Good Morning

Pick Up a Clicker!

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 - Buffers
What do you know about buffers?
• What are they used for?
• Why are they important?
• Anything else?
A buffer is made of a weak acid/weak base
conjugate pair in solution
• HF/KF
• HNO2/NaNO2
• NH4Cl/NH3
• H2CO3/NaHCO3
• KHCO3/K2CO3
NOT HCl/KCl or HNO3/NaNO3
A buffer resists change in pH when acid or base
is added to the solution

WHY?
 Major species in a buffer

HA, A¯, H2O

Equilibrium Linking Major Species

HA + H2O ⇄ A¯ + H3O+

When H3O+ is added to the solution, what

happens?
 HA + H2O ⇄ A¯ + H3O+

Le Chatelier’s principle says the reaction will

shift left, but how effective is this mechanism to
absorb added acid?

To answer that question we need to look

at the size of K for the reaction:
H3O+ + A¯  H2O + HA
Consider an acetate buffer equilibrium:

HAc + H2O ⇄ Ac¯ + H3O+

When a strong acid is added to a HAc/Ac¯ buffer solution,

1 1
K   5.5  10 4
H3O+ + Ac¯  H2O + HAc K a 1.8  105

The reaction goes effectively to completion due to the large K!

Virtually all the added acid is absorbed as long as there is

some acetate ion around to react with the added acid.
 HAc + H2O ⇄ Ac¯ + H3O+

Similarly for added OH¯ to an acetate buffer

1 K a 1.8  105
OH¯ + HAc  H2O + Ac¯ K     1 . 8  109

Kb K w 1x1014

It is a general result to say:

Strong acid added to weak base goes to completion

Strong base added to weak acid goes to completion

So if you have a buffer equilibrium: HA + H2O ⇄ A¯ + H3O+

Added H3O+ or OH¯ will be absorbed by the

reaction, buffering the pH.
 SUMMARIZE

HAc + H2O ⇄ Ac¯ + H3O+

H3O + Ac¯  H2O + HAc

+ K  5.5 104

OH¯ + HAc  H2O + Ac¯ K  1.8 109

Added H3O+ or OH¯ will be absorbed by the

reaction, buffering the pH.
So a buffer needs:
1) an acid/base equilibrium and
2) 2) reasonble amounts of both components of
the acid/base pair
Which of the following could be used to make a buffer?

1. HF and KF
2. CH3NH2 and CH3NH3Cl
3. NaOH and HCl
4. NaOH and HNO2
5. HCl and NH3
6. K2HPO4 and NaOH
7. K2HPO4 and HNO3
Calculation of buffer pH
What is the pH of a buffer made by mixing 0.10mol HF and
0.2mol NaF to 1000ml of water?

HF + H2O ⇄ F¯ + H3O+
I 0.1 0.2 0 (ignoring auto-ionization of water)
C -x +x +x
E 0.1-x 0.2-x x
Ka = 7.2x10-4
Make the usual approximations to get:
(0.2) x
Ka   7.2  104 Solving, x = [H3O+] = 3.6x10-4
0.1 pH = -log(3.6x10-4) = 3.4

Note that the pH depended on the ratio of base to acid and

on the value of the Ka.
Consider a hypochlorous buffer made by adding HOCl and
NaOCl to the same solution.

The governing equilibrium is

HOCl + H2O ⇄ OCl¯ + H3O+

[OCl  ][ H 3O  ]
Ka 
[ HOCl ]
As before, the hydrogen ion concentration depends on the
ratio of base and acid:

 [ HOCl ]
[ H 3O ]  K a
[OCl  ]
  [ HOCl ]
[ H 3O ]  K a 
[OCl ]
This can be rearranged by taking the negative log of both
sides:

 [ HOCl ]
 log[ H 3O ]   log K a  log 
[OCl ]

[OCl ]
pH  pK a  log
[ HOCl ]
Generalizing,
[base]
pH  pK a  log
[acid ]
 [base]
pH  pK a  log
[acid ]
aka the Henderson-Hasselbalch equation

Two important observations to be made here:

1. When the concentrations of weak acid and conjugate base
are equal, pH = pKa
2. This equation is based on assumed approximations.

[base  x ][ H 3O  ] [base][ H 3O  ]
Ka  
[acid  x ] [acid ]

When the approximations are not valid, the Henderson-

Hasselbalch equation is not valid.
 Over what pH range will a buffer
control the pH?
[base]
pH  pK a  log
[acid ]
There must be some weak base present to absorb added H+
and
There must be some weak acid present to absorb added OH¯

In practical terms, this means

[base] should be kept
between 0.1 and 10. [acid ]
pH = pKa ± 1

A buffer’s pKa defines its buffering range.

What acid/base pair would you choose to buffer at pH 6.5?

Table 17-1, p.822

 What acid/base pair would you choose to buffer at pH 5.0?

1. Ammonia/conj acid When given a Kb or pKb, you

2. Methylamine/conj acid
3. Ethylamine/conj acid
4. Aniline/conj acid
5. Pyridine/conj acid
6. I’m lost
must convert it to the pKa to
determine the pH range for the
buffer.
What acid/base pair would you choose to buffer at pH 7.4?
 You can use this equation to
calculate approximate buffer pH
[base]
pH  pK a  log
[acid ]
What is the pH of a buffer containing 0.15M NH3 and 0.40M
NH4ClO3? Ka (NH4+) = 5.55x10-10

pKa = -log(5.55x10-10) = 9.26 Note: This suggests way

too much precision – you
0.15 will be lucky to be at
pH  9.26  log  8.83 pH = 8.8±0.5
0.40
What is the approximate pH of a buffer that contains
0.2M KHCO3 and 0.3M K2CO3?

K+ is a spectator ion: active species are

HCO3¯ and CO3-2
Ka of the weak acid HCO3¯ is 5.6x10-11, pKa =10.3
base 0.3
pH  pKa  log  10.3  log  10.5
acid 0.2
What is the approximate pH of a buffer that contains
0.1M KH2PO4 and 0.3M K2HPO4?

1. 2.6
2. 7.7
3. 12.8
4. 1.7
5. 6.7
6. 11.8
A small note about nomenclature.

When we say we have a 0.20M fluoride buffer,

we mean that [HF]+[F¯] = 0.20

So a buffer that contains 0.20M H2CO3 and 0.10M

KHCO3 is called a 0.30M carbonate buffer.
Just to review where we are:

A buffer consists of a weak acid/weak base conjugate pair

A buffer works through Le Chatelier’s Principle

Because the reaction of a strong acid/base with a weak base/acid

goes to completion, virtually all added H+ or OH¯ is absorbed

The pH range of a given buffer pair is pKa ± 1

The pH of a buffer can be calculated using pH = pKa + log(b/a)

What molar ratio of NaH2PO4 to Na2HPO4 is required
to make a pH 7.5 phosphate buffer?

For phosphate, the three Ka values are:

7.5x10-3, 6.2x10-8, and 4.8x10-13.
pKa of H2PO4¯ is 7.2
1. 0.5
2. 2
3. 0.3
4. I am lost [base]
pH  pK a  log
[acid ]
A pH 7.5 phosphate buffer is made using 0.1 moles
NaH2PO4 and 0.2 moles Na2HPO4 dissolved in 1.0
liter of water. Remembering that the reaction of a
strong acid with a weak base goes to completion,
what is the pH after 0.1 moles of HNO3 is added?
For phosphate, the three Ka values are:
7.5x10-3, 6.2x10-8, and 4.8x10-13
Hint: first determine what is in
1. 0.5 solution after the strong acid/weak
2. 6.7 base reaction, and then use that to
3. 7.7 determine the pH
4. 6.9
5. I am lost
Effect of adding various amounts of strong acid to a
0.3M, pH 7.5 phosphate buffer.
Moles Moles Moles Moles Moles pH
HPO4¯2 H2PO4¯ H+ HPO4¯2 H2PO4¯
added after after
before before

0.2 0.1 0 0.2 0.1 7.5

0.2 0.1 0.05
0.2 0.1 0.1 0.1 0.2 6.9
0.2 0.1 0.15
0.2 0.1 0.2

Ignore any possible effects of dilution.

 How do you determine the
capacity of a buffer – how many
moles of strong acid or base it will
protect against?
 Buffer Capacity
A buffer works through Le Chatelier’s
Principle

HA + H2O ⇄ A¯ + H3O+

The number of moles of acid a buffer can absorb

is limited by the #moles of A¯

The number of moles of base a buffer can absorb

is limited by the #moles of HA
Could a 500ml solution of 0.2M KH2PO4/0.1M K2HPO4
buffer against addition of 30ml of added 2M KOH?
1. Yes
2. No
3. Lost I am

The number of moles of acid a buffer can absorb

is limited by the #moles of A¯

The number of moles of base a buffer can absorb

is limited by the #moles of HA
What is the maximum volume of added strong acid that a
500ml solution of 0.2M KH2PO4/0.1M K2HPO4 could buffer
against?

1. 10 ml of 1 M HCl
2. 25 ml of 1 M HCl
3. 40 ml of 1 M HCl
4. Lost I am
The number of moles of acid a buffer can absorb
is limited by the #moles of A¯

The number of moles of base a buffer can absorb

is limited by the #moles of HA
 Bottom line on buffer capacity:

to determine capacity vs. acid, look

at #moles of weak base present

to determine capacity vs. base,

look at #moles of acid present
 Titration

• Strong acid/strong base

• Strong acid/weak base
• Strong base/weak acid
Setup to Do pH Titration of an Acid or Base

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

 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

Titration of 50ml of 0.20M HNO3:
10.0 mL of 0.100 M NaOH Added
 Titration of 50ml of 0.20M HNO3:
50.0 mL (total) of 0.100 M NaOH Added
 Titration of 50ml of 0.20M HNO3:
100.0 mL (total) of 0.100 M NaOH Added
 Titration of 50ml of 0.20M HNO3:
150.0 mL (total) of 0.100 M NaOH Added
 Titration of 50ml of 0.20M HNO3:
200 mL (total) of 0.100 M NaOH Added
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
 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 ]
 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 ]
 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.

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.

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

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
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
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+
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!
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

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!
 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
 Titration of a polyprotic acid: H3PO4

• pKa values
• Species at 5ml
intervals
• pH of
amphoteric
salts
How to prepare a buffer
 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

What would be the ratio of Base/Acid that you would

use?

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

How much base and how much acid would you use to
make 1 liter of buffer?
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.
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¯
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
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

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.
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