Titration Curves for

Complex Acid/Base Systems

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Department of Chemistry
Faculty of Science

Complex Acid/Base Systems

Solutions of

two acids/bases of different strength

an acid or a base that has two or more

acidic or basic functional groups

an amphiprotic substance

Department of Chemistry
Faculty of Science

Mixtures of
Strong and Weak Acids/Bases

Example 1
Calculate the pH after the addition of 0.00,
10.00, 29.00 and 30.00 mL of 0.1000 M NaOH
in the titration of 25.00 mL of a mixture that
is 0.1200 M in HCl and 0.0800 M weak acid
HA (Ka = 1.00 x 104).
3

Department of Chemistry
Faculty of Science

Mixtures of Strong and

Weak Acids/Bases

(a) After addition of 0.00 mL KOH

HCl + H2O H3O+ + Cl
HA + H2O

H3O+ + A

Ka = 1.0 x 104

[H3O+] = cHCl + [A] = 0.1200 + [A]

Assume that [A] << cHCl (0.1200 M)
[H3O+] 0.1200 M
pH = log 0.1200 = 0.92
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Department of Chemistry
Faculty of Science

Mixtures of Strong and

Weak Acids/Bases

Check assumption :
[H3O+][A]
= Ka = 1.0 x 104
[HA]
[H3O+][A]
0.1200 [A]
=
= 1.2 x 103 [A]
1.0 x 104
1.0 x 104
Mass-balance equation : cHA = [HA] + [A] = 0.0800 M
[HA] =

1.2 x 103 [A] + [A] = 0.0800 M

[A] = 6.7 x 105 M
[A] << 0.1200 M

Department of Chemistry
Faculty of Science

Mixtures of Strong and

Weak Acids/Bases

(b) After addition of 10.00 mL KOH

cHCl = (25.00 x 0.1200) (10.00 x 0.1000) = 0.0571 M
25.00 + 10.00
[H3O+] = cHCl + [A] = 0.0571 + [A]
Assume that [A] << cHCl (0.0571 M)
[H3O+] 0.0571 M
pH = log 0.0571 = 1.24
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Department of Chemistry
Faculty of Science

Mixtures of Strong and

Weak Acids/Bases

Check assumption :
[H3O+][A]
= Ka = 1.0 x 104
[HA]
[HA] =

[H3O+][A]
0.0571 [A]
=
= 5.7 x 102 [A]
1.0 x 104
1.0 x 104

Mass-balance equation :

0.0800 x 25.00
M
35.00
5.7 x 102 [A] + [A] = 0.0571 M
cHA = [HA] + [A] =

[A] = 1.0 x 104 M

Department of Chemistry
Faculty of Science

Mixtures of Strong and

Weak Acids/Bases

(c) After addition of 29.00 mL KOH

cHCl = (25.00 x 0.1200) (29.00 x 0.1000)
25.00 + 29.00
= 1.85 x 103 M
cHA = 25.00 x 0.0800 = 3.70 x 102 M
25.00 + 29.00
[H3O+] = cHCl + [A] = 1.85 x 103 + [A]

***
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Department of Chemistry
Faculty of Science

Mixtures of Strong and

Weak Acids/Bases

Mass-balance equation :
[HA] + [A] = cHA = 3.70 x 102 M
[H3O+][A]
= Ka = 1.0 x 104
[HA]
[H3O+][A]
[HA] =
1.0 x 104
[H3O+][A]
+ [A] = 3.70 x 102
1.0 x 104
3.70 x 106
[A] =
[H3O+] + 1.00 x 104

Department of Chemistry
Faculty of Science

Mixtures of Strong and

Weak Acids/Bases

[H3O+] = 1.85 x 103 + [A]

=

***

3.70 x 106
+ [A]
[H3O+] + 1.00 x 10-4

[H3O+]2 (1.75 x 103) [H3O+] 3.885 x 106 = 0

[H3O+] =

(1.75 x 103) + (1.75 x 103)2 4( 3.885 x 106)

2

[H3O+] = 3.03 x 103 M

pH = 2.52

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Department of Chemistry
Faculty of Science

Mixtures of Strong and

Weak Acids/Bases

[H3O+] = [H3O+]HCl + [H3O+]HA

[H3O+] = cHCl + [A]
3.03 x 103 = 1.85 x 103 + [A]
[A] = 3.03 x 103 1.85 x 103
= 1.18 x 10 3 M

11

Department of Chemistry
Faculty of Science

Mixtures of Strong and

Weak Acids/Bases

(d) After addition of 30.00 mL KOH

cHCl = (25.00 x 0.1200) (30.00 x 0.1000)
25.00 + 30.00
= 3.000 3.000 = 0 M
55.00
cHA = 25.00 x 0.0800 = 3.64 x 102 M
25.00 + 30.00
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Department of Chemistry
Faculty of Science

Mixtures of Strong and

Weak Acids/Bases

[H3O+] = Ka cHA
[H3O+] = 1.00 x 104 x 3.64 x 102 = 1.91 x 103 M
pH = log 1.91 x 103 = 2.72

13

Department of Chemistry
Faculty of Science

Mixtures of Strong and

Weak Acids/Bases

Titration curve
12.0
10.0

pH

8.0

6.0

4.0

2.0

0.0

Ka = 108
Ka = 106
Ka = 104
Ka = 102

10

20

30

40

50

Volume of 0.1000 M NaOH (mL)

60

Curves for the titration of strong/

weak acid mixtures with 0.1000 M
NaOH. Each titration is on 25.00
mL of a solution that is 0.1200 M
in HCl and 0.0800 M in HA.

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Department of Chemistry
Faculty of Science

Polyfunctional
Acids and Bases

Phosphoric Acid System

H3PO4 + H2O

H3

H2PO4 + H2O
HPO4 + H2O
2

H3PO4 + 3H2O

O+

+ H2PO4

[H3O+] [H2PO4]
Ka1 =
= 7.11 x 103
[H3PO4]

H3O+ + HPO42 Ka2 =

H3

O+

3H3

+ PO4

O+

+ PO4

[H3O+] [HPO42]
= 6.34 x 108
[H2PO4]

[H3O+] [PO43]
Ka3 =
= 4.2 x 1013
[HPO42]
[H3O+]3 [PO43]
Ka =
[H3PO4]
= Ka1Ka2Ka3 = 2.0 x 1022

Department of Chemistry
Faculty of Science

15

Polyfunctional
Acids and Bases

Carbon Dioxide - Carbonic Acid System

[H2CO3]
= 2.8 x 103
[CO2(aq)]
[H3O+] [HCO3]
K1 =
= 1.5 x 104
[H2CO3]

CO2(aq) + H2O

H2CO3

H2CO3 + H2O

H3O+ + HCO3

HCO3 + H2O

H3O+ + CO32

K2 =

H3O+ + CO32

Ka2 =

CO2(aq) + 2H2O
HCO3 + H2O

Khydration =

[H3O+] [CO32]
= 4.69 x 1011
[HCO3]
[H3O+] [HCO3]
+

H3O + HCO3 Ka1 =

= 4.2 x 107
[CO2(aq)]
[H3O+] [CO32]
= 4.69 x 101611
[HCO3]

Department of Chemistry
Faculty of Science

Polyfunctional
Acids and Bases

Example 2
Calculate the pH of a solution that is 0.02500 M CO2 .
Mass-balance equation :
cCO = 0.02500 = [CO2(aq)] + [H2CO3] + [HCO3] + [CO32]
2

Khyd, Ka1, Ka2 are small :

([H2CO3] + [HCO3] + [CO32]) << [CO2(aq)]
cCO = 0.02500 [CO2(aq)]
2

Department of Chemistry
Faculty of Science

17

Polyfunctional
Acids and Bases

Charge-balance equation :
[H3O+] = [HCO3] + 2[CO32] + [OH]
Ka2 << Ka1 and the solution is acid :
2[CO32] + [OH] << [HCO3]
[H3O+] [HCO3]

18

Department of Chemistry
Faculty of Science

CO2(aq) + 2H2O

Polyfunctional
Acids and Bases

H3

Ka1 =

O+

+ HCO3

[H3O+]2
0.02500

[H3O+] [HCO3]
Ka1 =
= 4.2 x 107
[CO2(aq)]

= 4.2 x 107

[H3O+] = 1.02 x 104 M

pH = log 1.02 x 104 = 3.99

19

Department of Chemistry
Faculty of Science

Polyfunctional
Acids and Bases

Solutions of Diprotic Acids

H3O+ + HA

H2A + H2O
HA

+ H2O

MBE :

H3

O+

A2

Ka1 =

[H3O+] [HA]
(1)
[H2A]

[H3O+] [A2]
Ka2 =
[HA]

c H A = [H2A] + [HA] + [A2]

(2)
(3)

CBE :

[H3O+] = [HA] + 2[A2] + [OH]

In acidic solution : [H3O+] = [HA] + 2[A2]

(4)
20

10

Department of Chemistry
Faculty of Science

Polyfunctional
Acids and Bases

Ka1/Ka2 > 103

Assume negligible dissociation of HA
[A2] << [HA] , [H2A]
(4) :

[H3O+] = [HA]

(3) :

H2A

(5)

= [H2A] + [HA]

[H2A] = cH A [HA]
2

[H2A] = cH A [H3O+]

(6)
21

Department of Chemistry
Faculty of Science

Polyfunctional
Acids and Bases

Ka1 =
Ka1

[H3O+] [HA]
[H2A]

(1)

[H3O+]2
=
c H A [H3O+]
2

Assumption : [H3O+] << c H A

2

[H3O+] =

KaCH A
2

Solve the quadratic equation for [H3O+]

22

11

Department of Chemistry
Faculty of Science

Polyfunctional
Acids and Bases

Check the assumption : [A2] << [HA] , [H2A]

Ka2 =

[H3O+] [A2]
[HA]

[H3O+] = [HA]
[A2] = Ka2

23

Department of Chemistry
Faculty of Science

Polyfunctional
Acids and Bases

Example 3
Calculate the pH of 0.1000 M maleic acid solution.
(HOOC CH = CH COOH).
H2M + H2O

H3O+ + HM

Ka1 = 1.20 x 102

HM + H2O

H3O+ + M2

Ka2 = 5.96 x 107

Ka1/Ka2 is large (2.01 x 104) so the second

dissociation can be neglected.
[M2-] << [HM], [H2M]

24

12

Department of Chemistry
Faculty of Science

Ka1

Polyfunctional
Acids and Bases

[H3O+]2
=
= 1.20 x 102
c H M [H3O+]
2

[H3O+]2
= 1.20 x 102
0.1000 [H3O+]
[H3O+]2 + 1.20 x 102[H3O+] 1.20 x 103 = 0
[H3O+] =

1.20 x 102 + (1.20 x 102)2 4( 1.20 x 103)

2
[H3O+] = 2.92 x 102 M = [HM]
pH = log 2.92 x 102 = 1.53

Department of Chemistry
Faculty of Science

25

Polyfunctional
Acids and Bases

Check assumption :
Ka2

[H3O+][M2]
=
= 5.96 x 107
[HM]
[M2] = 5.96 x 107 M

[HM] = 2.92 x 102 M

[H2M] = 0.1000 2.92 x 102 = 7.08 x 102 M
[M2-] << [HM], [H2M]
26

13

Department of Chemistry
Faculty of Science

Polyfunctional
Acids and Bases

Example 4
Calculate the pH of 0.0400 M H2SO4 solution.
H2SO4 + H2O

H3O+ + HSO4

HSO4 + H2O

H3O+ + SO42

Ka2 = 1.20 x 102

[H3O+] = 0.0400 + [SO42]

[SO42] = [H3O+] 0.0400
Mass-balance equation :
c

H2SO4

= 0.0400 = [HSO4] + [SO42]

Department of Chemistry
Faculty of Science

H2SO4

27

Polyfunctional
Acids and Bases

= 0.0400 = [HSO4] + [SO42]

0.0400 = [HSO4] + [H3O+] 0.0400

[HSO4] = 0.0800 [H3O+]
Ka2

[H3O+] [SO42]
=
= 1.20 x 102
[HSO4]

Ka2

[H3O+] ([H3O+] 0.0400)

=
= 1.20 x 102
0.0800 [H3O+]

28

14

Department of Chemistry
Faculty of Science

Polyfunctional
Acids and Bases

[H3O+]2 0.0280 [H3O+] 9.60 x 104 = 0

[H3O+] = 0.0480 M
pH = 1.32

29

Department of Chemistry
Faculty of Science

Buffer Solutions
Involving Polyprotic Acids

1. H2A NaHA System

H2A + H2O

H3O+ + HA

Ka1

HA + H2O

H3O+ + A2

Ka2

Assumption :
The dissociation of HA to yield A2 is negligible.

30

15

Department of Chemistry
Faculty of Science

Polyfunctional
Acids and Bases

Example 5
Calculate the [H3O+] for a buffer solution that is
2.00 M in H3PO4 and 1.50 M in KH2PO4.
H3O+ + H2PO4

H3PO4 + H2O
H2PO4 + H2O

H3O+ + HPO42

Ka1 = 7.11 x 103

Ka2 = 6.34 x 108

Assume that dissociation of H2PO4 is negligible.

[PO43] << [H2PO4] and [HPO42]
31

Department of Chemistry
Faculty of Science

H3PO4 + H2O

Polyfunctional
Acids and Bases
H3O+ + H2PO4

Ka1 = 7.11 x 103

[H3PO4] cH PO = 2.00 M
3

[H2PO4] c KH PO = 1.50 M
2

Ka1
[H3

[H3O+] [H2PO4]
=
= 7.11 x 103
[H3PO4]
O+]

7.11 x 103 x 2.00

=
= 9.48 x 103 M
1.50
32

16

Department of Chemistry
Faculty of Science

Ka2 =

Polyfunctional
Acids and Bases

[H3O+] [HPO42]
= 6.34 x 108
[H2PO4]

9.48 x 103 [HPO42]

= 6.34 x 108
1.50
[HPO42] = 1.00 x 105 M

33

Department of Chemistry
Faculty of Science

Buffer Solutions
Involving Polyprotic Acids

2. NaHA Na2A System

HA + H2O

H3O+ + A2

(1)

HA + H2O

OH + H2A

(2)

Assumption :
The equilibrium (2) is negligible.
[H2A] << [HA] and [A2]
34

17

Department of Chemistry
Faculty of Science

Polyfunctional
Acids and Bases

Example 6
Calculate the [H3O+] for a buffer solution that is
0.0500 M in potassium hydrogen phtalate (KHP)
and 0.150 M in potassium phthalate (K2P).
HP + H2O

H3O+ + P2

Ka2 = 3.91 x 106

Kw
= 8.93 x 1012
Ka1
Assume that reaction of HP as a base is negligible.
HP + H2O

OH + H2P

Kb2 =

[H2P] << [HP] and [P2]

Department of Chemistry
Faculty of Science

HP + H2O

35

Polyfunctional
Acids and Bases
H3O+ + P2

Ka2 = 3.91 x 106

[HP] cKHP = 0.0500 M

[P2]
Ka2
[H3

O+]

cK P
2

= 0.150 M

[H3O+] [P2]
=
= 3.91 x 106
[HP]

3.91 x 106 x 0.0500

=
= 1.30 x 106 M
0.150
36

18

Department of Chemistry
Faculty of Science

Ka1 =

Polyfunctional
Acids and Bases
[H3O+] [HP]
= 1.12 x 103
[H2P]

(1.30 x 106)(0.0500)
= 1.12 x 103
[H2P]
[H2P] = 6.0 x 105 M

37

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