Nama : Siti Rahayu

NIM : 1806021

Kelas : A

Skoog Chapter 22

Jawaban :

22.1 Calculate the electrode potentials of the following half-cells

a. Ag+(0.0261 M)|Ag
b. Fe3+(6.72 x 10-4 M), Fe2+ (0.l00 M)|Pt
c. AgBr(sat'd), Br' (0.050 M)|Ag
Jawab :
0.0592 1
a) E = 0.799 = log
1 ¿¿
1
E = 0.799 – 0.0592 log
0.0261
E = 0.799 – 0.094
E = 0.705 V
0.100
b) E = 0.771 – 0.0592 log
6.72 x 10⁻ ⁴
E = 0.711 – 0.129
E = 0.642 V
c) E = 0.073 – 0.0592 log 0.05
E = 0.141 V

22.2 Calculate the electrode potentials of the following half-cells.

a. HCl(1.76 M) | H2(0.987 atm), Pt
b. IO3-(0.194 M), I2(2.00 x 10-4 M), H+ (3.50 X 10-3 M)| Pt
c. Ag,CrO.(sat'd),CrO,'-(0.0520 M)IAg
Jawab :
 0.0592 PH ₂
a) E = 0.000 - log
2 ¿¿
0.0592 0.987
E=- log
2 (1.76) ²
E = 0.015 V
0.0592 (2 x 10−4 )¹ /²
b) E = 1.178 - log
5 (0.194) ¿ ¿
E = 0.826 V
0.0592
c) E = 0.446 - log 0.0520
2
E = 0.446 + 0.038
E = 0.484 V

22.3 For each the following half-cells, compare the electrode potentials calculated from (1)
concentration and (2) activity data.
a. HCl(0.0200 M),NaCl(0.0300M)|H2(1.00 atm)|Pt
b. Fe(ClO4)2(0.0111 M),Fe(ClO4)3(0.0111M)|Pt

Jawab :
a) 2H+ + 2e- ↔ H2 E0 = 0.000 V
0.0592 1
(1) E = 0.000 – log [ ] = -0.101 V
2 (0.020)²
(2) Kekuatan ion : μ = ⅟₂ [0.02 x 1² + 0.03 x 1² + 0.05 x 1²] = 0.050
Dari tabel a2-1, ϒH+ = 0.86 dan αH+ = 0.86 x 0.02 = 0.0172
0.0592
E = 0.000 – log ¿] = 0.104 V
2
b) Fe3+ + e- ↔ Fe2+ E0 = 0.771 V
0.0111
(1) E = 0.771 – 0.0592 log = 0.771 V
0.0111
(2) μ = ⅟₂[0.0111 x 2² + 0.0111 x 3² + 2 x 0.0111 x 1² + 3 x 0.0111 x 1²]
μ = 0.100
dari tabel a2-1
ϒFe2+ = 0.40 dan αFe2+ = 0.04 x 0.0111 = 0.00444
 ϒFe3+ = 0.18 dan αFe3+ = 0.18 x 0.0111 = 0.00200
0.00444
E = 0.771 – 0.0592 log = 0.750 V
0.00200

22.4 For each the following half-cells, compare the electrode potentials calculated from (1)
concentration and (2) activity data.
a. Sn(ClO4)2(3.00 x 10-5 M), Sn(ClO4)4 (6.00 x 10-5 M)|Pt
b. SN(ClO4)2(3.00 x 10-5 M), Sn(ClO4)4 (6.00 x 10-5 M), NaClO4 (0.0800 M)|Pt

Jawab :
a) Sn2+ + 2e- ↔ Sn2+ E0 = 0.154 V
0.0592 ¿
(1) E = 0.154 – log [3.00 x 10 ⁻⁵ ¿ −5 ]= 0.163 V
2 (6.00 x 10 )
(2) μ = ⅟₂ [3.00 x 10⁻⁵ x 2² + 6.00 x 10⁻⁵ x 4² + 6.00 x 10⁻⁵ x 1² + 24 x 10⁻⁵ x
1²] = 6.9 x 10⁻⁴
Dari persamaan a2-3
0.509(2)² √ 6.9 x 10 ⁻ ⁴
-log ϒSn2+ = = 0.05085
1+ 3.28 x 0.6 √ 6.9 x 10⁻ ⁴
ϒSn2+ = 0.890 dan αSn2+ = 0.890 x 3.00 x 10⁻⁵ = 2.67 x 10⁻⁵
0.509(4 )² √6.9 x 10 ⁻ ⁴
-log ϒSn4+ = = 0.195
1+ 3.28 x 1.1 √ 6.9 x 10 ⁻ ⁴
ϒSn4+ = 0.638 dan αSn4+ = 0.638 x 6.00 x 10⁻⁵ = 3.83 x 10⁻⁵
0.0592 (2.67 x 10−5)
E = 0.154 - log [ ]= 0.159 V
2 (3.83 x 10 ⁻⁵)
b) (1) dari jawaban no 4a, E = 0.163 V
(2) disini kontribusi spesi timah untuk μ diabaikan dan μ = 0.0800
0.509 (2)² √ 0.080
-log ϒSn2+ = = 0.3699
1+ 3.28 x 0.6 √ 0.080
ϒSn2+ = 0.427 dan αSn2+ = 0.427x 3.00 x 10⁻⁵ = 1.28 x 10⁻⁵
0.509(4 )² √ 0.080
-log ϒSn4+ = = 1.140
1+ 3.28 x 1.1 √ 0.080
ϒSn4+ = 0.072 dan αSn4+ = 0.072 x 6.00 x 10⁻⁵ = 4.35 x 10⁻⁶
 0.0592 (1.28 x 10−5 )
E = 0.154 - log [ ] = 0.140 V
2 (4.35 x 10⁻ ⁶)

22.5 Calculate the potential of a silver electrode in contact with the following:
a. a solution that is 0.0150 M in I2 and saturated with AgI.
b. a solution that is 0.0040M in CN- and 0.0600M in Ag(CN)2-.
c. The solution that results from mixing 25.0mL of 0.0500 KBr with 20.0mL of
0.100 M Ag+
d. The solution that results from mixing 25.0mL of 0.0500 Ag +with 20.0mL of
0.100 M KBr

Jawab :
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 x 0.0500 = 1.25
mmol Ag+ = 20.0 x 0.100 = 2.00
Kelebihan Br⁻ = 2.00 – 1.25 = 0.75 mmol dalam total volume 45.0 mL
0.75
[Br⁻] = = 0.0167 M
45.0
E = 0.073 – 0.0592 log (0.0167) = 0.178 V

22.6 Calculate the electrode potentials for the following systems:

a. Cr2O72- (4.00 x 10-3 M), Cr3+ (2.00 x 10-2 M), H+(0.100 M)|Pt
b. UO22++(0.200 M), U4+ (0.100 M), H+ (0.500 M)|Pt

Jawab :
0.0592 (2.00 x 10−2 )²
a) E = 1.33 - log [ ]= 1.20 V
6 (4.00 x 10⁻ ³)(0.100) ¹⁴
0.0592 0.100
b) E = 0.334 - log =0.307 V
2 0.200 x (0.600) ⁴
22.7 Calculate the theoretical potential of each of the following cells. Is the cell reaction
spontaneous as written or spontaneous in the opposite direction?
a. Pt|Cr3+ (1.00 x 10-4 M), Cr2+ (2.00 x 10 -3 M) || Pb2+ (5.60 x 10 -2 M)|Pb
b. Hg|Hg22+ +(2.00 x 10 -2M) || H+ (1.00 x 10 -2M), V3+ (3.00 x 10 -2M), VO (2.00
x 10 -3 M)|Pt
c. Pt|Fe3+ (4.00 x 10 -2 M), Fe2+ (3.00 x 10-5 M) || Sn2+ (5.50 x 10 -2 M), Sn4+ (3.50
x 10 -4 M)|Pt

Jawab :
0.0592
a) Ekanan = -0.126 - log ¿-0.159 V
2
2 x 10 ⁻ ³
Ekiri = -0.408 – 0.0592 log = -0.485 V
1 x 10⁻ ⁴
Esel = -0.159 – (-0.485)= 0.326 V
Sel spontan, reaksi oksidasi tertulis di kiri, reduksi di kanan
b) disebelah kanan kita memiliki VO2+ + 2H+ + e- ↔ V3+ + H2O
3.00 x 10⁻ ²
Ekanan = 0.359 – 0.0592 log = 0.053 V
(2.00 x 10−3)(1.00 x 10−2) ²
0.0592 1
Ekiri = 0.788 - log = 0.738 V
2 2 x 10⁻ ²
Esel = 0.053 – 0.738 = -0.685 V
Sel tidak spontan dalam arah yang dipertimbangkan (oksidasi di kiri, reduksi
di kanan), tetapi spontan dalam arah yang berlawanan
0.0592 5.50 x 10 ⁻ ²
c) Ekanan = 0.154 - log = 0.089 V
2 ( 3.50 x 10− 4 )
3.00 x 10 ⁻ ⁵
Ekiri = 0.771 – 0.0592 log = 0.956 V
(4.00 x 10−2 )
Esel = 0.089 – 0.956 = -0.867 V
Sel tidak spontan dalam arah yang dipertimbangkan, melainkan spontan pada
arah yang berlawanan (reduksi di kiri, oksidasi di kanan)

22.8 Calculate the theoretical potential of each of the following cells. Is the cell reaction
spontaneous as written or spontaneous in the opposite direction?
 a. Bi|BiO+ (0.0400 M), H+ (0.200 M) || I- (0.100 M), AgI (sat'd)|Ag
b. Zn|Zn2+(7.50 X 10-4M)||Fe(CN)64- (4.50 x 10-2M),Fe(CN)63- (7.00 x10-2M)| Pt
c. Pt2H2 (0.200 atm)|HCI (7.50 X 10-4M), AgCI (sat'd)|Ag

Jawab :
1. a) Ekanan = -0.151 – 0.0592 log 0.100 = -0.092
0.0592 1
Ekiri = 0.320 - log = 0.265 V
3 ( 0.0400 ) (0.200) ²
Esel = -0.092 – 0.265 = -0.357 V tidak spontan seperti yang tertulis
4.50 x 10 ⁻²
b) Ekanan = 0.36 – 0.0592 log −2 = 0.37 V
(7.00 x 10 )
0.0592 1
Ekiri = -0.763 -
2
log = 0.265 V
(7.00 x 10−⁴ )
Esel = 0.37 – (-0.86) = 1.23 V spontan seperti yang tertulis
(oksidasi di kiri)
c) Ekanan = 0.222 – 0.0592 log (7.50 x 10⁻⁴) = 0.407 V
0.0592 0.200
Ekiri = 0.000 -
2
log −⁴ = -0.164 V
(7.50 x 10 )²
Esel = 0.407 – (-0.164) = 0.571 V spontan seperti yang tertulis
(oksidasi di kiri)

22.9 Compute Eo for the process

Ni(CN)42- + 2e- ⇌ Ni(s) + 4CN-

Given that the formation constant for the complex is 1.0 x 1022.
Jawab :
Ni2+ + 2e– ⇌ Ni(s) E0 = – 0.250 V
Ni(CN)42– + 2e– ⇌ Ni(s) + 4CN– E0 = ?
0.0592 1
E¿ 2+¿/ ¿ = −250− log ¿
¿
2 ¿ ¿
K f =¿ ¿ ¿4
0.0592
E = −250− log Kf ¿ ¿ ¿ ¿
2
 reaksi kedua :
0.0592
E = −E0 − log Kf ¿ ¿ ¿ ¿
2
0.0592
When [CN–]4/[Ni(CN)42–] = 1.00, E = −250− log Kf
2

0.0592
E0 = −250− L og 1 x 1022=−0.90V
2

22.10 The solubility product constant for PbI2 is 7.1 x 10-9 at 25oC. Calculate Eo for the process
PbI2 (s) + 2e- ↔ Pb(s) + 2I2
Jawab :
Pb2+ + 2e– ⇌ Pb(s) E0 = – 0.126 V
PbI2 (s) + 2e– ⇌ Pb(s) + 2I– E0 = ?
0.0592 1
E Pb 2+¿/ Pb = −0.126− log ¿
¿
2 ¿¿
0.0592
E PbI / Pb = E0 − log ¿ ¿¿ ¿
2
2
Ksp= ¿ ¿ = 7.1 x 10−9
E 0.0592
Pb 2+¿/ Pb=−0.126− log¿ ¿¿¿ ¿¿
2

Dimana :
¿¿
2
0.0592 [ 1.00 ]
E0 =−0.126− log =−0.367 V
2 7.1 x 10−9

22.11 Calculate the standard potential for the half-reaction

BiOCl(s) + 2H+ + 3e– ⇌ Bi(s) + Cl– + H2O
Given that Ksp for BiOCI has a value of 8.1 x 10−1 9

Jawab :
BiO+ + 2H+ + 3e– ⇌ Bi(s) + H2O E0 = +0.320 V
BiOCl(s) + 2H+ + 3e– ⇌ Bi(s) + Cl– + H2O E0 = ?
 0.0592 [ Bi ]
E BiO + ¿/Bi
¿ = +0.320− log ¿ ¿ ¿
3
0.0592
E BiO + ¿/Bi = E0 − log ¿ ¿¿
¿
3
Ksp= [BiO+¿ ¿ ¿ = 8.1 x 10−1 9
E 0.0592
BiO+ ¿/Bi =+ 0.320V − log¿ ¿¿¿ ¿
3

Dimana :
¿¿
2
0.0592 [ 1.00 ] M
E0 =+0.320− log
3 8 .1 x 10−19 M
E0 =−0.037 V

22.12 Calculate the standard potential for the half-reaction

Al ¿ ¿
If the formation constant for the complex is log 1.3 x 1013

Jawab :
Al3+ + 3e– ⇌ Al(s) E0 = – 1.662 V
Al ¿ ¿ E0 = ?
0.0592 [ Al]
E Al 3+ ¿/ Al
¿ = – 1.662 V − log ¿ ¿ ¿
3
K f =¿ ¿ ¿
0.0592
E = −1.662 V − log Kf ¿ ¿ ¿ ¿ ¿
3
0 0.0592
E=E − log ¿ ¿¿ ¿ ¿
3
Dimana :
¿¿¿¿

0.0592
E0 = −1.662 V − log Kf
3
0.0592
E0 = −1.662 V − log ¿ ¿ ¿ ¿
3
 0.0592
E0 = −1.662 V − log 1.3 x 1013
3
E0 =−1.92V

22.13 From the standard potentials

Tl+ + e- ⇌ Tl(s) E0 =−0.336 V
TlCl(s) ⇌ Tl(s) + Cl−¿¿ E0 =−0.557 V
Calculate the solubility product constant for TlCl

Jawab :
1
E = −0.336 V −0.592 log +¿ ¿
[Tl ]
[Cl ]−¿
E = −0.336 V −0.592 log ¿
Ksp
Dimana :
¿ ¿TlCl = - 0.557 V
1
−0.557 = −0.336 V −0.592 log
Ksp
Ksp= 1.85 x 10-4

22.14 From the standard potentials

Ag2SeO4(s) + 2e ⇌ 2Ag(s) + SeO42- E0 =+0.355 V
Ag+ (s) + 2e ⇌ 2Ag(s) E0 =+0.799 V
Calculate the solubility product constant for TlCl.

Jawab :
Ag2SeO4(s) + 2e ⇌ 2Ag(s) + SeO42- E0 =+0.355 V
Ag+ (s) + 2e ⇌ 2Ag(s) E0 =+0.799 V
0 0.0592 [ Ag]
E =0.799 V − log ¿ ¿ ¿
1
0.0592
E0 =0.799 V − log ¿ ¿ ¿
2
 Dimana :
¿ Ag2SeO4 = 0.355 V
0.0592
0.355 V =0.799 V − log ¿ ¿ ¿
2
0.0592 1.00
0.355 V =0.799 V − log
2 [ Ksp ]
1.00
0.355 V – 0.799 V = - 0.0296 log
[ Ksp ]
−0.444 1.00
=log
0.296 [ Ksp ]
15=log 1−log Ksp
Log Ksp = - 15
Ksp = 1 x 10-15

22.15 Suppose that we wish to produce a current of 0.0750 A in the cell.

Pt|V3+ (3.7 x 10-5 M), V2+ (4.48 x 10-1 M) || Br - (0.0850 M). AgBr(sat'd)|Ag
As a result of its design, the cell has an internal resistance of 4.87Ω. Calculate

the initial potential of the cell.

Jawab :
E = 0.073 – 0.0592 log (0.0850) = 0.136 V
right
E 0.448
¿=−0.256−0.592 log =−0.498V ¿
3.7 x10 −5

E¿−¿¿= 0.0136 — 0.498=0.634 V

Ecell =E¿ −E¿−IR=0.634−0.075 x 4.78=0.268V ¿

22.16 The cell

Pt|V(OH)4+ (2.67 x 10 -4 M), VO2+ (3.42 x l0 -2M), H+ (4.81 x 10-3 M)||Cu2+ (2.50 x 10-2M)|Cu
has an internal resistance of 3.81 Ω . What will be the initial potential if a current of 0.0750A
is drawn from this cell?
Jawab :

E = 0.337 – 0.0592log 1
right =0.242 V
2.5 x 10−2
 E 3.42 x10 −2
¿=1.00−0.592log ¿¿
(2.67 x10 ¿¿−4 )¿¿¿

E¿−¿¿= 0.242 V — 0.601 V =−0.359 V

Ecell =E¿ −E¿−IR =−0.359 V −0.0750 x3.81=−0.644V ¿

22.17 The resistance of galvanic cell

Pt|Fe(CN)64- (4.42 x 10-2M), Fe(CN)63- (8.93 x 10-3 M) || Ag+ (5.75 x 10-1M)|Ag
is 3.85 Ω . calculate the initial potential when 0.0442 A is drawn from this cell.

Jawab :
1
Eright = 0.337 – 0.0592 log = 0.242 V
2,50 x 10−2
3,42 x 10−2
Eleft = 1,00 – 0,0592 log 2 = 0,601 V
2,67 x 10−4 x ( 4,81 x 10−3 )
Eright – Eleft = 0.242 – 0.601 = –0.359 V
Ecell = Eright – Eleft – IR = –0.359 – 0.0750 × 3.81 = –0.644 V
Ecell = 0,24 V