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Schedule
8:10-9:00 Questions
9:00-9:45 Test on Acids and Bases
9:45-12:00 Buffers and titration curves
Chapter 15 – Titration Curves

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Titration

• Strong acid/strong base


• Strong acid/weak base
• Strong base/weak acid

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Setup to Do pH Titration of an Acid or Base

Photo © Brooks/Cole, Cengage Learning Company. All rights reserved.

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Titration of 50ml of 0.20M HNO3 with
0.100M NaOH: No NaOH Added

Of solution in
the beaker
(called analyte)

From the burette, called the titrant

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Titration of 50ml of 0.20M HNO3:
10.0 mL of 0.100 M NaOH Added

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Titration of 50ml of 0.20M HNO3:
50.0 mL (total) of 0.100 M NaOH Added

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Titration of 50ml of 0.20M HNO3:
100.0 mL (total) of 0.100 M NaOH Added

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Titration of 50ml of 0.20M HNO3:
150.0 mL (total) of 0.100 M NaOH Added

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Titration of 50ml of 0.20M HNO3:
200 mL (total) of 0.100 M NaOH Added

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Titration of 50ml of 0.20M HNO3 with
0.100 M NaOH

The terms
equivalence point
and end point
mean the same
thing.

Note: at the equivalence point the number of moles of


OH¯ added = the number of moles of H3O+ titrated
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Strong base/weak acid titration
Unlike the titration of a
strong acid, the pH of a
weak base is buffered at pH
valued of pKa ± 1.

[base]
pH  pK a  log
[acid ]

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The endpoint of the titration is at 50 mL of added OH¯.
The midpoint is halfway, at 25 ml of added OH¯.

At the midpoint, pH = pKa.

In other words, the pKa can


be read directly from the
titration curve.

[base]
pH  pK a  log
[acid ]

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Below is shown the titration of a weak base with HClO4.
For this buffer it shows how the pH changes with added
strong acid.

It can be thought of as a buffer profile.

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Each point in this titration is the result of a separate experiment.

Point by point is shown buffer pH for a given buffer composition.

In sum, it shows how the pH changes with added strong acid.

It gives you the pKa of the weak acid/base buffer pair.

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What percent of the NH3 has been converted to NH4+ after
25ml of HClO4 have been added?

NH3 + H3O+  NH4+ + H2O

Titration of 100 ml of 0.05M NH3

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What is the pKa of the conjugate weak acid? a. 11
b. 3
[base] c. 9.3
pH  pK a  log
[acid ] d. 4.7
e. lost

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What percent of the NH3 has been converted to NH4+ after
20ml of HClO4 has been added?

After 40ml of HClO4 has been added?


After 50 ml?
Titration of 100 ml of 0.05M NH3

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What are the major species in solution at the end of the
titration?

a. ClO4¯, NH3, H3O+ b. HClO4, NH3


c. ClO4¯, NH4+, H3O+ d. HClO4, NH4+

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If the volume of the analyte NH3 is 100 mL, what was its
concentration at the start of the titration?

a. 0.10M b. 0.20M
c. 0.05M d. Lost!

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What is buffering region here, in terms of mL HClO4 added?

Does a buffering range of pH = pKa ± 1 seem about right?

Titration of 100 ml of 0.05M NH3

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How would you calculate the pH at the endpoint of this titration
of 100 ml of 0.05M NH3?
Hint: first you need to know what will react with water, and its
concentration!

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What is the pH at the midpoint of a HOCl titration (Ka = 3.5x10-8)
1. 7.5
2. 6.5
3. Lost

What is the pH at the midpoint of a OCl¯ titration (Kb = 2.9x10-7)


4. 7.5
5. 6.5
6. lost
Consider the titration of 0.20M HOCl. What is the concentration of
OCl¯ at the midpoint of the titration (ignoring dilution)?
1. 0.20M
2. 0.10M
3. Not possible to determine without more information
4. lost
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Titration of a polyprotic acid: H3PO4
pKa1 = 2.1 pKa2 = 7.2 pKa3 = 12.3

• pKa values
• Species at 5ml
PO4-3
intervals
• pH of
amphoteric
HPO4-2
salts

H2PO4¯

H3PO4

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How to prepare a buffer

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How to prepare a buffer
Suppose you wanted to make a pH 7.4 phosphate buffer

Given that pKa1 = 2.12, pKa2 = 7.21, and pKa3 =12.3, what
chemicals would you use from this list:
H3PO4, KH2PO4, K2HPO4, K3PO4 KH2PO4, K2HPO4

What would be the ratio of Base/Acid


[base] that you would
use? 7.4  7.2  log
[acid ]

Suppose you wanted a 0.20M, pH 7.4 phosphate buffer.


How much base and how much conjugate acid would
you use to make 1 liter of buffer? 26
The steps for a buffer preparation calculation:

1. Determine the weak acid/weak base couple


using the pH of the buffer as a guide
2. Determine the ratio of base to acid in the buffer
using pH = pka + log(B/A)
3. Determine the actual concentrations of B and A
to be used based on the desired buffer
concentration and the B/A ratio.

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Example: Make a 0.15M pH 6.7 carbonate buffer.

1. Determine the weak acid/weak base couple


using the pH of the buffer as a guide

For H2CO3, pKa1 = 6.4, pKa2 = 10.3

Choose the weak acid with pKa1 = 6.4, and its


conjugate base: H2CO3/HCO3¯

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Example: Make a 0.15M pH 6.7 carbonate buffer.

2. Determine the ratio of base to acid in the buffer


using pH = pka + log(B/A)

6.7 = 6.4 + log([HCO3¯]/[H2CO3])

[HCO3¯]/[H2CO3] = 2.0

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Example: Make a 0.15M pH 6.7 carbonate buffer.

3. Determine the actual concentrations of B and A


to be used based on the desired buffer
concentration and the B/A ratio.

[HCO3¯]/[H2CO3] = 2.0

[HCO3¯] + [H2CO3] = 0.15

Solve these two equations for the two unknowns:

[HCO3¯] = 0.10M [H2CO3] = 0.05M


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Try a problem: What would you need in solution to
have a 0.30M, pH 7.1, hypochlorous buffer?
HClO: pKa= 7.4
1. Determine the weak acid/weak base couple
using the pH of the buffer as a guide
2. Determine the ratio of base to acid in the buffer
using pH = pka + log(B/A)
3. Determine the actual concentrations of B and A
to be used based on the desired buffer
concentration and the B/A ratio.

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Could you prepare this buffer using only HClO and KOH?

How many moles of HClO would you use to prepare 1.0L of


0.30M, pH 7 buffer?
1. 0.1
2. 0.2
3. 0.3
4. lost

About how many moles KOH would you expect to need to


make 1.0L the buffer?
5. 0.1
6. 0.2
7. 0.3
8. lost

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