Skoog/Holler/Crouch

Principles of Instrumental Analysis, 6th ed.

Chapter 24
Instructors Manual

CHAPTER 24
24-1. (a)

2Pb2+ +2H2O U Pb(s) + O2 +4H+

Pb2+ + 2e U Pb(s)

E0 = 0.126V

O2(g) + 4H+ + 4e U 2H2O

E0 = 1.229 V

Eright = 0.126
Eleft = 1.299

0.0592
1
= 0.1556 V
log
2
0.100

0.0592
1
= 1.1862 V
log
4
0.800 (0.200) 4

Ecell = 0.1566 1.1862 = 1.342 V

(b)
24-2. (a)

0.250 0.950 = 0.238 V

To lower M1 to 2.00 104.
E1 = EM0 1

0.0592
1
log
= EM0 1 0.109 V
2
2 104

M2 begins to deposit when

E2 = EM0 2 0.0592 log

1
= EM0 2 0.0592
0.100

When E2 = E1, the concentration of M1 will be reduced to 2.00 104 and M2will not
have begun to deposit. That is,
EM0 2 0.0592 = EM0 1 0.109 V

EM0 2 EM0 1 = E 0 = 0.109 ( 0.0592) = 0.050 V

Principles of Instrumental Analysis, 6th ed.

Chapter 24

Charge on M2

Charge on M1

1
2
3
2
2

2
2
1
1
3

(a)
(b)
(c)
(d)
(e)
24-3. Ag+ + e U Ag(s)

E0 = EM0 2 EM0 1 , V
0.109 + 0.0592 = 0.050
0.109 + 0.0296 = 0.079
0.219 + 0.020 = 0.199
0.219 + 0.0296 = 0.189
0.073 + 0.0296 = 0.043

E0 = 0.799 V

Cu2+ + 2e U Cu(s)

E0 = 0.337 V

BiO+ + 2H+ + 3e U Bi(s) + H2O

E0 = = 0.320 V

(a) First, we calculate the potentials vs. Ag-AgCl needed to reduce the concentrations to
106 M. For Ag+,
Ecell = 0.799 0.0592 log

1
0.199 = 0.444 0.199 = 0.245 V
1.00 106

For Cu2+
Ecell = 0.337

0.0592
1
log
0.199 = 0.040 V
2
1.0 106

For BiO+
Ecell = 0.320

0.0592
1
log
0.199 = 0.009 V
6
3
1.0 10 (0.5) 2

Bi(s) begins to deposit when

Ecell = 0.320

0.0592
1
log
0.199 = 0.084 V
3
0.0550 (0.5) 2

Cu(s) begins to deposit when

Ecell = 0.337

0.0592
1
log
0.199 = 0.111 V
2
0.125
2

Principles of Instrumental Analysis, 6th ed.

Chapter 24

(b) Silver could be separated from BiO+ and Cu2+ by keeping the cell potential greater
than 0.111 V. Cu2+ and BiO+ cannot be separated by controlled-potential electrolysis.
24-4. We calculate the potentials at which the silver salts first form
For I, Ecell = 0.244 (0.151 0.0592 log 0.0250) = 0.300 V
For Br, Ecell = 0.244 (0.073 0.0592 log 0.0250) = 0.076 V
For Cl, Ecell = 0.244 (0.222 0.0592 log 0.0250) = 0.073 V
(a)

AgI forms first at a potential of 0.0300 V (galvanic cell).

(b)

When [I] 105 M

Ecell = 0.244 (0.151 0.0592 log 105) = 0.099 V

AgBr does not form until Ecell = 0.076 V so the separation is feasible if the Ecell does is
kept above 0.076 V.
(c)

I could be separated from Cl by maintaining the cell potential above 0.073 V.

(d)

For [Br] 105 M

Ecell = 0.244 (0.073 0.0592 log 105) = 0.125 V

But AgCl forms at a cell potential of 0.073 V, so separation is not feasible.

24-5. (a)

(b)

Ecell = 0.854

0.0592
1
log 6 0.244 = 0.432 V
2
10

Kf = 1.8 107 =

[Hg(SCN) 2 ]
[Hg(SCN) 2 ]
=
2
2+
[Hg ][SCN ]
[Hg 2+ ](0.150) 2

[Hg(SCN)2] + [Hg2+] = 106

Because of the large amount of SCN, we can safely assume that [Hg2+] << [Hg(SCN)2]
Substituting into the expression for Kf, we find

Principles of Instrumental Analysis, 6th ed.

1.8 107 =

Chapter 24

1.00 106
[Hg 2+ ] (0.150) 2

[Hg2+] = 2.47 10-12

0.0592
1
log
0.244 = 0.266 V
2
2.47 1012

Ecell = 0.854
(c)

With a large [Br], we can assume [Hg2+] + [HgBr42-] [HgBr42-] = 1.00 106
0.0592
(0.150) 4
log
0.244 = 0.101 V
2
1.00 106

Ecell = 0.223
24-6. (a)

Co2+ + 2e U Co(s)
To deposit 0.270 g of Co(s) would require the following charge
Q = 0.270 g

1 mol Co
2 mol e
1F
96485 C

= 8.841 102 C

58.93 g
mol Co
mol e
F

Q = It so t = Q/I
t = 8.841 102 C/0.750 C/s = 1178.8 s or 19.6 min
(b)

3 Co2+ + 4 H2O U Co3O4(s) + 8H+ + 2e

Q = 0.270 g

3 mol Co2+ consumed per 2 mol e

1 mol Co
2 mol e
1F
96485 C

= 2.947 102 C

58.93 g
3 mol Co
mol e
F

t = 2.947 102 C/0.750 C/s = 392.95 s or 6.55 min

24-7. (a)

Q = 0.300 g

1 mol Tl
3 mol e
1F
96485 C

= 4.249 102 C

204.37 g
mol Tl
mol e
F

t = Q/I = 4.249 102 C/0.905 C/s = 469.5 s or 7.83 min

(b)

2Tl+ + 3 H2O U Tl2O3(s) + 6H+ + 4 e-

2 mol Tl+ consumed per 4 mol e

Principles of Instrumental Analysis, 6th ed.

Q = 0.300 g

Chapter 24

1 mol Tl
4 mol e
1F
96485 C

=283.27 C

204.37 g
2 mol Tl
mol e
F

t = 283.27 C/0.905 C/s = 313.00 s or 5.22 min

(c)

Proceeding as in part (a), with the only difference being 1 mol e/mol Tl
Q = 141.63 C
t = 156.5 s or 2.61 min

24-8. Sample 1 at 1.0V

at 1.80 V

11.63 C

68.60 C

2 mol CCl4
1 mol e

= 1.25 104mol CCl4

96485 C
2 mol e

2 mol CHCl3
1 mol e

= 2.370 104 mol CHCl3

96485 C
6 mol e

original no. mol CHCl3 = 2.370 104 1.205 104 = 1.165 104
1.205 104 mol CCl4 153.82 g CCl4 / mol CCl4
100% = 2.47% CCl4
0.750 g sample
1.165 104 mol CHCl3 119.37 g CHCl3 / mol CHCl3
100% = 1.85% CHCl3
0.750 g sample

In a similar manner, we can calculate the other percentages as shown in the spreadsheet.

Principles of Instrumental Analysis, 6th ed.

Chapter 24

24-9. 1 mol As2O3 = 2 mol HAsO32- = 2 mol I2 = 4 mol e

Q = 0.1276 C/s (11 min 60 s/min + 54 s) = 91.106 C
Mass As2O3 =

%As2O3 =

1 mol As 2 O3
197.8 g As 2 O3
91.106 C

= 0.04669

96485 C/mol e
4 mol e
mol

0.04669 g
100 = 0.731
6.39

24-10. The equivalent mass of an acid is that mass that contains one mole of titratable H+.
0.0441 C/s 266 s

equiv mass =

1F
1 equiv HA

= 1.216 104 equiv HA

96485 C
F

0.0809 g HA
= 665 g/equiv
1.216 104 equiv HA

24-11. 1 mol C6H5NH2 = 3 mol Br2 = 6 mol e

Q = (3.76 0.27) min 60 s/min 1.00 103 C/s = 0.2094 C
mol C6H5NH2 = 0.2094 C

1 mol C6 H 5 NH 2
1 mol e

= 3.617 107
96485 C
6 mol e

mass C6H5NH2 = 3.617 107 mol C6 H 5 NH 2

= 33.7 g
24-12. The spreadsheet is attached.

93.128 g
106 g/g
mol C6 H 5 NH 2

Principles of Instrumental Analysis, 6th ed.

Chapter 24