Ch312 Lecture05 Ch9 10 11 w09

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 
14
12
10
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
Expanded View of Equivalence Point
14
12
10
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

Ch312 Lecture05 Ch9 10 11 w09

Uploaded by

Copyright:

Available Formats

Ch312 Lecture05 Ch9 10 11 w09

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Ch312 Lecture05 Ch9 10 11 w09

Uploaded by

Copyright:

Available Formats

Indicators for Acid-Base Titrations (Sec.

Automated titrators determine the -100

endpoint electronically by numerically -200

calculating the 2nd derivative -300

analyte = strong acid

analyte = strong base

equivalence pt. volume:

3 pH at the equivalence pt.

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

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

4 pH after the equivalence pt. =

1/2 eq. pt. pH = pKa

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

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

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

Strengths of conjugate bases:

[H+]2 = Ka1 Ka2

Potassium hydrogen phthalate, KHP, is a salt of the

Titration of 10 mL of 0.100 M Leucine

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

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

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

Calculate the titration curve for the titration of 50.0 mL of

equivalence pt. volumes (Ve1 & Ve2) =

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) =

You might also like