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

1
Acid-Base indicators are themselves weak
acids…..

e.g. phenolthalein
H2In = HIn- = In2-

2
 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
-100
Automated titrators determine the
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
2
titrant = strong base
3
1

mL base 

analyte = strong base

titrant = strong acid

mL acid 

3
 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
 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 

5
 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-

6
 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

7
2 pH before the equivalence pt.

3 pH at the equivalence pt.

4 pH after the equivalence pt. =

same as SA-SB titration

8
Weak Acid - Strong Base Titration (both monoprotic)
(analyte) (titrant)

mol salt [OH-] = Mb(Vb beyond eq.pt.)

pH  pKa  log
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 

9
 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.

10
 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.

11
Example: Calculate the pH of a 0.050M solution of sodium leucinate

The Intermediate Form

The pH of a Zwitterion Solution - Leucine (HL form)

12
13
 assume:
K a1K a2CHL  K wK a1 KwKa1 << Ka1Ka2CHL
[H ] 
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.

14
 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 =

15
pt C: 1st eq. pt (HL) =

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

16
 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) =

17
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) =

18
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

19