Indicators for Acid-Base Titrations (Sec.

9-6)
transition range needs to match the
endpoint pH as closely as possible in
order to minimize titration error
Acid-Base indicators are themselves weak
acids…..

e.g. phenolthalein
H2In = HIn- = In2-
 Ch 10: Acid-Base Titrations
Titration of 0.10 M HCl by 0.10 M NaOH

14

12

10

8
phenolthalein 8.0-9.6

pH
6

0
0 10 20 30 40 50 60 70 80 90 100

mL OH-

2nd Derivative

300

200

100
d2 pH/d mL2

0
49.5 49.6 49.7 49.8 49.9 50 50.1 50.2 50.3 50.4 50.5

Automated titrators determine the -100

endpoint electronically by numerically -200

calculating the 2nd derivative -300

mL base
 Acid-Base Titrations Curves - pH (or pOH)
as a function of mL of titrant added

analyte = strong acid

4
titrant = strong base
2
3
1

mL base 

analyte = strong base

titrant = strong acid

mL acid 
 I. Strong Acid-Strong Base
Titration Curves (Sec. 10-1)
50 mL of 0.100 M HCl is titrated with 0.100 M NaOH.
Calculate the titration curve for the analysis.

equivalence pt. volume:

1 Initial pH
2 pH before the equivalence pt.

3 pH at the equivalence pt.

4 pH after the equivalence pt.
Strong Acid - Strong Base Titration (both monoprotic)
(analyte) (titrant)

[H+] = MaVa - MbVb [OH-] = Mb(Vb beyond eq.pt.)

Vtotal Vtotal

Eq. Pt. pH
=7

[H+] = CHA so pH = -log CHA

mL base 
 Titration of 0.10 M HCl by 0.10 M NaOH

14

12

10

phenolthalein 8.0-9.6
8
pH

6
methyl red 4.2-6.2
4

0
0 10 20 30 40 50 60 70 80 90 100

mL OH-
 Titration Error
Titration of 0.10 M HCl by 0.10 M NaOH
Expanded View of Equivalence Point
14

12

10

phenolthalein 8.0-9.6
8
pH

0.02 mL/50 mL
4
=0.04% error!
2

0
49 49.1 49.2 49.3 49.4 49.5 49.6 49.7 49.8 49.9 50 50.1 50.2 50.3 50.4 50.5 50.6 50.7 50.8 50.9 51

mL OH-
 II. Weak Acid-Strong Base
Titration Curve (Sec. 10-2)
50 mL of a 0.100 M soln of the weak acid HA, Ka = 1.0 x 10-5,
is titrated with 0.100 M NaOH. Calculate the titration curve for
the analysis.
[H ][A  ]
HA = H+ + A- Ka 
[HA]
equivalence pt. volume:

1 Initial pH
2 pH before the equivalence pt.
3 pH at the equivalence pt.

4 pH after the equivalence pt. =

same as SA-SB titration
Weak Acid - Strong Base Titration (both monoprotic)
(analyte) (titrant)

mol salt
pH  pKa  log [OH-] = Mb(Vb beyond eq.pt.)
mol acid Vtotal
Buffer region
Eq. Pt. Hydrolysis of the
conjugate base

1/2 eq. pt. pH = pKa

[ H ]  K C when x  C

a HA HA

mL base 
 Ch 11: Titrations in Diprotic Systems
Biological Applications - Amino Acids (Sec. 11-1)

R = (CH3)2CHCH2 -

low pH high pH
 Finding the pH in Diprotic Systems (Sec. 11-2)

1. The acidic form H2L+

The strength of H2L+ as an acid is much, much greater than HL -

Ka1 = 10-2.328 = 4.7 x 10-3

Ka2 = 10-9.744 = 1.8 x 10-10

So assume the pH depends only on H2L+ and ignore the

contribution of H+ from HL.
Calculate the pH of 0.050M H2L+
 2. The basic form L-

Ka1 = 10-2.328 = 4.7 x 10-3 Ka2 = 10-9.744 = 1.8 x 10-10

Strengths of conjugate bases:

for L- Kb1 = Kw/Ka2 = 1.01 x 10-14/1.8 x 10-10 = 5.61 x 10-5
for HL Kb2 = Kw/Ka1 = 1.01 x 10-14/4.7 x 10-3 = 2.1 x 10-12
Since the second conj. base HL is so weak, we'll assume all the
OH- comes from the L- form.
Example: Calculate the pH of a 0.050M solution of sodium leucinate
The Intermediate Form
The pH of a Zwitterion Solution - Leucine (HL form)
 assume:
K a1K a2CHL  K wK a1
[H ] 
 KwKa1 << Ka1Ka2CHL
K a1  CHL Ka1 << CHL

K a1K a2CHL
[H ] 

so [H]  K a1K a2
CHL

[H+]2 = Ka1 Ka2

-log [H+]2 = - log Ka1 - log Ka2
2 pH = pKa1 + pKa2

pK a1  pK a2 pH of a solution of a diprotic
pH 
2 zwitterion
 Example:
pH of the Intermediate Form of a Diprotic Acid

Potassium hydrogen phthalate, KHP, is a salt of the

intermediate form of phthalic acid. Calculate the pH of
0.10M KHP and 0.010M KHP.
 Titration Curve for the Amino Acid Leucine

Titration of 10 mL of 0.100 M Leucine

with 0.100 M NaOH

14

12

10

8
pH

0
0 5 10 15 20 25 30 35
mL NaOH
equivalence pt. volumes (Ve1 & Ve2) =

pt A: init. pH (H2L+ treat as monoprotic weak acid) =

pts B and D: 1st and 2nd half eq. pt's =

pt C: 1st eq. pt (HL) =

pt E: 2nd eq. pt (L-) =

 Example p. 233:
Titration of Sodium Carbonate (soda ash)

Calculate the titration curve for the titration of 50.0 mL of

0.020 M Na2CO3 with 0.100 M HCl.

equivalence pt. volumes (Ve1 & Ve2) =

pt A: init. pH (CO32- treat as monoprotic weak base) =

pts B and D: 1st and 2nd half eq. pt's =

pt C: 1st eq. pt (HCO3-) =

pt E: 2nd eq. pt (H2CO3 treat as monoprotic weak acid) =

pt E: 2nd eq. pt (H2CO3 treat as monoprotic weak acid) =
Buffers of Polyprotic Acids and Bases
Fractional Composition Diagram H 3PO4
H3PO4 H2PO4- HPO42- PO43-

1.00
0.90
0.80
0.70
0.60

alpha
0.50
0.40
0.30
0.20
0.10
0.00
0 2 4 6 8 10 12 14
pH