15 Titration Curves for Complex Acid/Base Systems

(1) Two acids or two bases of different strength.

(2) An acid or a base that has two or more acids or bases of different strengths
(3) An amphiprotic substance

15A Mixtures of Strong and Weak Acids or Strong and weak

Bases
Ex. 15-1,2 Calculate the pH of a mixture (25 mL) that is 0.1200 M in HCl and
0.0800 M in HA (Ka = 1.00 × 10-4) during its titration with 0.1000 M KOH
at (a) 0.00 mL (b) 5.00 mL and (c) 29.00 mL.
(a) 0.00 mL KOH added
[H3O+] = cHCl + [A-] = 0.1200 + [A-] ≈ 0.1200 M, pH = 0.92
(assume [A-] << 0.1200M)
Check this assumption:
[A - ] Ka 1.00 × 10 −4 −4 [A - ]
= = = 8.33 × 10 , [HA ] =
[HA ] [ H 3 O + ] 0.1200 8.33 × 10 −4
cHA = [HA] + [A-] = 0.0800 M
[A - ]
−4
+ [A - ] ≈ (1.20 × 10 3 )[A - ] = 0.0800 M , [A-] = 6.7× 10-5 M
8.33 × 10
(b) After adding 5.00 mL of base
25.00 × 0.1200 − 5.00 × 0.100
c HCl = = 0.0833 M
25.00 + 5.00
[H3O+] = 0.0833 + [A-] ≈ 0.0833 M, pH = 1.08
Check this assumption:
[A - ] 1.00 × 10 −4 [A - ]
= = 0.001200 M , [HA ] = , cHA = [HA] + [A-]
[HA ] 0.0833 0.001200
[A - ] 0.0800 × 25.00
[HA ] = + [A - ] ≈ (8.34 × 10 2 )[A - ] = = 0.0667 M
0.001200 30.00
[A-] = 8.0 × 10-5 M ( << 0.0833 M )
(c) After adding 29.00 mL of base
25.00 × 0.1200 − 29.00 × 0.100
c HCl = = 1.85 × 10 −3 M
25.00 + 29.00

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 25.00 × 0.0800
c HA = = 3.70 × 10 − 2 M
25.00 + 29.00
[H3O+] = cHCl + [A-] = 1.85×10-3 + [A-], cHA = [HA] + [A-] = 3.70×10-2 M
[H 3 O + ][A - ] [H 3 O + ][A - ]
[HA ] = , + [A - ] = 3.70 × 10 2
1.00 × 10 −4 1.00 × 10 −4

3.70 × 10 −6 3.70 × 10 −6
[A - ] = + −3
, [H 3 O ] = 1.85 × 10 +
[H 3 O + ] + 1.00 × 10 − 4 [H 3 O + ] + 1.00 × 10 −4
[H3O+]2 + (1.00 × 10-4) [H3O+] = (1.85 × 10-3) [H3O+] + 1.85 × 10-7 + 3.7 × 10-6
[H3O+]2 - (1.75 × 10-3) [H3O+] - 3.885 × 10-6 = 0
[H3O+] = 3.03 × 10-3 M, pH = 2.52
3.03 × 10-3 – 1.85 × 10-3 = 1.18 × 10-3 ([H3O+] from HA)
1.85 × 10-3 ([H3O+] from HCl)

Fig 15-1 Curves for the titration of

strong acid/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.

15B Polyfunctional Acids and Bases

15B-1 The phosphoric acid system
[H 3O + ][H 2 PO -4 ]
H3PO4 + H2O ⇔ H2PO4- + H3O+ K a1 = = 7.11 × 10 − 3
[H 3PO 4 ]
[H 3O + ][HPO 24- ]
H2PO4- + H2O ⇔ HPO42- + H3O+ K a2 = = 6.32 × 10 −8
[H 2 PO -4 ]

HPO42- + H2O ⇔ PO43- + H3O+ [H 3O + ][PO34- ]

K a3 = = 4.5 × 10 −13
[HPO 24 - ]
Ka1 > Ka2 > Ka3

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 H3PO4 + 3H2O ⇔ PO43- + 3H3O+
[H 3O + ]3[PO 34- ]
K a1K a2 K a3 =
[H 3PO 4 ]

= 7.11 × 10 − 3 × 6.32 × 10 −8 × 4.5 × 10 −13 = 2.0 × 10 − 22

15B-2 The carbon dioxide carbonic acid system

[H 2 CO 3 ]
CO2(aq) + H2O ⇔ H2CO3 K hyd = = 2.8 × 10 − 3
[CO 2 (aq)]
[ H 3 O + ][HCO 3- ]
H2CO3 + H2O ⇔ H3O + HCO3 + -
K1 = = 1.5 × 10 − 4
[H 2 CO 3 ]
[ H 3 O + ][CO 32- ]
-
HCO3 + H2O ⇔ H3O + CO3 + 2-
K2 = -
= 4.69 × 10 −11
[HCO 3 ]
----------------------------------------------------------------------------------------
CO2(aq) + 2H2O ⇔ H3O+ + HCO3-
[ H 3 O + ][HCO 3- ]
K a1 = = 2.8 × 10 −3 × 1.5 × 10 − 4 = 4.2 × 10 −7
[CO 2 (aq)]
[ H 3 O + ][CO 32- ]
-
HCO3 + H2O ⇔ H3O + CO3 + 2-
K2 = -
= 4.69 × 10 −11
[HCO 3 ]

Ex. 15-3 Calculate the pH of a solution that is 0.02500 M CO2.

cCO 2 = 0.02500 = [CO 2 (aq)] + [H 2 CO 3 ] + [HCO 3- ] + [CO 32- ]
[CO 2 (aq)] >> [H 2 CO 3 ] + [HCO 3- ] + [CO 32- ], [CO 2 (aq)] ≈ cCO 2 = 0.02500 M
From charge-balance [H3O+] = [HCO3-] + 2[CO32-] + [OH-],
2[CO32-] + [OH-] << [HCO3-] → [H3O+] ≈ [HCO3-]
[H 3O + ]2
K a1 = = 4.2 × 10 −7 , [ H 3 O + ] = 0.02500 × 4.2 × 10 -7 = 1.02 × 10 − 4 M
[CO 2 (aq)]
pH = -log(1.02 × 10-4 ) = 3.99

15C Buffer Solutions Involving Polyprotic Acids

Ex. 15-4 Calculate the [H3O+] for a buffer solution that is 2.00 M in H3PO4 and
1.50M in KH2PO4.
[H 3O + ][H 2 PO -4 ]
= 7.11 × 10 − 3
- +
H3PO4 + H2O ⇔ H2PO4 + H3O K a1 =
[H 3PO 4 ]

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 [H 3O + ][HPO 24- ]
H2PO4- + H2O ⇔ HPO42- + H3O+ K a2 = = 6.32 × 10 −8
[H 2 PO -4 ]
Assume: [HPO42-] and [PO43-] << [H2PO4-] and [H3PO4]
[H 3 PO 4 ] ≈ cH3PO 4 = 2.00 M, [H 2 PO -4 ] ≈ cH PO- = 1.50 M
2 4

+ 7.11×10 -3 × 2.00
[H 3 O ] = = 9.48 × 10 −3 M
1.50
Check the assumption
[H 3 O + ][HPO 24- ] 9.48 ×10 −3 [HPO 24- ]
= = 6.34 ×10 −8
[H 2 PO -4 ] 1.50
[HPO42-] = 1.00 × 10-5 M and [PO43-] < [HPO42-] the assumption is valid

*For a buffer prepared from NaHA and Na2A

HA- + H2O ⇔ H2A + OH- is disregarded
[H2A] << [HA-] and [A2-]
Ex. 15-5 Calculate the [H3O+] for a buffer solution that is 0.0500 M in potassium
hydrogen phthalate (KHP) and0.150M in potassium phthalate (K2P).
[H 3 O + ][P 2- ]
-
HP + H2O ⇔ +
H3O + P 2-
K a2 = -
= 3.91×10 −6
[HP ]
Assume: [H2P] is negligible
[HP - ] ≈ cKHP = 0.0500 M, [P 2- ] ≈ cK 2P = 0.150 M

3.91×10 -6 × 0.0500
+
[H 3 O ] = = 1.30 × 10 −6 M
0.150
Check the assumption
(1.30 × 10 -6 )(0.0500)
= K a1 = 61.12 × 10 −3
[H 2 P]
[H2P] = 6 × 10-5 M and [H2P] << [HP-] and [P2-], the assumption is valid

15D Calculation of the pH of Solution of NaHA

[H 3 O + ][A 2- ]
HA- + H2O ⇔ A2- + H3O+ K a2 =
[HA - ]
K w [H 2 A][OH - ]
HA- + H2O ⇔ H2A + OH- K b2 = =
K a1 [HA - ]
For mass balance: cNaHA = [H2A] + [HA-] + [A2-]

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For charge balance: [Na+] + [H3O+] = [OH-] + [HA-] + 2[A2-] = cNaHA+ [H3O+]
[H2A] + [HA-] + [A2-]+ [H3O+] = [OH-] + [HA-] + 2[A2-]
[H3O+] = [A2-] + [OH-]- [H2A]
[H 3 O + ][HA - ] K a2 [HA - ]
[H 2 A] = , [A ] =
2-

K a1 [H 3 O + ]
K a2 [HA - ] Kw [H 3 O + ][HA - ]
[H 3 O + ] = + − ( × [H3O+] )
[H 3 O + ] [H 3 O + ] K a1

[H 3 O + ]2 [HA - ] + 2 ⎛ [HA ] ⎞
-

→ [H 3 O ] ⎜⎜ + 1⎟⎟ = K a2 [HA - ] + K w
+ 2
[H 3 O ] = K a2 [HA ] + K w −
-

K a1 ⎝ K a1 ⎠

+K a2 [HA - ] + K w + K a2 C NaHA + K w
[H 3 O ] = → [H 3 O ] =
[HA - ] C
1+ 1 + NaHA
K a1 K a1
if CNaHA/Ka1 >> 1 and Ka2CNaHA >> Kw

→ [H3O + ] ≅ K a1K a 2
Ex. 15-6 Calculate the [H3O+] of a 1.00 × 10-3 M Na2HPO4 solution.
Ka2 = 6.32 × 10-8 and Ka3 = 4.5 × 10-13
CNa2HPO4/Ka2 = (1.00 × 10-3)/(6.32 × 10-8) >> 1
and Ka3CNa2HPO4 = 4.5 × 10-13 × 1.00 × 10-3 < Kw

K a3C Na 2 HPO 4 + K w
+ 4.5 × 10 −13 × 10 −3 + 10 −14 = 8.1 × 10-10
[H 3O ] = =
1+
C Na 2 HPO 4 10 −3
K a2 6.32 × 10 −8

Ex. 15-7 Find the [H3O+] of a 0.0100 M NaH2PO4 solution.

Ka1= 7.11 × 10-3 and Ka2= 6.32 × 10-8
CNaH2PO4/Ka1 = 0.0100/7.11 × 10-3
and Ka2CNaH2PO4 = 6.32 × 10-8 × 0.0100 >> Kw

K a2C NaH 2 PO 4 + K w 6.32 × 10 −8 × 10 − 2 = 1.62 × 10-5

[H3O + ] = =
C NaH 2 PO 4 10 − 2
1+ 1+
K a1 7.11× 10−3

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Ex. 15-8 Calculate the [H3O+] of a 0.100 M NaHCO3 solution.
CO2 + 2H2O ⇔ H3O+ + HCO3-
[ H 3 O + ][HCO 3- ]
K a1 = = 2.8 × 10 −3 × 1.5 × 10 − 4 = 4.2 × 10 −7
[CO 2 (aq)]
[ H 3 O + ][CO 32- ]
-
HCO3 + H2O ⇔ H3O + CO3 + 2-
K2 = -
= 4.69 × 10 −11
[HCO 3 ]
∵ CNaHA/Ka1 >> 1 and Ka2CNaHA >> Kw

[H 3 O + ] = 4.2 × 10 −7 × 4.69 × 10 −11 = 4.4 × 10 −9 M

15E Titration Curves for Polyfunctional Acids

Fig. 15-2 Titration of 20.00 mL of

0.1000 M H2A with 0.1000 M
NaOH. For H2A, Ka1 = 1.00×
10-3 and Ka2 = 1.00 × 10-7. The
method of pH calculation is
shown for several points and
regions on the titration curve.

Volume of 0.100 M NaOH, mL

Ex. 15-9. Construct a curve for the titration of 25.00 mL of 0.1000 M maleic acid,
HOOC-CH=CH-COOH, with 0.1000 M NaOH.
H2M + H2O ⇔ H3O+ + HM- Ka1 = 1.3 × 10-2
HM- + H2O ⇔ H3O+ + M2- Ka2 = 5.9 × 10-7
Ka1/Ka2 is large (2 × 104)
Initial pH [H3O+] ≈ [HM-], [H2M] + [HM-] ≈ 0.1000
[H2M] = 0.1000 - [HM-] = 0.1000 - [H3O+]
−2 [H 3 O + ] 2
K a1 = 1.3 × 10 =
0.1000 − [H 3 O + ]
[H3O+]2 + 1.3 × 10-2 [H3O+] - 1.3 × 10-3 = 0
[H3O+] = 3.01 × 10-2, pH = 2 - log 3.01 = 1.52
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First Buffer Region: addition of 5.00 mL of base
CNaHM ≈ [HM-] = 5.00 × 0.1000/30.00 = 1.67 × 10-2 M
CH2M ≈ [H2M] = (25.00 - 5.00) × 0.1000/30.00 = 6.67 × 10-2 M
[H3O+] << CH2M or CHM- is not valid
[HM-] = 1.67 × 10-2 + [H3O+] - [OH-]
[H2M] = 6.67 × 10-2 - [H3O+] + [OH-]
[H 3O + ](1.67 × 10 − 2 + [H 3O + ])
K a1 = = 1.3 × 10 − 2
6.67 × 10 − 2 − [H 3O + ]
[H3O+]2 + 2.97 ×10-2 [H3O+] - 8.67 ×10-4 = 0
[H3O+] = 1.81 ×10-2 pH = -log 1.81 × 10-2 = 1.74
Just Prior to First Equivalence Point
CNaHM ≈ [HM-] = 24.90 × 0.1000/49.90 = 4.99 × 10-2 M
CH2M ≈ [H2M] = (25.00 – 24.90) × 0.1000/49.90 = 2.00 × 10-4 M
Mass balance: CH2M + CNaHM = [H2M] + [HM-] + [M2-]
Charge balance : [H3O+] + [Na+] = [HM-] + 2[M2-] + [OH-]
CNaHM = [HM-] + 2[M2-] – [H3O+] → [H3O+] = CH2M + [M2-] – [H2M]

+ K a 2 [HM - ][H 3 O + ][HM - ] [HM-] ≈ 4.99 × 10-2 M,

[H 3 O ] = c H 2 M + −
[H 3 O + ] K a1 CH2M = 2.00 × 10-4 M
⎛ [HM - ] ⎞ Ka1 = 1.3 × 10-2
[H 3 O + ]2 ⎜⎜1 + ⎟⎟ − cH 2M [H 3 O + ] − K a 2 [HM - ] = 0
⎝ K a1 ⎠ Ka2 = 5.9 × 10-7

[H3O+]2 + 2.00 ×10-4 [H3O+] – 2.94 ×10-8 = 0

[H3O+] = 1.014 ×10-4 pH = 3.99
at adding 24.99 mL of titrant, [H3O+] = 8.01 ×10-5 pH = 4.10
First Equivalence Point
[HM-] ≈ CNaHM = 25.00 × 0.1000/50.00 = 5.00 × 10-2 M

+ K a2 C NaHM 5.9 × 10 −7 × 5.00 × 10 −2

[H 3 O ] = =
1 + C NaHM / K a1 1 + (5.00 × 10 − 2 ) /(1.3 × 10 − 2 )
= 7.80 × 10-5 pH = -log (7.80 × 10-5) = 4.11
Just After the First Equivalence Point
CHM- = [25.00-(25.01-25.00)] × 0.1000/50.01 = 0.04997 M
CM2-= (25.01 - 25.00) × 0.1000/50.01 = 1.996 × 10-5 M
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Mass balance: CHM- + CM2- = [H2M]+[HM-]+[M2-]=0.04997+1.996×10-5=0.049999 M
Charge balance : [H3O+] + [Na+] = [HM-] + 2[M2-] + [OH-]
[Na+] = 25.01 × 0.1000/50.01 = 0.05001 M
[H3O+] = [M2-] – [H2M] – (0.05001 – 0.049999)
+ K a 2 [HM - ] [H 3 O + ][HM - ]
[H 3 O ] = +
− − 1.9996 × 10 −5
[H 3 O ] K a1

1.9996 ×10 −5 ± (1.9996 ×10 −5 ) 2 − 4 × 4.8438 × (−2.948 ×10 −8 )

= = 7.40 × 10 −5 M
2 × 4.8438

pH = 4.13
Second Buffer Region : addition of 25.50 mL of NaOH
[M2-] ≈ CNa2M ≈ (25.50 - 25.00) × 0.1000/50.50 = 0.050/50.50 M
[HM-] ≈ CNaHM ≈ [25.00-(25.50-25.00)] × 0.1000/50.50 = 2.45/50.50 M
[H3O+] = 5.9 × 10-7 (2.45/50.50) /(0.050/50.50) = 2.89 × 10-5 M
[H3O+] << CNa2M and CNaHM is valid and pH = -log 2.89 × 10-5 = 4.54
Just Prior to Second Equivalence Point
at adding 49.90 and 49.99 mL of titrant, M2- >> HM-
at adding 49.90 mL CHM- = 1.335 × 10-4 and CM2- = 0.3324
M2- + H2O ⇔ HM- + OH-
K w [OH − ][HM - ] [OH − ](1.335 × 10 −4 + [OH - ]) 1.00 × 10 −14
K b1 = = = = −7
= 1.69 × 10 −8
K a2 [M ] 2-
(0.03324 − [OH ]) -
5.9 × 10

[OH-]2 + (1.335 × 10-4 + Kb1) [OH-] – 0.03324 Kb1 = 0

[OH-] = 4.10 × 10-6 M → pOH = 5.39 → pH = 14 – 5.39 = 8.61
at adding 49.90 mL: [OH-] = 1.80 × 10-5 M → pH = 9.26
Second Equivalence Point: addition of 50.00 mL of NaOH
[Na2M] = 0.0333 M
K w [OH - ][HM - ]
K b1 = = 2 -
= 1.69 × 10 −8
M2- + H2O ⇔ OH- + HM-
Ka2 [M ]
[OH-] ≈ [HM-], [M2-] = 0.0333 - [OH-] ≅ 0.0333
[OH-]2/0.0333 = 1.69 × 10-8, [OH-] = 2.38 × 10-5
pH = 14.00 – (- log 2.38 × 10-5) = 9.38
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 pH Just Beyond the Second Equivalence Point: add 50.01 mL of NaOH
cM2- =25.00 × 0.1/75.01 =0.03333 M
excess [OH-] = 1.00 × 0.01/75.01 = 1.3333 × 10-5 M
[M2-] = cM2- – [HM-] = 0.0333 – [HM-], [OH-] = 1.3333 × 10-5 + [HM-]
[OH - ][HM - ] [HM - ](1.3333 ×10 −5 + [HM - ])
K b1 = =
[M 2- ] 0.03333 − [HM - ]
[HM-]2 + (1.33 × 10-5 + Kb1) [HM-] – 0.03333 Kb1 = 0
[HM-] = 1.807 × 10-5 M
[OH-] = 1.3333 × 10-5 + 1.807 × 10-5 = 3.14 × 10-5 M
pOH = 4.50 and pH = 14 – pOH = 9.50
add 50.10 mL of NaOH pH = 10.14
pH Beyond the Second Equivalence Point: add 51.00 mL of NaOH
[OH-] = 1.00 × 0.1000/76.0 = 1.32 × 10-3
pH = 14.00 - (- log 1.32 × 10-3) = 11.12

Volume of 0.1000 M NaOH, mL Volume of 0.1000 M NaOH, mL

Volume of 0.1000 M HCl, mL
Fig. 15-3 Titration curve for Fig. 15-4 Curve for the Fig. 15-5 Curve for the
25.00 mL of 0.1000 M titration of 0.1000 M H3PO4 titration of 25.00 mL of
maleic acid, H2M, with (A), 0.1000M oxalic acid 0.1000M Na2CO3 with
0.1000 M NaOH. (B), and 0.1000 M 0.1000 M HCl.
H2SO4(C).

15F Titration Curves for Polyfunctional Bases

2- - - K w 1.00 × 10 −14 −4
CO3 + H2O ⇔ HCO3 + OH K b1 = = = 2 . 13 × 10
K a 2 4.69 × 10 −11
K w 1.00 × 10 −14 −11
HCO3- + H2O ⇔ H2CO3 + OH- K b2 = = = 6. 7 × 10
K a1 1.5 × 10 − 4

100
15G Titration Curves for Amphiprotic Species
In NaH2PO4 solution: can be titrate with a standard base solution
H2PO4- + H2O ⇔ HPO42- + H3O+ K a2 = 6.32 × 10 −8
K w 1.00 × 10 −14
-
H2PO4 + H2O ⇔ OH + H3PO4 -
K b3 = = −3
= 1.41× 10 −12
K a1 7.11 × 10
In Na2HPO4 solution: can be titrate with a standard acid solution
HPO42- + H2O ⇔ PO43- + H3O+ K a3 = 4.5 ×10 −13
K w 1.00 × 10 −14
2-
HPO4 + H2O ⇔ OH + H2PO4 - -
K b2 = = −8
= 1.58 × 10 −7
K a2 6.32 × 10

15H The Composition of Solutions of a Polyprotic Acid as a

Function of pH
[H 2 M] [HM - ] [M 2 - ]
α0 = α1 = α2 =
CT CT CT

CT = [H2M] + [HM-] + [M2-] α0 + α1 + α2 = 1

[H 3O + ]2 K a1[H 3O + ]
α0 = α1 =
[H 3O + ]2 + K a1[H 3O + ] + K a1K a2 [H 3O + ]2 + K a1[H 3O + ] + K a1K a2
K a1K a2
α2 =
[H3O + ]2 + K a1[H3O + ] + K a1K a2

Fig 15-6 Composition of HM

solution as a function of pH. Fig. 15-7
Fig. 15-7 Titration of 25.00 mL of 0.1000 M maleic acid with 0.1000 M NaOH. The
solid curves are plots of alpha values as a function of volume. The broken
curve is a plot of pH as a function of volume.
101
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