCOO- ]
1 x 1 = M2 x 50
1
[HCOO-] = = 2 x 10−2 M
50

2 x 10−2
pH = 3.75 + log 8 x 10−3 = 4.15

[H3O+]= 10-pH = 10- 4.15 = 7.2 x 10-5

 [H3O⁺]
Check if 𝑥 100 ‹ 10 % Then approximation is valid
[𝐻𝐶𝑂𝑂𝐻]
7.2 x10−5
𝑥 100 = 0.018 %
0.4

The approximation is valid.

∴ NO change in pH occur after 50 times dilution) ∆PH = 0(

② Effect of adding strong acid or base:

Buffer solution resist the pH change after addition of small amount of
strong acid or base.
Example: Calculate the pH change that take place when 100 mL portion
of: a) 0.05 M NaOH b) 0.05 M HCl
is added seperately to 400 mL of buffer solution of (0.2M) NH3 and
(0.3M) NH4Cl (Kb = 1.75x10-5) .
Solution:
a. The original buffer before addition
NH4Cl → NH4+ + Cl-
Kw 10−14
NH4+ + H2O ⇌ NH3 + H3O+ Ka = = = 5.7 x 10−10
Kb 1.75 x 10−5

NH3 + H2O ⇌ NH4+ + OH- Kb = 1.75x10−5

because Kb >> Ka the solution is assumed to be basic
𝐂𝐬𝐚𝐥𝐭
pOH = pKb + 𝐥𝐨𝐠 (for basic buffer)
𝐂𝐛𝐚𝐬𝐞

pKb = - log Kb = - log (1.75 x 10-5) = 4.75

 𝐶𝑁𝐻4 𝐶𝑙 0.3
pOH = pKb + log = 4.76 + log = 4.93
𝐶𝑁𝐻3 0.2

[OH-]= 10-pOH = 10- 4.93 = 1.17 x 10-5

To check the validity of approximation we calculate [OH-] then
[OH−]
Check if 𝑥 100 ‹ 10 % Then approximation is valid
[𝐵𝑎𝑠𝑒]

1.17 𝑥 10−5
Then x 100 = 5.85 x 10-3 % (approximation is valid)
0.2

pH =14 - 4.93 = 9.07

b. after addition of strong base or acid
1) addition of NaOH converts part of NH4+ in the buffer to NH3
NH4+ + OH- ⇌ NH3 + H2O ( OH- from NaOH)
The analytical concentration of NH3 and NH4Cl become :
original No.of moles of NH3 + moles of produced NH3
𝐶𝑁𝐻3 =
Total New volume (L)

original No.of mmoles of NH3 + mmoles of produced NH3

Or 𝐶𝑁𝐻3 =
Total New volume (mL)

No.of moles of produced NH3 = No. of moles of reacted NaOH

M𝑁𝐻3 V𝑁𝐻3 + MNaOH VNaOH
𝐶𝑁𝐻3 =
V𝑁𝐻3 +VNaOH

400x0.2+100x0.05 85
𝐶𝑁𝐻3 = [400+100}
= = 0.17M
500

original No. of moles of NH4 + − moles of reacted NH4 +

CNH4+ =
Total New volume(L)

original No. of mmoles of NH4 + − mmoles of reacted NH4 +

Or CNH4+ =
Total New volume(mL)
No. of moles of consumed NH4+ = No. of moles of reacted NaOH
M𝑁𝐻4 𝐶𝑙 V𝑁𝐻4 𝐶𝑙 − MNaOH VNaOH
𝐶𝑁𝐻4𝐶𝑙 =
𝑉𝑁𝐻4 𝐶𝑙+ VNaOH

400x0.3−100x0.05 115
𝐶𝑁𝐻4𝐶𝑙 = [400+100]
= = 0.23M
500

0.23
pOH = 4.76+ log = 4.89 (Henderson equation )
0.17

[OH-]= 10-pOH = 10- 4.93 = 1.17 x 10-5

To check the validity of approximation we calculate
[OH− ]
if 𝑥 100 ‹ 10 % Then approximation is valid
[𝐵𝑎𝑠𝑒]

1.17 𝑥 10−5
Then x 100 = 5.85 x 10-3 (approximation is valid)
0.2

pH =14 - 4.89 = 9.11

∆pH = 9.11 − 9.07 = 0.04

2) addition of HCl converts part of NH3 to NH4Cl

NH3 + H3O+ ⇌ NH4+ + H2O (H3O+ from HCl)
original No.of moles of NH3 − moles of reacted NH3
CNH3 =
Total New volume (L)

original No.of mmoles of NH3 − mmoles of reacted NH3

Or CNH3 =
Total New volume (mL)

No.of moles of consumed NH3 = No. of moles of reacted HCl

M𝑁𝐻3 V𝑁𝐻3 − MHCl VHCl
𝐶𝑁𝐻3 =
V𝑁𝐻3 +VHCl
 400 x 0.2 − 100 x 0.05
𝐶𝑁𝐻3 = [400+100}
= 0.150M

original No of moles of NH4 + + moles of produced NH4 +

𝐶NH4+ =
Total New volume (L)

original No of mmoles of NH4 + + mmoles of produced NH4 +

Or 𝐶NH4 + =
Total New volume (mL)

No. of moles of produced NH4 = No. of moles of reacted HCl

M𝑁𝐻4 𝐶𝑙 V𝑁𝐻4 𝐶𝑙 + MHCl VHCl
𝐶𝑁𝐻4𝐶𝑙 =
V𝑁𝐻4 𝐶𝑙 + VHCl

400 x 0.3 + 100 x 0.05

𝐶𝑁𝐻4𝐶𝑙 = [400+100]
= 0.25M

𝑁𝐻4 𝐶𝑙
pOH= pKb + log ( Henderson equation )
C𝑁𝐻3

0.25
pOH = 4.76 + log = 4.98
0.15

[OH-]= 10-pOH = 10- 4.98 = 1.05 x 10-5

To check the validity of approximation we calculate [OH-] then
[OH− ]
Check if 𝑥 100 ‹ 10 % Then approximation is valid
[𝐵𝑎𝑠𝑒]

1.05 𝑥 10−5
Then x 100 = 5. 51 x 10-3 (approximation is valid)
0.2

pH =14 - 4.98 = 9.02

∆pH = 9.02 − 9.07 = − 0.05

Addition ∆𝐩𝐇
100 mL 0.05 M NaOH 0.04
100 mL 0.05 M HCl - 0.05
Exercise:
Calculate the pH change that take place when 100 mL portion of:
a) 0.05 M NaOH b) 0.05 M HCl is added seperately to 400 mL of
buffer solution of (0.1M) CH3COOH and (0.2M) CH3COONa (Ka =
1.74x10-5) .
Hint:
CH3COOH + NaOH ⇌ CH3COONa + H2O
CH3COO- + HCl ⇌ CH3COOH

Preparation of buffer:
To prepare a buffer, it is to choose the acid with the pKa close to the
desired pH. Usually, buffers have a useful pH range = pKa ± 1, but the
closer it is to the weak acid's pKa, is the better .
Example:
Describe how you might prepare approximately (500 mL) of pH 4.5
buffer solution from 1 M acetic acid (CH3COOH) and sodium acetate
(CH3COONa) (82.03 g /mole) , (Ka=1.74 x10-5) .
Solution:
For acidic buffer(pH= 4.5)
CH3COOH + H2O ⇌ CH3COO- + H3O+
𝐂𝐬𝐚𝐥𝐭
pH = pKa + log ( Henderson equation for acidic buffers)
𝐂𝐚𝐜𝐢𝐝
pKa = - log( 1.74 x 10-5) = 4.76
[𝑪𝑯𝟑 𝑪𝑶𝑶− ]
4.5 = 4.76 + log
[𝑪𝑯𝟑 𝑪𝑶𝑶𝑯]

[𝑪𝑯𝟑 𝑪𝑶𝑶− ]
4.5 = 4.76 + log
[𝟏]

4.5 – 4.76 = log [CH3COO-] – log 1

log [CH3COO-]= - 0.26
[CH3COO-] = 10-0.26 = 0.549 M
Mass of CH3COONa needed = Molarity(M) x V(liter) x Mwt
500
Mass of CH3COONa = 0.549(mol/L) x 𝐿 x 82.03(g/mol) = 22.52 g
1000

The required buffer is to be made by dissolution of 22.52 g of

CH3COONa and completing the volume to 500 mL with 1M CH3COOH

Buffer capacity
It is defined as the number of moles of an acid or base added to 1 liter
of a buffer solution to cause its pH to change by 1 unit.

Buffer capacity depends on the amount of acid and base used to prepare
the buffer. For example, if you have a 1-L buffer solution made of (1
M CH3COOH and 1 M CH3COONa ) and a 1-L buffer solution that is (
0.1 M CH3COOH and 0.1 M CH3COONa) , although they will both
have the same pH, the first buffer solution will have a greater buffer
capacity because it has a higher amount of CH3COOH and CH3COO-.

To calculate buffer capacity, we use the following formula:

β = n / ΔpH

β is buffer capacity (it is unitless)

n is the number of moles of an acid or base (that were added to the
buffer) per liter of the buffer
𝑁𝑜.𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑎𝑐𝑖𝑑 𝑜𝑟 𝑏𝑎𝑠𝑒 𝑎𝑑𝑑𝑒𝑑
n=
𝑣𝑜𝑙 𝑜𝑓 𝑏𝑢𝑓𝑓𝑒𝑟(𝐿)
ΔpH is the difference between the initial pH of the buffer and the pH of
the buffer after the acid or base is added

The higher the capacity ( β ) , the more acid and base can be added to
the buffer before its pH changes significantly.

Example:
A volume of 150 mL of 0.2 M HCl was added to 600 mL of buffer with
a pH of 7.39. which gives the buffer solution a new pH of 7.03. What is
the capacity of this buffer solution?

Solution:

No. of moles = Molarity (M) x V(L)

Number of moles of HCl = 0.2 M × 0.150 L = 0.03 mol

𝑁𝑜.𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑎𝑐𝑖𝑑 𝑜𝑟 𝑏𝑎𝑠𝑒 𝑎𝑑𝑑𝑒𝑑 0.03 𝑚𝑜𝑙𝑒
n= = = 0.05 mol/L
𝑣𝑜𝑙 𝑜𝑓 𝑏𝑢𝑓𝑓𝑒𝑟(𝐿) 0.6 𝐿

n = 0.05 mol/L

ΔpH = |7.03 – 7.39| = 0.36

𝒏 𝟎.𝟎𝟓
β= = = 0.14
𝚫𝐩𝐇 𝟎.𝟑𝟔

Thus, the buffer capacity of our buffer solution is 0.14.