Skoog/Holler/Crouch Chapter 22

Principles of Instrumental Analysis, 6th ed. Instructor’s Manual

CHAPTER 22
22-1. (a)
0.0592 1 1
E = 0.799 − log +
= 0.799 − 0.0592 log
1 [Ag ] 0.0261

E = 0.799 – 0.094 = 0.705 V

(b)
0.100
E = 0.771 − 0.0592 log = 0.771 − 0.129 = 0.642 V
6.72 × 10−4

(c)
E = 0.073 – 0.0592 log 0.05 = 0.141 V

22-2. (a)
0.0592 pH 0.0592 0.987
E = 0.000 − log + 2 2 = − log = 0.015 V
(1.76 )
2
2 [H ] 2

(b)
( 2 × 10−4 )
1/ 2
0.0592
E = 1.178 − log = 0.826 V
5 (0.194)(3.5 × 10−3 )6

(c)
0.0592
E = 0.446 − log 0.0520 = 0.446 + 0.038 = 0.484 V
2

22-3. (a) 2H+ + 2e– U H2 E0 = 0.000 V

(1) E = 0.000 – (0.0592/2) log[1/(0.020)2] = –0.101 V

(2) ionic strength μ = ½[0.02 × 12 + 0.03 × 12 + 0.05 × 12] = 0.050

From Table a2-1, γ H+ = 0.86 and aH+ = 0.86 × 0.02 = 0.0172

E = 0.000 – (0.0592/2) log[1.00/(0.0172)2] = –0.104 V

(b) Fe3+ + e– U Fe2+ E0 = 0.771 V

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Principles of Instrumental Analysis, 6th ed. Chapter 22

(1) E = 0.771 – 0.0592 log (0.0111/0.0111) = 0.771 V

(2) μ = ½[0.0111 × 22 + 0.0111 × 32 +2 × 0.0111 × 12 + 3 × 0.0111 × 12]

= 0.100

From Table a2-1,

γ Fe = 0.40
2+ and aFe2+ = 0.40 × 0.0111 = 0.00444

γ Fe = 0.18
3+ and aFe3+ = 0.18 × 0.0111 = 0.00200

E = 0.771 – 0.0592 log[0.00444/0.00200] = 0.750 V

22-4. (a) Sn4+ + 2e– U Sn2+ E0 = 0.154 V

(1) E = 0.154 – (0.0592/2) log[3.00 × 10–5/6.00 × 10–5] = 0.163 V

(2) μ = ½[3.00 × 10–5 × 22 + 6.00 × 10–5 × 42 + 6.00 × 10–5 × 12 + 24 ×10–5 × 12]

= 6.9 × 10–4

From Equation a2-3,

0.509(2) 2 6.9 ×10−4

− log γ Sn 2+ = = 0.05085
1 + 3.28 × 0.6 6.9 × 10−4

γ Sn = 0.890
2+ and aSn 2+ = 0.890 × 3.00 × 10−5 = 2.67 × 10–5

0.509(4) 2 6.9 × 10−4

− log γ Sn 4+ = = 0.195
1 + 3.28 × 1.1 6.9 ×10−4

γ Sn = 0.638
4+ and aSn 4+ = 0.638 × 6.00 × 10–5 = 3.83 × 10–5

E = 0.154 – (0.0592/2) log[(2.67 × 10–5)/(3.83 × 10–5)] = 0.159 V

(b) (1) As in Solution 22-4a, E = 0.163 V

(2) Here the contribution of the tin species to μ is neglible and μ = 0.0800

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Principles of Instrumental Analysis, 6th ed. Chapter 22

0.509(2) 2 0.080
− log γ Sn 2+ = = 0.3699
1 + 3.28 × 0.6 0.080

γ Sn = 0.427
2+ and aSn 2+ = 0.427 × 3.00 × 10−5 = 1.28 × 10–5

0.509(4) 2 0.080
− log γ Sn 4+ = = 1.140
1 + 3.28 ×1.1 0.080

γ Sn = 0.072
4+ and aSn 4+ = 0.072 × 6.00 × 10–5 = 4.35 × 10–6

E = 0.154 – (0.0592/2) log[(1.28 × 10–5)/(4.35 × 10–6)] = 0.140 V

22-5. (a) E = – 0.151 – 0.0592 log(0.0150) = –0.043 V

(0.0040) 2
(b) E = − 0.31 − 0.0592 log = –0.10 V
0.0600

(c) mmol Br– = 25.0 × 0.0500 = 1.25

mmol Ag+ = 20.0 × 0.100 = 2.00

excess Ag+ = 2.00 – 1.25 = 0.75 mmol in a total volume of 45.0 mL

[Ag+] = 0.75/45.0 = 0.0167 M

1
E = 0.799 − 0.0592 log = 0.694 V
0.0167

(d) mmol Br– = 20.0 × 0.100 = 2.00

mmol Ag+ = 25.0 × 0.0500 = 1.25

excess Br– = 2.00 – 1.25 = 0.75 mmol in a total volume of 45.0 mL

[Br–] = 0.75/45.0 = 0.0167 M

E = 0.073 – 0.0592 log(0.0167) = 0.178 V

0.0592 ⎡ (2.00 ×10−2 ) 2 ⎤

22-6. (a) E = 1.33 − log ⎢ −3 14 ⎥
= 1.20 V
6 ⎣ (4.00 ×10 )(0.100) ⎦

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Principles of Instrumental Analysis, 6th ed. Chapter 22

0.0592 0.100
(b) E = 0.334 − log = 0.307 V
0.200 × ( 0.600 )
4
2

0.0592 1
22-7. (a) Eright = − 0.126 − log = –0.159 V
2 5.6 ×10−2

2 × 10−3
Eleft = − 0.408 − 0.0592 log = –0.485
1×10−4

Ecell = –0.159 – (–0.485) = 0.326 V

The cell is spontaneous as written oxidation on the left, reduction on the right

(b) On the right we have VO2+ + 2H+ + e– U V3+ + H2O

3.00 ×10−2
Eright = 0.359 − 0.0592 log = 0.053 V
(2.00 × 10−3 )(1.00 × 10−2 ) 2

0.0592 1
Eleft = 0.788 − log = 0.738 V
2 2 ×10−2

Ecell = 0.053 – 0.738 = –0.685 V

The cell is not spontaneous in the direction considered (oxidation on the left,

eduction on the right), but is spontaneous in the opposite direction

0.0592 5.50 × 10−2

(c) Eright = 0.154 − log = 0.089 V
2 (3.50 × 10−4 )

3.00 × 10−5
Eright = 0.771 − 0.0592 log = 0.956 V
(4.00 × 10−2 )

Ecell = 0.089 – 0.956 = –0.867 V

The cell is not spontaneous in the direction considered, but instead is spontaneous

n the opposite direction (reduction on the left, oxidation on the right).

22.8. (a) Eright = –0.151 – 0.0592 log 0.100 = –0.092 V

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Principles of Instrumental Analysis, 6th ed. Chapter 22

0.0592 1
Eleft = 0.320 − log = 0.265 V
(0.0400) ( 0.200 )
2
3

Ecell = –0.092 – 0.265 = –0.357 V Not spontaneous as written

4.50 × 10−2
(b) Eright = 0.36 − 0.0592 log = 0.37 V
(7.00 × 10−2 )

0.0592 1
Eleft = − 0.763 − log = –0.855
2 (7.50 × 10−4 )

Ecell = 0.37 – (–0.86) = 1.23 V Spontaneous as written (oxidation on left)

(c) Eright = 0.222 – 0.592 log (7.50 × 10–4) = 0.407 V

0.0592 0.200
Eleft = 0.000 − log = –0.164 V
2 (7.50 × 10−4 ) 2

Ecell = 0.407 – (–0.164) = 0.571 V Spontaneous as written (oxidation on left)

22-9. Ni2+ + 2e– U Ni(s) E0 = –0.250 V

Ni(CN)42– + 2e– U Ni(s) + 4CN– E0 = ?

0.0592 1
ENi2+ /Ni = − 0.250 − log
2 [Ni 2+ ]

[Ni(CN) 4 2− ]
Kf =
[Ni 2+ ][CN − ]4

0.0592 K [CN − ]4
E = − 0.250 − log f
2 [Ni(CN) 4 2− ]

For the 2nd reaction,

0.0592 [CN − ]4
E = E0 − log
2 [Ni(CN) 4 2− ]

0.0592
When [CN–]4/[Ni(CN)42–] = 1.00, E = E0 = −0.250 − log K f
2
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Principles of Instrumental Analysis, 6th ed. Chapter 22

0.0592
E 0 = − 0.250 − log1× 1022 = –0.90 V
2

22-10. Pb2+ + 2e– U Pb(s) E0 = –0.126 V

0.0592 1
EPb2+ /Pb = − 0.126 − log
2 [Pb 2+ ]

PbI2(s) + 2e– U Pb(s) + 2I– E0 = ?

0.0592
EPbI2 /Pb = E 0 − log[I − ]2
2
Ksp = [Pb2+][I–]2 = 7.1 × 10–9

0.0592 [I − ]2
EPb2+ /Pb = − 0.126 − log
2 K sp

When [I–] = 1.00, E = E0

0.0592 (1.00) 2
E 0 = − 0.126 − log = –0.367 V
2 7.1× 10−9

22-11. Proceeding as in Solution 22-10, we obtain,

E0 = –0.037 V

22-12. Proceeding as in Solution 22-9, we find

E0 = –1.92 V

1 [Cl− ]
22-13. E = − 0.336 − 0.0592 log = − 0.336 − 0.0592 log
[Tl+ ] K sp

When [Cl–] = 1.00, E = E0TlCl = –0.557 V

–0.557 = –0.336 – 0.0592 log(1.00/Ksp)

Ksp = 1.85 × 10–4

22-14. Proceeding as in Solution 22-13, we obtain

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Principles of Instrumental Analysis, 6th ed. Chapter 22

Ksp = 1.0 × 10–15

22-15. Eright = 0.073 – 0.0592 log (0.0850) = 0.136 V

0.448
Eleft = − 0.256 − 0.0592 log = –0.498 V
3.7 ×10−5

Eright – Eleft = 0.136 – (–0.498) = 0.634 V

Ecell = Eright – Eleft – IR = 0.634 – 0.075 × 4.87 = 0.268 V

1
22-16. Eright = 0.337 − 0.0592 log = 0.242 V
2.50 ×10−2

3.42 ×10−2
Eleft = 1.00 − 0.0592 log = 0.601 V
2.67 ×10−4 × (4.81× 10−3 ) 2

Eright – Eleft = 0.242 – 0.601 = –0.359 V

Ecell = Eright – Eleft – IR = –0.359 – 0.0750 × 3.81 = –0.644 V

22-17. Proceeding as in Solution 22-16, we obtain,

Ecell = 0.24 V

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Principles of Instrumental Analysis, 6th ed. Chapter 22

22-18. (a) The spreadsheet follows.

(b) The values of γ± compare quite well to those of MacInnes at the lower ionic strengths. At

the higher ionic strengths there is a small deviation with the calculated values being a

little lower than MacInnes’s values. A look at MacInnes’s book reveals that he used

experimental values of γ± when possible and used the Debye-Hückel equation to

interpolate between experimental values. This probably accounts for the differences

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Principles of Instrumental Analysis, 6th ed. Chapter 22

seen. Likewise the E0 values show small differences which may be attributed to the

differences in γ values.

(c) The desriptive statistics are shown in the spreadsheet that follows.

(d) The mean value using our calculations is 0.2222 ± 0.0002 V. The mean of MacInnes

values is 0.22250 ± 0.00007 V. These results are very close. Also, the 95% CI for our

results is

95% CI = 0.2222 ± 0.0002. Hence, we can be 95% certain that the mean lies within the

interval 0.2220 to 0.2224 if the only uncertainties are random. We can also conclude that

MacInnes’s results are very precise and of extremely high quality.