Scribd
Upload
9 views39 pages

Chapter 10

The document covers the principles and calculations involved in acid-base titrations, including titrations of strong acids with strong bases, weak acids with strong bases, and weak bases with strong acids. It provides detailed steps to determine the equivalence point, pH calculations before, at, and after the equivalence point, as well as considerations for diprotic systems. Key formulas and examples are presented to illustrate the concepts effectively.

Uploaded by

sjkim1850
Copyright
© All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
9 views39 pages

Chapter 10

The document covers the principles and calculations involved in acid-base titrations, including titrations of strong acids with strong bases, weak acids with strong bases, and weak bases with strong acids. It provides detailed steps to determine the equivalence point, pH calculations before, at, and after the equivalence point, as well as considerations for diprotic systems. Key formulas and examples are presented to illustrate the concepts effectively.

Uploaded by

sjkim1850
Copyright
© All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd

Chapter 10

Acid-Base Titrations
Titration of Strong Base with Strong Acid
• 50.00 mL of 0.02000 M KOH with 0.1000 M HBr

1/Kw Kw
H+ + OH- H 2O H 2O H+ + OH-
1014

The first step with titration is to find Ve needed to


reach the equivalence point.

Ve (mL) ´ 0.1000 M = 50.00mL ´ 0.02000 M


Ve = 10.00mL
1.
Starting 2.
point Before
eq. point

3.
At
eq. point

4.
After
eq. point
1.
Starting • 50.00 mL of 0.02000 M KOH with 0.1000 M HBr
point
Ve = 10.00mL

pH = pK w - pOH
pH = 14 - (- log(0.02))
pH = 12.30
2.
Before • 50.00 mL of 0.02000 M KOH with 0.1000 M HBr
eq. point
Ve = 10.00mL
VHBr = 3.00mL

• pH is determined by the excess OH- Consider


à Dilution factor
VHBr = 3.00mL
- 7.00 50.00
[OH ] = 0.02000 M ´ ( )´( ) = 0.0132 M
10.00 50.00 + 3.00

Original Remaining Dilution pH = pK w - pOH


conc. fraction factor pH = 14 - (- log(0.0132))
pH = 12.12
VHBr = 9.50mL pH = 10.99
3.
At • 50.00 mL of 0.02000 M KOH with 0.1000 M HBr
eq. point
VHBr = 10.00mL Ve = 10.00mL

Kw
H 2O H+ + OH-

• pH is determined by the dissociation of water

pH = 7.00
4.
After • 50.00 mL of 0.02000 M KOH with 0.1000 M HBr
eq. point
Ve = 10.00mL
VHBr = 10.50mL

• pH is determined by the excess of H+ Consider


à Dilution factor
VHBr = 10.50mL
+ 0.50
[ H ] = 0.1000 M ´ ( ) = 8.26 ´ 10 - 4 M
50.00 + 10.50

Original Dilution
pH = - log(8.26 ´ 10 -4 ) = 3.08
conc. factor

VHBr = 11.00mL pH = 2.79


Titration of Weak Acid with Strong Base
• 50.00 mL of 0.02000 M MES (pKa = 6.15) with 0.1000 M NaOH

O NHCH2CH2SO3 + OH- O NCH2CH2SO3 + H2O

HA A-
Strong + weak à complete reaction!

The first step with titration is to find Ve needed to


reach the equivalence point.

Ve (mL) ´ 0.1000 M = 50.00mL ´ 0.02000 M


Ve = 10.00mL
4.
After
eq. point

3.
At
eq. point

2.
Before
eq. point

1.
Starting
point
• 50.00 mL of 0.02000 M MES (pKa = 6.15) with 0.1000 M NaOH

1. Ve = 10.00mL
O NHCH2CH2SO3
Starting
point Ka
HA H+ + A-

+ - 2
[ H ][ A ] x
= = Ka
[ HA] F-x

x = 1.19 x 10-4

pH = 3.93
• 50.00 mL of 0.02000 M MES (pKa = 6.15) with 0.1000 M NaOH
2. Ve = 10.00mL
Before VNaOH = 3.00mL
eq. point

HA + OH- A- + H2O

A mixture of HA and A- buffer

[ A- ] 3
pH = pK a + log
[ HA] pH = 6.15 + log 10 = 5.78
7
10

VNaOH = 5.00mL
• 50.00 mL of 0.02000 M MES (pKa = 6.15) with 0.1000 M NaOH
2. Ve = 10.00mL
Before VNaOH = 5.00mL
eq. point

HA + OH- A- + H2O

A mixture of HA and A- buffer

pH = pK a + log 1
pH = pK a pH = 6.15

1
When Vb = Ve
2
• 50.00 mL of 0.02000 M MES (pKa = 6.15) with 0.1000 M NaOH
3.
Ve = 10.00mL
VNaOH = 10.00mL
At
eq. point
HA + OH- A- + H2O

then, just A-

A- + H2O HA + OH-
K w = K a Kb

[ HA][OH - ] x2 K w 10 -14
-
= = Kb Kb = = -6.15 = 1.43 ´ 10 -8
[A ] F-x K a 10

50.00 x = 1.54 x 10-5 M


F = (0.02000) ´ ( ) = 0.0167 M
50.00 + 10.00
pH + pOH = pKw = 14
Original Dilution
conc. factor pH = 9.18
• 50.00 mL of 0.02000 M MES (pKa = 6.15) with 0.1000 M NaOH
4. Ve = 10.00mL
After VNaOH = 10.10mL
eq. point

• pH is determined by the excess of OH- Consider


à Dilution factor
VNaOH = 10.10mL
- 0.10
[OH ] = 0.1000 M ´ ( ) = 1.66 ´ 10 - 4 M
50.00 + 10.10

Original Dilution
conc. factor pOH = - log(1.66 ´ 10 -4 ) = 3.78

pH + pOH = pKw = 14
pH = 10.22
• At Vb = Ve, the curve is steepest
• At Vb = ½ Ve, pH=pKa
and the slope is minimal
• pH at eq. point, > 7

Maximum
buffer
capacity at
pH = pKa
Titration of Weak Base with Strong Acid
• 25.00 mL of 0.08364 M pyridine (Kb = 1.69 x 10-9) with 0.1067 M HCl

N + H+ NH

Strong + weak à complete reaction!

The first step with titration is to find Ve needed to


reach the equivalence point.

Ve (mL) ´ 0.1067 M = 25.00mL ´ 0.08364 M


Ve = 19.60mL
• 25.00 mL of 0.08364 M pyridine (Kb = 1.69 x 10-9) with 0.1067 M HCl
Ve = 19.60mL
1.
Starting Kb
point B + H2O BH+ + OH-

+ - 2
[ BH ][OH ] x
= = Kb
[ B] F-x

pH + pOH = pKw = 14
• 25.00 mL of 0.08364 M pyridine (Kb = 1.69 x 10-9) with 0.1067 M HCl
2. Ve = 19.60mL
Before VHCl = 4.63mL
eq. point

B + H+ BH+

A mixture of B and BH+ buffer

[ B] K w = K a Kb pK w = pK a + pK b
pH = pK a + log
[ BH + ]

14.97
pH = 5.23 + log 19.60 = 5.74
4.63
19.60
• 25.00 mL of 0.08364 M pyridine (Kb = 1.69 x 10-9) with 0.1067 M HCl
2. Ve = 19.60mL
Before VHCl = 9.80mL
eq. point

B + H+ BH+

A mixture of B and BH+ buffer

pH = pK a + log 1
pH = pK a pH = 5.23

1
When Vb = Ve
2
• 25.00 mL of 0.08364 M pyridine (Kb = 1.69 x 10-9) with 0.1067 M HCl
3. VHCl = 19.60mL
Ve = 19.60mL
At
eq. point
B + H+ BH+
then, just BH+

BH+ H+ + B
K w = K a Kb
+ 2
[ H ][ B ] x
+
= = Ka Kw 10 -14
[ BH ] F-x Ka = = = 5.92 ´ 10 -6
K b 1.69 ´ 10 -9

25.00 x = 5.24 x 10-4 M


F = (0.08364) ´ ( ) = 0.0469 M
25.00 + 19.60
Original Dilution pH = 3.28
conc. factor
• 25.00 mL of 0.08364 M pyridine (Kb = 1.69 x 10-9) with 0.1067 M HCl
4. Ve = 19.60mL
After VHCl = 21.60mL
eq. point

• pH is determined by the excess of H+ Consider


à Dilution factor
VHCl = 21.60mL
+ 2.00
[ H ] = 0.1067 M ´ ( ) = 4.58 ´ 10 -3 M
25.00 + 21.60

Original Dilution
conc. factor pH = - log(4.58 ´ 10 -3 ) = 2.34
Titrations in Diprotic Systems
• 50.0 mL, 0.0200 M H2A titrated with 0.100 M NaOH
pKa1 (H2A) = 4.00, pKa2 (H2A) = 10.00

Ka1 Ka2
H 2A HA- + H+ HA- A2- + H+
H2A + OH- HA- + H2O
HA- + OH- A2- + H2O

The first step with titration is to find Ve needed to


reach the equivalence point.

Ve1 (mL) ´ 0.1000 M = 50.00mL ´ 0.0200 M


Ve1 = 10.00mL
Ve 2 = 2 ´ Ve1 = 20.00mL
6.
5. after
at 2nd eq.
4. 2nd eq.
pH between
1st and
2nd eq.

3.
at
1st eq.

1. 2.
Starting Before
point 1st eq.

VNaOH (mL)
• 50.0 mL, 0.0200 M H2A titrated with 0.100 M NaOH
pKa1 (H2A) = 4.00, pKa2 (H2A) = 10.00
1.
Starting Ve1 = 10.00mL
point Ve 2 = 20.00mL
Ka1
H 2A HA- + H+

[ H + ][ HA- ] x2 x2
= = K a1 = 10 - 4.00
[ H 2 A] F-x 0.0200 - x

x = 1.37 x 10-3 M

pH = 2.86
• 50.0 mL, 0.0200 M H2A titrated with 0.100 M NaOH
2. pKa1 (H2A) = 4.00, pKa2 (H2A) = 10.00
Before Ve1 = 10.00mL
1st eq.
VNaOH = 5.00mL Ve 2 = 20.00mL

H2A + OH- HA- + H2O

a mixture of H2A and HA- buffer

5
[ HA- ]
pH = pK a1 + log pH = 4.00 + log 10 = 4.00
[ H 2 A] 10 - 5
10
VNaOH = 6.00mL
???
• 50.0 mL, 0.0200 M H2A titrated with 0.100 M NaOH
pKa1 (H2A) = 4.00, pKa2 (H2A) = 10.00
3.
at Ve1 = 10.00mL
1st eq. Ve 2 = 20.00mL
VNaOH = 10.00mL

H2A + OH- HA- + H2O

HA- + H2O H2A + OH-

HA- A2- + H+

pK1 + pK 2
+ FK1 K 2 + K1 K w pH =
[H ] = 2
K1 + F
Regardless of F
pH = 7
• 50.0 mL, 0.0200 M H2A titrated with 0.100 M NaOH
4. pKa1 (H2A) = 4.00, pKa2 (H2A) = 10.00
between Ve1 = 10.00mL
1st and
2nd eq. VNaOH = 15.00mL Ve 2 = 20.00mL

HA- + OH- A2- + H2O

a mixture of HA- and A2- buffer

5.00
[ A2- ]
pH = pK a 2 + log pH = 10.00 + log 10.00 = 10.00
[ HA- ] 10.00 - 5.00
10.00
VNaOH = 17.00mL
???
• 50.0 mL, 0.0200 M H2A titrated with 0.100 M NaOH
pKa1 (H2A) = 4.00, pKa2 (H2A) = 10.00
5.
at Ve1 = 10.00mL
2nd eq. Ve 2 = 20.00mL
VNaOH = 20.00mL

HA- + OH- A2- + H2O

A2- + H2O HA- + OH-

[ HA- ][OH - ] x2 x2 -4
= = Kb = 10
2- F-x
[A ] F-x

50´ 0.0200
F=
70

pH = 11.06
• 50.0 mL, 0.0200 M H2A titrated with 0.100 M NaOH
pKa1 (H2A) = 4.00, pKa2 (H2A) = 10.00
6.
after Ve1 = 10.00mL
2nd eq. Ve 2 = 20.00mL
VNaOH = 22.00mL

• pH is determined by the excess of OH- Consider


à Dilution factor

- 2.00
[OH ] = 0.100 M ´ ( ) = 2.60 ´ 10 -3 M
50.00 + 22.00

Original pOH = - log(2.60 ´ 10 -3 ) = 2.59


Dilution
conc. factor
pH = 11.41
Example for your own thought!

• 50.0 mL, 0.0200 M Na2CO3 titrated with 0.100 M HCl

pKa1 = 6.352, pKa2 = 10.329


Using a Gran Plot to Find the End point (page 218)
Derive each equation for
• Weak acid with strong base
• Weak base with strong acid

The beauty of a Gran plot is that it enables us to use data


taken before the end point to find the end point.
Finding the End Point with a pH Electrode
• A problem with using derivatives to find the end point is that
titration data are least accurate right near the end point
(buffering is minimal and electrode response is sluggish).
• A Gran plot is a graph of Vb × 10-pH versus Vb.
• A Gran plot uses data from before the end point to locate the
end point.
• The slope of the linear portion of the graph is Ka and the
x-intercept is Ve.
Weak acid vs. Strong base (Vb)

Weak base vs. Strong acid (Va)


Finding the End Point with Indicators
Thymol Blue

K1 [Y - ]
R Y- + H+ pH = pK1 + log
[ R]

pH [Y-]:[R] color
0.7 1:10 Red
1.7 1:1 Orange
2.7 10:1 Yellow
• The closer the point of color change is to pH 5.54, the more
accurate will be the end point .

In general, we seek an indicator whose transition range


overlaps the steepest part of the titration curve as closely as
possible.
The Leveling Effect

HClO4 + H2O H3O+ + ClO4-


HCl + H2O H3O+ + Cl-

HClO4 + CH3CO2H CH3CO2H2+ + ClO4- K = 1.3 x 10-5

HCl + CH3CO2H CH3CO2H2+ + Cl- K = 2.8 x 10-9


Homework

Derive each equation for


• Weak acid with strong base
• Weak base with strong acid

You might also like