Chapter 17: Applications of

Standard Electrode Potentials

• How to calculate thermodynamic cell potentials.
• How to calculate equilibrium constants for redox reactions.
• How to construct redox titration curves.

Calculating Potentials of
Electrochemical Cells
計算出的電位potential (有時稱為熱力學位
能thermodynamic potential)是理論值，因
為它們指的是沒有電流的電池。如果電池
中有電流，則必須考慮其他因素。

電化學電池的熱力學位能是右側電極的電
位與左側電極的電位之間的差值。

2
Calculating Potentials of
Electrochemical Cells
Ecell  Eright  Eleft
Ecell  0  Eright  Eleft at equilibrium
G 0 0
nFEcell
In K eq    Nernst equation
RT RT
0
nEcell n  Eright
0
 Eleft
0
 at 25C
log K eq  
0.0592 0.0592

aA + bB + …+ ne- cC + dD + …

⋯
ln 非平衡狀態(E = 量測值)
⋯
3

Calculate the thermodynamic potential of the following cell and

the free energy change associated with the cell reaction:
Cu Cu 2  0.0200 M  Ag +  0.0200 M  Ag

Solution

1
EAg+ Ag
 0.799  0.0592 log  0.6984 V
0.0200
0.0592 1
ECu 2+ Cu  0.337  log  0.2867 V
2 0.0200

Ecell  Eright  Eleft  E  ECu 2+ Cu  0.6984  0.2867   0.412 V

Ag + Ag

G   nFEcell   2  96, 485 C  0.412 V   79,503 J 18.99 kcal 

4
Calculate the potential of the following cell and indicate the
reaction that would occur spontaneously if the cell were short-
circuited.

Solution

6
Calculate the cell potential for

Solution

The negative sign indicates that the cell reaction as considered

為nonspontaneous反應，若要使這反應發生，必須施
加外部電壓並構造一個電解池。 7

Calculate the potential for the following cell using (a)

concentrations and (b) activities:

8
(b) To calculate activity coefficients for Zn2+ and [SO42-],

10
In Table 8-2, we find αSO42- = 0.4 nm and αZn2+ = 0.6 nm.

11

離子強度對Galvanic cell電位的影響

12
Calculate the potential required to initiate deposition of copper from a
solution that is 0.010 M in CuSO4 and contains sufficient H2SO4 to give a
pH of 4.00.

is nonspontaneous
13

Determining Standard Potentials

Experimentally
• 電化學資料庫數據中的半反應標準電極電位，都不能
在實驗室中直接測量。
• SHE 是一個假想的電極，就像反應物和產物處於單位
活性或壓力的任何電極系統一樣。
• 這些電極系統無法在實驗室中製備，因為無法製備含
有活性恰好為 1 的離子的溶液。
• 在高離子強度下，以Debye-Hückel 方程式或擴展式計
算活性係數的表現不佳，並且沒有獨立的方法來確定
此類溶液中的活性係數。
• 在低離子強度溶液中收集的數據，則能推斷出較有效
估計的理論標準電極電位。

14
 Calculating Redox Equilibrium
Constants

隨著反應的進行，Cu(II)離子的濃度
增加，Ag(I)離子的濃度減少。

達到平衡時兩邊半電池電位相同

0
nEcell
0
n( Eright  Eleft
0
)
log K eq  
0.0592 0.0592
15

Calculate the equilibrium constant for the reaction shown in

Solution

16
Calculate the equilibrium constant for the reaction

Solution

2
 Fe 2 
log 
0.0592
EFe3 Fe 2
 E 0
Fe3 Fe2
 2
2  Fe3 
3
0.0592  I  
EI  /I  E 0
I3 /I
 log 
3
2  I3 

At equilibrium,
EFe3 Fe2
 EI  I
3

2 3
0.0592  Fe 2  0.0592  I  
E 0
Fe3 Fe2
 log  EI0  I
 log 
2 3 
 Fe 
2 3
2  I3 
17


2 EFe0 3 Fe2
 EI0 
3 I   log
 Fe 2 
2
 I  
 log 
3

0.0592  Fe3 
2
 I3 
2
 Fe 2   I3 
 log 2
 log 3
 Fe3   I  
2
 Fe 2   I3 
 log 2 3
 Fe3   I  

log
2
 Fe2   I3 


2 EFe0 3 Fe2  EI0 
3 I 
3 2  3
 Fe   I  0.0592

log K eq 

2 EFe0 3 Fe2
 EI0 
3 I  
2  0.771  0.536 
 7.94
0.0592 0.0592

K eq  antilog 7.94  8.7  107

18
Electrode Potentials During Redox
Titrations

• 電壓變化是添加滴定劑的函數
• 在整個滴定過程中系統始終處
於平衡狀態
• 滴定曲線分為三個區域
 當量點之前
 當量點點
 當量點之後

19

K ≈ 1016 in 1 M HClO4

(1) before the equivalence point

20
20
before the equivalence point: V = ½ Ve

E  0.526 V  E  - E 
E   0.767 V  E 0

21

(2) at the equivalence point

at the equivalence point, [Ce3+] = [Fe3+] and [Ce4+] = [Fe2+]

2E+ = 2.467 V → E+ = 1.23 V

E = E+ - E(SCE) = 1.23 – 0.241 = 0.99 V

當量點電壓與反應物的濃度和體積無關
22
(3) after the equivalence point

when V = 2Ve

E  1 .46 V  E  - E 
E   1 .70 V  E 0
23

Derive an expression for the equivalence-point potential in

the titration of is 0.0500 M U4+ with 0.1000 M Ce4+.
Assume both solutions are 1.0 M in H2SO4.

Solution

0.0592  U 4 
Eeq  E 0
UO 22 U 4
 log 4
2  UO 2 2   H  

0.0592 Ce3 
Eeq  E0'
Ce 4 Ce3
 log
1 Ce 4 

 U 4 
2 Eeq  2 E 0
UO 2 2 U 4
 0.0592 log 4
 UO 22   H  

 U 4   Ce3 
3Eeq  2 E 0
UO2 2 U 4
 E 0'
Ce4 Ce3
 0.0592 log 4
 UO 2 2   Ce 4   H   24
at equivalence,

 U 4   Ce 4  2 and  UO 2 2   Ce3  2

0
2 EUO 2
U 4
 ECe
0'
4
Ce3 0.0592 2 Ce 4  Ce3 
Eeq  2
 log 4
3 3 2 Ce3  Ce 4   H + 
0
2 EUO 2
/ U 4
 ECe
0'
4
/Ce3 0.0592 1
 2
 log 4
3 3  H + 

在此滴定中，等當點電位取決於 pH 值。

25

The Titration Curve

Consider the titration of 50.00 mL of 0.0500 M Fe2+ with 0.1000 M
Ce4+ in a medium that is 1.0 M H2SO4 at all times.

(a) Initial Potential

don’t have enough information to calculate an initial potential

(b) Potential after the addition of 5.00 mL of Cerium(IV)

26
(c) Equivalence-Point potential

(d) Potential after adding 25.10 mL of Cerium(IV)

27

28
 Calculate data and construct a titration curve for the reaction of
50.00 mL of 0.02500 M U4+ with 0.1000 M Ce4+ The solution is
1.0 M H2SO4 throughout the titration (for the sake of simplicity,
assume that [H+] for this solution is also about 1.0 M).

Solution

29

(1) Potential After Adding 5.00 mL of Ce4+

4 mmol U 4
original amount U  50.00 mL U 4+
 0.02500
mL U 4
 1.250 mmol U 4 
mmol Ce 4
amount Ce 4  added  5.00 mL Ce 4  0.1000
mL Ce 4
 0.5000 mmol Ce 4
amount U 4 remaining  1.250 mmol U 4+  0.2500 mmol UO 2 2
1 mmol U 4+

1 mmol UO 2 2+
 1.000 mmol U 4
total volume of solution = (50.00 + 5.00)mL = 55.00 mL

4 1.000 mmol U 4+
concentration U remaining 
55.00 mL 30
 1 mmoL UO 2 2+
0.5000 mmol Ce 4+ 
2 mmol Ce 4+
concentration UO 2 2+ formed 
55.00 mL
0.2500 mmol UO 2 2

55.00 mL

Applying the Nernst equation for UO22+ gives

0.0592  U 4 
E  0.334  log 4
2  UO 2 2   H  

0.0592  U 4 
 0.334  log
 UO 2 2  1.00 
4
2
Substituting concentrations of the two uranium species gives
0.0592 1.000 mmol U 4+ 55.00 mL
E  0.334  log
2 0.2500 mmol UO 2 2+ 55.00 mL
 0.316 V
31

(2) Equivalence-Point Potential

Eeq 
 2E 0
UO 22 U 4
0
 ECe 4
Ce3  
0.0592
log
1
4
3 3  H  

2  0.334  1.44 0.0592 1

Eeq   log
1.00 
4
3 3
2  0.334  1.44
  0.703 V
3

(3) Potential After Adding 25.10 mL of Ce4+

total volume of solution = 75.10 mL

mmol U 4+
original amount U 4+
 50.00 mL U 4+
 0.02500
mLU 4+
 1.250 mmol U 4+
32
 mmol Ce 4+
amount Ce 4+ added  25.10 mL Ce 4+  0.1000
mLCe 4+
 2.510 mmol Ce4+

2 mmol Ce3
1.250 mmol U 4+ 
mmol U 4+
concentration of Ce3 formed 
75.10 mL

concentration of Ce4+ remaining

4 3 1 mmol Ce 4
2.510 mmol Ce  2.500 mmol Ce 
mmol Ce3

75.10 mL

Substituting into the expression for the formal potential gives

2.500 75.10
E  1.44  0.592 log  1.30 V
0.010 75.10
33

Effect of Variables on Redox

Titration Curves
• Reactant concentration 反應
物濃度
 氧化/還原反應的滴定曲線通
常與分析物和試劑濃度無關

• 反應的完全性
 隨著反應變得更加完全，氧化
/還原滴定的等當點區域中的
電位變化變得更大。

34
 General Redox Indicators
• 一般氧化還原指示劑的顏色變化僅取決於系統的電位。
• 質子參與許多指示劑的還原。 因此發生顏色變化的電
位範圍(轉變電位)通常取決於 pH 值。
• 產生典型通用指示劑全部顏色變化所需的電位變化，
可以使用下列方程來確定。

0.0592
E  EIn0 
n

35

General Redox Indicators

Color: Color: Transition
Indicator Conditions
Oxidized Reduced Potential, V
5-Nitro-1,10-phenanthroline
Pale blue Red-violet +1.25 1 M H2SO4
iron(II) complex
2,3’-Diphenylamine dicarboxylic 7-10 M
Blue-violet Colorless +1.12
acid H2SO4
1-10- phenanthroline iron(II)
Pale blue Red +1.11 1 M H2SO4
complex
5-Methyl 1,10- phenanthroline
Pale blue Red +1.02 1 M H2SO4
iron(II) complex
Yellow- 0.5 M
Erioglaucin A Blue-red +0.98
green H2SO4
Diphenylamine sulfonic acid Red-violet Colorless +0.85 Dilute acid
Diphenylamine Violet Colorless +0.76 Dilute acid
p-Ethoxychrysoidine Yellow Red +0.76 Dilute acid
Methylene blue Blue Colorless +0.53 1 M acid
Indigo tetrasulfonate Blue Colorless +0.36 1 M acid
Phenosafranine Red Colorless +0.28 1 M acid
36
*Data in part from I. M. Kolthoff and V. A. Stenger, Volumetric Analysis, 2nd ed., Vol. 1,
p. 140, New York: Interscience, 1942.
 Important Equations

Ecell = Eright − Eleft

Ecell = 0 = Eright − Eleft at equilibrium
0
∆G 0 nFEcell
In K eq = − =
RT RT
0
nEcell n ( Eright
0 0
− Eleft )
log K eq = =
0.0592 0.0592

37

38