Buffers

Buffer Problems
Chem 220
Exploration 4C
You should memorize the buffer formulas. They look like the Ka definition but have
added restrictions.
Ka =
Ka =
[H+]MNaA
MHA
[H+]MB
MBHCl
if [H+] and [OH] << MNaA and MHA

if [H+] and [OH] << MB and MBHCl
Many of these problems demonstrate the properties of a buffer.

pH is unchanged by dilution (as long as the restrictions hold.)
pH change due to added strong acid or base is resisted (since strong acids or
bases are exchanged for weak acids and bases.)
4C-6 pH of a solution containing 0.75 M lactic acid and 0.25 M sodium lactate.
Use the buffer formula:
[H+]MNaA [H+](0.25)
1.410-4 =
=
if [H+] and [OH] << .25 and .75
0.75
MHA
[H+] = 4.2010-4; pH = 3.38
Yes, 10-4 and 10-11 << 0.25 and 0.75
4C-7 pH of a solution containing 0.25 M NH3 and 0.40 M NH4Cl.

Use the buffer formula:
[H+]MB [H+](0.25)
5.7010-10 =
=
if [H+] and [OH] << .25 and .40
0.40
MBHCl
[H+] = 9.1210-10; pH = 9.04
Yes, 10-10 and 10-5 << 0.25 and 0.40
4C-8 Calculate the ratio of sodium benzoate to benzoic acid that will produce
a pH 4.30 buffer. Use the buffer formula:
[H+]MNaA (10!4.30 )M NaA M NaA
6.2810-5 =
=
;
= 1.25
MHA
M HA
M HA
4C-9 What is the pH of 70 g NH4Cl and 600 mL concentrated aqueous NH3 (14.5 M)
diluted to 1.0 L ?
70 g NH4Cl mol NH4Cl
600 mL
= 1.31 M NH4Cl
14.5 M NH3 = 8.70 M NH3
L
53.49 g NH4Cl
1000 mL
[H+](8.70)
Buffer! 10-9.244 =
; pH = 10.066
Yes, 10-4 and 10-10 << 1.31 and 8.70
1.31
What happens to pH if dilute 5 mL buffer to 500 mL using water?
[H+ ](8.70/100)
10-9.244 =
; pH = 10.066 Yes, 10-4 and 10-10 << 0.0131 and 0.0870
1.31/100
The pH remains unchanged as long as the assumptions hold.
(Using the K, charge, and mass balance method shows diluting to 5 L gives
pH = 10.03, diluting to 20 L gives pH = 9.94)
1
4C-10 How does the pH of 400 mL of water change when

a. 100 mL 0.0500 M NaOH is added?
Dilution!
100
100 + 400
0.0500 M NaOH = 0.0100 M NaOH; pH = 12.000
pH 12 is a 5 order increase from pH 7 so [H+] changes by 105

b. 100 mL 0.0500 M HCl is added?
Dilution!
100
100 + 400
0.0500 M HCl = 0.0100 M HCl; pH = 2.000
pH 2 is a 5 order decrease from pH 7 so [H+] changes by 105

4C-11 How does pH of 400 mL of 0.200 M NH3 and 0.300 M NH4Cl change when
10-9.244 =
[H+ ]0.200
0.300
; pH = 9.068
Yes, 10-9 and 10-5 << 0.200 and 0.300
a. 100 mL of 0.0500 M NaOH is added?

Dilution!
400
0.300 M NH4+ = 0.240 M NH4+
400 + 100
400
0.200 M NH3
= 0.160 M NH3
400 + 100
100
0.050 M NaOH = 0.010 M NaOH
400 + 100
Reaction! Strong base NaOH will convert NH4+ to NH3. Calculate new M.
(M are just the recipe, this is an equivalent, easier, recipe.)
0.240 M NH4+ ! 0.010 M NaOH
0.160 M NH3 + 0.010 M NaOH
Buffer!
10-9.244 =
[H+ ]0.170
0.230
1 mol NH4+
= 0.230 M NH4+
1 mol NaOH
1 mol NH3
= 0.170 M NH3.
1 mol NaOH
; pH = 9.113
Yes, 10-9 and 10-5 << 0.170 and 0.230

pH changes from 9.068 to 9.113, much less than from pH 7 to 12 in 4C-10a!
b. 100 mL of 0.0500 M HCl is added?
Dilution!
400
0.300 M NH4+
400 + 100
400
0.200 M NH3
400 + 100
100
0.050 M HCl
400 + 100
= 0.240 M NH4+
= 0.160 M NH3
= 0.010 M HCl
Reaction! Strong acid HCl will convert NH3 to NH4+. Calculate new M.
0.160 M NH3 ! 0.010 M HCl
1 mol NH3
= 0.150 M NH3
1 mol HCl
1 mol NH4+
+
0.240 M NH4 + 0.010 M HCl
= 0.250 M NH4+
1 mol HCl
[H+ ]0.150
Buffer!
=
; pH = 9.022
0.250
Yes, 10-9 and 10-5 << 0.150 and 0.250
pH changes from 9.068 to 9.022, much less than from pH 7 to 2 in 4C-10b!
10-9.244
4C-12 What is the pH of 20.00 mL of 0.0800 M NH3 added to

a. 40.00 mL of water?
Ka =
20.00
0.0800 M NH3 = 0.02667 M NH3
20.00 + 40.00
[H+ ][NH3 ]
-9.244 ; [H+][OH-] = 10-14
+ = 10
charge:
mass:
solve:
[H+] + [NH4+] = [OH-]

0.02667 = [NH3] + [NH4+]
[H+] = 1.48110-11; pH = 10.829
Dilution!
[NH4 ]
b. 40.00 mL of 0.0300 M HCl?

Dilution!
20.00
0.0800 M NH3 = 0.02667 M NH3
20.00 + 40.00
40.00
0.0300 M HCl = 0.0200 M HCl
20.00 + 40.00
0.026667 M NH3 ! 0.0200 M HCl
0.0200 M HCl
Buffer!
1 mol NH3
= .006667 M NH3
1 mol HCl
1 mol NH4Cl
= 0.0200 M NH4Cl
1 mol HCl
[H+ ]0.006667
= 10-9.244; [H+] = 1.71010-9; pH = 8.767
0.0200
Yes, 10-9 and 10-5 << 0.006667 and 0.0200
Ka =
c. 40.00 mL of 0.0300 M NH4Cl?

Dilution!
Buffer!
20.00
0.0800 M NH3 = 0.02667 M NH3
20.00 + 40.00
40.00
0.0300 M NH4Cl = 0.0200 M NH4Cl
20.00 + 40.00
[H+ ]0.026667
Ka =
= 10-9.244; [H+] = 4.27610-10; pH = 9.369
0.0200
Yes, 410-10 and 210-5 << 0.026667 and 0.0200
d. 40.00 mL of 0.0400 M HCl?

Dilution!
20.00
0.0800 M NH3 = 0.02667 M NH3
20.00 + 40.00
40.00
0.0400 M HCl = 0.02667 M HCl
20.00 + 40.00
0.026667 M NH3 ! 0.026667 M HCl
0.026667 M HCl
Ka =
charge:
mass:
solve:
[H+ ][NH3 ]
[NH4+ ]
1 mol NH3
= .00000 M NH3
1 mol HCl
1 mol NH4Cl
= 0.02667 M NH4Cl
1 mol HCl
= 10-9.244; [H+][OH-] = 10-14
[H+] + [NH4+] = [OH-] + [Cl-]

0.026667 = [NH3] + [NH4+] ; 0.026667 = [Cl-]
[H+] = 3.90310-6; pH = 5.409
e. 40.00 mL of 0.0400 M NH4Cl?

Dilution!
Buffer!
20.00
0.0800 M NH3 = 0.02667 M NH3
20.00 + 40.00
40.00
0.0400 M NH4Cl = 0.02667 M NH4Cl
20.00 + 40.00
[H+ ]0.026667
= 10-9.244; [H+] = 5.70210-10; pH = 9.244
0.02667
Yes, 610-10 and 210-5 << 0.026667 and 0.026667
Ka =
f. 40.00 mL of 0.0400 M NaOH?

Dilution!
20.00
0.0800 M NH3 = 0.02667 M NH3
20.00 + 40.00
40.00
0.0400 M NaOH = 0.02667 M NaOH
20.00 + 40.00
mass balance on hydroxide: 0.02667 + [NH4+] + [H+] = [OH-] but we expect

[NH4+] + [H+] << .02667; [OH-] = 0.02667; pH = 14 pOH = 12.426
Weak base is irrelevant in the presence of a strong base. (Le Chatelier)
4C-13 0.10 M NaOH added to a 25.0 mL sample of 0.10 M acetic acid.
a. 0 mL added
[H+ ][CH3COO! ]
Ka =
= 1.7510-5
A solution of acetic acid.
[CH3COOH]
charge: [H+] = [OH-] + [CH3COO-]
mass:
0.100 = [CH3COOH] + [CH3COO-]
solve:
[H+] = 0.0013; pH = 2.88
4
b. 5.0 mL added
Dilution!
25
0.100 M CH3COOH = 0.08333 M CH3COOH
25 + 5
5
0.100 M NaOH
= 0.01667 M NaOH
25 + 5
Reaction! Strong base NaOH will convert CH3COOH to CH3COONa.

0.08333 M CH3COOH ! 0.01667 M NaOH
0.01667 M NaOH
Buffer!
1 mol CH3COOH
= 0.06667 M CH3COOH
1 mol NaOH
1 mol CH3COONa
= 0.01667 M CH3COONa.
1 mol NaOH
[H+ ]0.01667
; [H+] = 7.0210-5; pH = 4.15
0.06667
Yes, 0.00007 and 1.410-10 << 0.01667 and 0.06667
Ka =
c. 10.0 mL added
Dilution!
25
25 + 10
10
0.100 M NaOH
= 0.02857 M NaOH
25 + 10

0.07143 M CH3COOH ! 0.02857 M NaOH
0.02857 M NaOH
Buffer!
1 mol CH3COOH
= 0.04286 M CH3COOH
1 mol NaOH
1 mol CH3COONa
= 0.028577 M CH3COONa.
1 mol NaOH
[H+ ]0.02857
; [H+] = 2.6310-5; pH = 4.58
0.04286
Yes, 0.00003 and 3.810-10 << 0.02857 and .04286
Ka =
d. 15.0 mL added
Dilution!
25
25 + 15
15
0.100 M NaOH
= 0.03750 M NaOH
25 + 15

0.06250 M CH3COOH ! 0.03750 M NaOH
0.03750 M NaOH
Buffer!
Ka =
1 mol CH3COOH
= 0.02500 M CH3COOH
1 mol NaOH
1 mol CH3COONa
= 0.03750 M CH3COONa.
1 mol NaOH
[H+ ]0.03750
; [H+] = 1.1710-5; pH = 4.93
0.02500
Yes, 0.00001 and 8.610-10 << 0.03750 and 0.02500
e. 20.0 mL added
Dilution!
25
25 + 20
20
0.100 M NaOH
= 0.04444 M NaOH
25 + 20

0.05556 M CH3COOH ! 0.04444 M NaOH
0.04444 M NaOH
Buffer!
Ka =
1 mol CH3COOH
= 0.01112 M CH3COOH
1 mol NaOH
1 mol CH3COONa
= 0.04444 M CH3COONa.
1 mol NaOH
[H+ ]0.04444
; [H+] = 4.3810-6; pH = 5.36
0.01111
Yes, 0.000004 and 2.310-9 << 0.04444 and 0.01111

f. 25.0 mL added
Dilution!
25
25 + 25
25
0.100 M NaOH
= 0.05000 M NaOH
25 + 25

0.05000 M CH3COOH ! 0.05000 M NaOH
0.05000 M NaOH
Ka =
1 mol CH3COONa
= 0.05000 M CH3COONa.
1 mol NaOH
[H+ ][CH3COO! ]
= 1.7510-5
[CH 3COOH]
charge:
mass:
solve:
1 mol CH3COOH
= 0.0000 M CH3COOH
1 mol NaOH
A solution of sodium acetate.
[Na+] + [H+] = [OH-] + [CH3COO-]

0.05000 = [CH3COOH] + [CH3COO-]
0.05000 = [Na+]
[H+] = 1.8710-9; pH = 8.73
g. 30.0 mL added
Dilution!
25
25 + 30
30
0.100 M NaOH
= 0.05454 M NaOH
25 + 30

0.05454 M NaOH ! 0.04545 M CH3COOH
0.04545 M CH3COOH
1 mol NaOH
= 0.009091 M NaOH
1 mol CH3COOH
1 mol CH3COONa
= 0.04545 M CH3COONa.
1 mol CH3COOH
Mass balance on hydroxide: 0.009091 + [CH3COOH] + [H+] = [OH-] but we

expect [CH3COOH] + [H+] << .009091; [OH-] = 0.009091; pH = 14 pOH = 11.96
6
h. 35.0 mL added
Dilution!
25
0.100 M CH3COOH = 0.041667 M CH3COOH
25 + 35
35
0.100 M NaOH
= 0.058333 M NaOH
25 + 35

0.058333 M NaOH ! 0.041667 M CH3COOH
0.041667 M CH3COOH
1 mol NaOH
= 0.01667 M NaOH
1 mol CH3COOH
1 mol CH3COONa
= 0.041667 M CH3COONa.
1 mol CH3COOH
Mass balance on hydroxide: 0.01667 + [CH3COOH] + [H+] = [OH-] but we

expect [CH3COOH] + [H+] << .01667; [OH-] = 0.01667; pH = 14 pOH = 12.22
Results from Problem 4C-13

Answers to Problems 4D-1, 4D-2, 4D-3, 4D-4, 4D-5 can be found in Exploration 4D
on the module web site, http://chemistry.beloit.edu/Rain/pages/titr.html

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Buffer Problems

if [H+] and [OH] << MNaA and MHA

Many of these problems demonstrate the properties of a buffer.

Yes, 10-4 and 10-11 << 0.25 and 0.75

4C-7 pH of a solution containing 0.25 M NH3 and 0.40 M NH4Cl.

Yes, 10-10 and 10-5 << 0.25 and 0.40

4C-10 How does the pH of 400 mL of water change when

0.0500 M NaOH = 0.0100 M NaOH; pH = 12.000

pH 12 is a 5 order increase from pH 7 so [H+] changes by 105

0.0500 M HCl = 0.0100 M HCl; pH = 2.000

pH 2 is a 5 order decrease from pH 7 so [H+] changes by 105

Yes, 10-9 and 10-5 << 0.200 and 0.300

a. 100 mL of 0.0500 M NaOH is added?

Yes, 10-9 and 10-5 << 0.170 and 0.230

4C-12 What is the pH of 20.00 mL of 0.0800 M NH3 added to

[H+] + [NH4+] = [OH-]

b. 40.00 mL of 0.0300 M HCl?

c. 40.00 mL of 0.0300 M NH4Cl?

= 10-9.244; [H+] = 4.27610-10; pH = 9.369

d. 40.00 mL of 0.0400 M HCl?

= 10-9.244; [H+][OH-] = 10-14

[H+] + [NH4+] = [OH-] + [Cl-]

e. 40.00 mL of 0.0400 M NH4Cl?

f. 40.00 mL of 0.0400 M NaOH?

mass balance on hydroxide: 0.02667 + [NH4+] + [H+] = [OH-] but we expect

Reaction! Strong base NaOH will convert CH3COOH to CH3COONa.

Reaction! Strong base NaOH will convert CH3COOH to CH3COONa.

Reaction! Strong base NaOH will convert CH3COOH to CH3COONa.

Yes, 0.00001 and 8.610-10 << 0.03750 and 0.02500

Reaction! Strong base NaOH will convert CH3COOH to CH3COONa.

Yes, 0.000004 and 2.310-9 << 0.04444 and 0.01111

Reaction! Strong base NaOH will convert CH3COOH to CH3COONa.

A solution of sodium acetate.

[Na+] + [H+] = [OH-] + [CH3COO-]

Reaction! Strong base NaOH will convert CH3COOH to CH3COONa.

Mass balance on hydroxide: 0.009091 + [CH3COOH] + [H+] = [OH-] but we

Reaction! Strong base NaOH will convert CH3COOH to CH3COONa.

Mass balance on hydroxide: 0.01667 + [CH3COOH] + [H+] = [OH-] but we

Results from Problem 4C-13

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