Fundamentals of Analytical Chemistry: 8th ed.

Chapter 18

Chapter 18

18-1 (a) Oxidation is a process in which a species loses one or more electrons.

(b) An oxidizing agent is an electron acceptor.

(c) A salt bridge is a device that provides electrical contact but prevents mixing of dissimilar solutions in

an electrochemical cell.

(d) A liquid junction is the interface between dissimilar liquids. A potential develops across the interface.

(e) The Nernst equation relates the potential to the concentrations (strictly, activities) of the participants in

an electrochemical reaction.

18-2 (a) The electrode potential is the potential of an electrochemical cell in which a standard hydrogen electrode

acts as the reference electrode on the left and the half-cell of interest is on the right as written in cell notation.

(b) The formal potential of a half-reaction if the potential of the system (measured against the standard

hydrogen electrode) when the concentration of each solute participating in the half-reaction has a

concentration of exactly one molar and the concentrations of all other constituents of the solution are carefully

specified.

(c) The standard electrode potential for a half-reaction is the potential of a cell consisting of the half-reaction

of interest on the right and a standard hydrogen electrode on the left as written in cell notation. The activities

of all of the participants in the half-reaction are specified as having a value of unity. The additional

specification that the standard hydrogen electrode is the reference electrode implies that the standard potential

for the half-reaction is always a reduction potential.

(d) A liquid-junction potential is the potential that develops across the interface between two dissimilar

solutions.

(e) An oxidation potential is the potential of an electrochemical cell in which the cathode is a standard

hydrogen electrode and the half-cell of interest acts as anode.

18-3 (a) Reduction is the process whereby a substance acquires electrons; a reducing agent is a supplier of

electrons.
Fundamentals of Analytical Chemistry: 8th ed. Chapter 18

(b) A galvanic cell is one in which a spontaneous electrochemical reaction occurs and is thus a source of

energy. The reaction in an electrolytic cell is forced in a nonspontaneous direction through application of

an external source of electrical energy.

(c) The anode of an electrochemical cell is the electrode at which oxidation occurs. The cathode is the

electrode at which reduction occurs.

(d) In a reversible cell, alteration of the direction of the current simply causes a reversal in the

electrochemical process. In an irreversible cell, reversal of the current results in a different reaction at one

or both of the electrodes.

(e) The standard electrode potential is the potential of an electrochemical cell in which the standard

hydrogen electrode acts as the reference electrode on the left and all participants in the right-hand electrode

process have unit activity. The formal potential differs in that the molar concentrations of the reactants and

products are unity and the concentrations of other species in the solution are carefully specified.

18-4 The first standard potential is for a solution that is saturated with I2 and has an I2 (aq) activity significantly

less than one. The second potential if for a hypothetical half-cell in which the I2 (aq) activity is unity.

Such a half-cell, if it existed, would have a greater potential because the driving force for the reduction

would be greater at the higher I2 concentration. The second half-cell potential, although hypothetical, is

nevertheless useful for calculating electrode potentials for solutions that are undersaturated in I2.

18-5 It is necessary to bubble hydrogen through the electrolyte in a hydrogen electrode in order to keep the

solution saturated with the gas. Only under these conditions is the hydrogen activity constant so that the

electrode potential is constant and reproducible.

18-6 The potential in the presence of base would be more negative because the nickel ion activity in this

solution would be far less than 1 M. Consequently the driving force for the reduction if Ni (II) to the

metallic state would also be far less, and the electrode potential would be significantly more negative. (In
Fundamentals of Analytical Chemistry: 8th ed. Chapter 18

fact the standard electrode potential for the reaction Ni(OH ) 2  2e  


Ni( s )  2OH  has a value of –0.72

V, whereas the standard electrode potential for Ni 2  2e  


Ni( s ) is –0.250 V.)

18-7 (a) 2Fe 3  Sn 2  2Fe 2  Sn 4

(b) Cr( s )  3Ag   Cr 3  3Ag ( s )


(c) 2 NO 3  Cu( s )  4H   2 NO 2 ( g )  2H 2 O  Cu 2

 2
(d) 2MnO 4  5H 2SO3  2Mn 2  5SO 4  4H   3H 2 O

3 4
(e) Ti3  Fe(CN ) 6  H 2 O  TiO 2  Fe(CN) 6  2H 

(f) H 2 O 2  2Ce 4  O 2 ( g )  2Ce 3  2H 

(g) 2Ag ( s)  2I   Sn 4  2AgI ( s)  Sn 2

2
(h) UO2  Zn( s)  4H   U 4  Zn 2  2H 2O

 
(i) 5HNO 2  2MnO 4  H   5NO3  2Mn 2  3H 2 O

 
(j) H 2 NNH 2  IO3  2H   2Cl   N 2 ( g )  ICl 2  3H 2 O

18-8 (a) Oxidizing agent Fe3+; Fe 3  e  


Fe 2

Reducing agent Sn2+; Sn 2 


Sn 4  2e 

(b) Oxidizing agent Ag+; Ag   e  


Ag ( s )

Reducing agent Cr; Cr ( s ) 


Cr 3  3e 


(c) Oxidizing agent NO3-; NO 3  2H   e  

NO 2 ( g )  H 2 O

Reducing agent Cu; Cu( s ) 


Cu 2  2e 
Fundamentals of Analytical Chemistry: 8th ed. Chapter 18


(d) Oxidizing agent MnO4-; MnO 4  8H   5e  

Mn 2  4 H 2 O

2
Reducing agent H2SO3; H 2SO 3  H 2 O 

SO 4  4 H   2e 

3 4
(e) Oxidizing agent Fe(CN)63-; Fe(CN ) 6  e 

Fe(CN ) 6

Reducing agent Ti3+; Ti3  H 2 O 


TiO 2  2 H   e 

(f) Oxidizing agent Ce4+; Ce 4  e  


Ce 3

Reducing agent H2O2; H 2 O 2 


O 2 ( g )  2H   2e 

(g) Oxidizing agent Sn4+; Sn 4  2e  


Sn 2

Reducing agent Ag; Ag ( s )  I  


AgI ( s )  e 

2
(h) Oxidizing agent UO22+; UO 2  4 H   2e  

U 4  2 H 2 O

Reducing agent Zn; Zn( s ) 


Zn 2  2e 


(i) Oxidizing agent MnO4-; MnO 4  8H   5e  

Mn 2  4 H 2 O


Reducing agent HNO2; HNO 2  H 2 O 

NO 3  3H   2e 

 
(j) Oxidizing agent IO3-; IO3  6H   2Cl   4e  

ICl 2  3H 2 O

Reducing agent H2NNH2; H 2 NNH 2 


N 2 ( g )  4 H   4e 

 
18-9 (a) MnO4  5VO 2  11H 2O  Mn 2  5V(OH) 4  2H 

(b) I 2  H 2S( g )  2I   S( s )  2H 

2 2
(c) Cr2 O7  3U 4  2H   2Cr 3  3UO 2  H 2O
Fundamentals of Analytical Chemistry: 8th ed. Chapter 18

(d) 2Cl   MnO 2 ( s)  4H   Cl 2 ( g )  Mn 2  2H 2 O


(e) IO3  6H   5I   3I 2  H 2 O

 
(f) IO3  2I   6H   6Cl   3ICl 2  3H 2 O

2  3 2
(g) HPO3  2MnO 4  3OH   PO4  2MnO 4  2H 2 O

 2
(h) SCN   BrO3  H 2 O  SO 4  HCN  Br   H 


(i) V2  2V(OH) 4  2H   3VO 2  5H 2O


(j) 2MnO4  3Mn 2  4OH   5MnO2 ( s)  2H 2O


18-10 (a) Oxidizing agent MnO4-; MnO 4  8H   5e  

Mn 2  4 H 2 O


Reducing agent VO2+; VO 2  3H 2 O 

V(OH ) 4  2 H   e 

(b) Oxidizing agent I2; I 2 (ag )  2e  


2I 

Reducing agent H2S; H 2S( g ) 


S( s )  2H   2e 

2
(c) Oxidizing agent Cr2O72-; Cr2 O 7  14H   6e  

2Cr 3  7H 2 O

2
Reducing agent U4+; U 4  2 H 2 O 

UO 2  4 H   2e 

(d) Oxidizing agent MnO2; MnO 2 ( s )  4H   2e  


Mn 2  2H 2 O

Reducing agent Cl-; 2Cl  


Cl 2 ( g )  2e 

  1
(e) Oxidizing agent IO3 ; IO3  6H   5e  

I 2  3H 2 O
2

1
Reducing agent I-; I  

I2  e
2

  
(f) Oxidizing agent IO3 ; IO3  6H   2Cl   4e  

ICl 2  3H 2 O
Fundamentals of Analytical Chemistry: 8th ed. Chapter 18


Reducing agent I-; I   2Cl  

ICl 2  2e 

 2
(g) Oxidizing agent MnO4-; MnO 4  e  

MnO 4

2 3
Reducing agent HPO32-; HPO3  3OH  

PO4  2 H 2 O  2e 


(h) Oxidizing agent BrO3-; BrO3  6H   6e  

Br   3H 2 O

2
Reducing agent SCN-; SCN   4H 2 O 

SO 4  HCN  7H   6e 


(i) Oxidizing agent V(OH)4+; V(OH ) 4  2H   e  

VO 2  3H 2 O

Reducing agent V2+; V 2  H 2 O 


VO 2  2H   2e 


(j) Oxidizing agent MnO4-; MnO 4  4 H   3e  

MnO 2 ( s )  2H 2 O

Reducing agent Mn2+; Mn 2  2 H 2 O 


MnO 2 ( s )  4 H   2e 

18-11 (a)

AgBr ( s )  e  

Ag ( s )  Br  V 2 

V 3  e 
4  3
Tl3  2e  

Tl Fe(CN ) 6 
Fe(CN ) 6  e 

V 3  e  

V 2 Zn( s ) 

Zn 2  2e 
3 4
Fe(CN ) 6  e  

Fe(CN ) 6 AgBr ( s )  e  

Ag ( s )  Br 
2 2
S2 O8  2e  

2SO 4 Tl 

Tl3  2e 
Fundamentals of Analytical Chemistry: 8th ed. Chapter 18

(b), (c) E
2 2 2.01
S2 O8  2e  

2SO 4
1.25
Tl3  2e  

Tl
3 4 0.36
Fe(CN ) 6  e  

Fe(CN ) 6
0.073
AgBr ( s )  e  

Ag ( s )  Br 
-0.256
V 3  e  

V 2
-0.763
Zn 2  2e  

Zn( s )

18-12 (a)

Sn( s ) 

Sn 2  2e  2H   2e  

H2 (g)

Ag   e  

Ag ( s ) Fe 2 

Fe 3  e 

Sn 4  2e  

Sn 2 H2 (g) 

2 H   2e 

Fe 3  e  

Fe 2 Sn 2 

Sn 4  2e 

Sn 2  2e  

Sn( s ) Co( s ) 

Co 2  2e 

(b), (c) E

Ag   e  

Ag ( s ) 0.799

Fe 3  e  

Fe 2 0.771

Sn 4  2e  

Sn 2 0.154

2H   2e  

H2 (g) 0.00

Sn 2  2e  

Sn( s ) -0.136

Co 2  2e  

Co( s ) -0.277
Fundamentals of Analytical Chemistry: 8th ed. Chapter 18

18-13 (a)

0.0592  1 
ECu  0.337  log    0.297 V
2  0.0440 

(b)

K CuCl  1.9  10 7  [Cu  ][Cl  ]

0.0592  1  0.0592  [Cl  ] 
ECu  0.521  log  
  0.521  log  
1  [Cu ]  1  K CuCl 
0.0592  0.0750  0.0592
 0.521  log  7 
 0.521  log( 3.95  105 )
1  1.9  10  1
 0.521  0.331  0.190 V

(c)

K Cu ( OH)2  4.8  10 20  [Cu 2 ][OH  ]2

0.0592  1  0.0592  [OH  ]2 


ECu  0.337  log    0.337  log
2 2
 [Cu ]  2  K Cu ( OH ) 
 2 
0.0592  0.0400 
2
0.0592
 0.337  log    0.337 
 20 
log( 3.33  1016 )
2  4.8  10  2
 0.337  0.489   0.152 V

(d)

2
[Cu( NH 3 ) 4 ]
 4  5.62  1011 
[Cu 2 ][ NH 3 ]4

0.0592  1  0.0592   4 [ NH 3 ]4 
ECu  0.337  log  2
  0.337  log  
2 
2  [Cu ]  2  [Cu( NH 3 ) 4 ] 
0.0592  5.62  1011 0.128 
4
0.0592
 0.337  log    0.337 
 log( 6.03  109 )
2  0 .0250  2
 0.337  0.290  0.048 V
Fundamentals of Analytical Chemistry: 8th ed. Chapter 18

(e)

[CuY 2 ]
2
  4 K CuY  3.6  10 9   6.3  1018   2.3  1010
[Cu ]cT
[CuY 2 ]  4.00  10 3
cT  2.90  10 2   4.00  10 3   0.0250

0.0592  1  0.0592   4 K CuY 2  cT 

ECu  0.337  log  2
  0.337  log  2

2  [Cu ]  2  [CuY ] 
0.0592  2.3  1010 0.0250  0.0592
 0.337  log  3
  0.337  log(1.4  1011 )
2  4.00  10  2
 0.337  0.33  0.007 V

18-14 (a)

0.0592  1 
E Zn  0.763  log     0.799 V
2  0.0600 

(b)

K Zn( OH)2  3.0  10 16  [Zn 2 ][OH  ]2

0.0592  1  0.0592  [OH  ]2 


E Zn  0.763  log    0.763  log
2 2
 [Zn ]  2  K Zn( OH ) 
 2 
0.0592  0.0100 
2
0.0592
 0.763  log    0.763 
16 
log( 3.33  1011 )
2  3.0  10  2
 0.763  0.341   1.10 V

(c)

2
[Zn( NH 3 ) 4 ]
 4  7.76  108 
[Zn 2 ][ NH 3 ]4

0.0592  1  0.0592   4 [ NH 3 ]4 
E Zn  0.763  log  2
  0.763  log  
2 
2  [Zn ]  2  [Zn( NH 3 ) 4 ] 
0.0592  7.76  108 0.250 
4
0.0592
 0.763  log    0.763 
 log( 3.03  108 )
2  0.0100  2
 0.763  0.251   1.01 V
Fundamentals of Analytical Chemistry: 8th ed. Chapter 18

(d)

[ZnY 2 ]
2
  4 K ZnY  5.2  10 2   3.2  1016   1.7  1015
[Zn ]cT
[ZnY 2 ]  5.00  10 3
cT  4.45  10 2   5.00  10 3   0.0395

0.0592  1  0.0592   4 K ZnY2  cT 

E Zn  0.763  log  2
  0.763  log  2

2  [ Zn ]  2  [ ZnY ] 
0.0592  1.7  1015 0.0395  0.0592
 0.763  log  3
  0.763  log(1.3  1016 )
2  5.00  10  2
 0.763  0.477   1.24 V

18-15

2H   2e  

H2 (g)

0.0592  p H 2  0.0592  1.00 


E  Eo  log  0.00  log
2  a   
2
2  [ H ]     
 2 2
 H   H 

The ionic strength of the solution  is given by


1
2
0.0100  12   0.0100  12   0.0100
From Table 10-2

 H   0.913
0.0592  1.00 
E  0.00  log    0.00  0.121   0.121 V
2 
 0.0100  0.913 
2
2

2
18-16 PtCl4  2e  

Pt( s )  4Cl  E o  0.73 V

(a)

0.0592  0.1492  
4
E P t  0.73  log    0.73  ( 0.051)  0.78 V

2  0.0263 

(b)
Fundamentals of Analytical Chemistry: 8th ed. Chapter 18

0.0592  2.50  10 3 
E P t  0.154  log    0.154  ( 0.044)  0.198 V
2 
2  7.50  10 

(c)

0.0592  1.00 
   0.355 V
E P t  0.000  log
2  1.00  10 6  
2
 

(d) VO 2  2H   e  

V 3  H 2 O E o  0.359 V

E P t  0.359 
0.0592 
log 
0.0586  2   0.359  0.149  0.210 V
2 
2  0.0353  0.100 

(e) 2 Fe 3  Sn 2 

2 Fe 2  Sn 4

0.0918 mmol SnCl 2 1 mmol Sn 2

mmol Sn 2 consumed    25.00 L  2.30 mmol Sn 2
mL mmol SnCl 2

0.1568 mmol FeCl 3 1 mmol Fe 3

mmol Fe 3 consumed    25.00 L  3.920 mmol Fe 3
mL mmol FeCl 3
1 mmol Sn 4
mmol Sn 4 formed  3.920 mmol Fe 3   1.960 mmol Sn 4
2 mmol Fe 3
mmol Sn 2 remaining  2.30  1.960  0.340 mmol Sn 2

0.0592  0.340 / 50.0 

E P t  0.154  log    0.154  ( 0.023)  0.177 V
2  1.960 / 50.0 


(f) V(OH ) 4  V 3 

2VO 2  2H 2 O


 0.0832 mmol V(OH ) 4 
mmol V(OH ) 4 consumed   25.00 L  2.08 mmol V(OH ) 4
mL
Fundamentals of Analytical Chemistry: 8th ed. Chapter 18

0.01087 mmol V2 (SO 4 ) 3 2 mmol V 3

mmol V 3 consumed    50.00 L  1.087 mmol V 3
mL mmol V2 (SO 4 ) 3
2 mmol VO 2
mmol VO 2 formed  1.087 mmol V 3   2.174 mmol VO 2
mmol V 3
 
mmol V(OH ) 4 remaining  2.08  1.087  0.993 mmol V(OH ) 4


E P t  1.00  0.0592 log 
2.174 / 75.00 
  1.00  0.139  0.86 V
2 
 0.993 / 75.000.1000 

18-17 (a)

 0.0813 
E P t  0.36  0.0592 log    0.36  0.068  0.29 V
 0.00566 

(b)

 0.0400 
E P t  0.771  0.0592 log    0.771  0.022  0.749 V
 0.00845  2 

(c) pH  5.55 [H 3O ]  2.82  106

0.0592  1.00 
  0.000  0.329   0.329 V
E P t  0.000  log
2  2.82  10 6  
2
 

(d)

 0.0789 
E P t  1.00  0.0592 log    1.00  0.106  0.894 V
2 
 0.19960.0800 

(e)

0.0607 mmol Ce(SO 4 ) 2 1 mmol Ce 4

mmol Ce 4 consumed    50.00 L
mL mmol Ce(SO 4 ) 2
 3.04 mmol Ce 4

2 0.100 mmol FeCl 2 1 mmol Fe 2

mmol Fe consumed    50.00 L  5.00 mmol Fe 2
mL mmol FeCl 2
mmol Fe 3 formed  mmol Ce 4 consumed  3.04 mmol Fe 3
mmol Fe 2 remaining  5.00  3.04  0.196 mmol Fe 2
Fundamentals of Analytical Chemistry: 8th ed. Chapter 18

 1.965 / 100.0 
E P t  0.68  0.0592 log    0.68  ( 0.011)  0.69 V
 3.04 / 100.0 

(f)


V(OH ) 4  V 3 

2VO 2  2H 2 O


 0.0628 mmol V(OH ) 4 
mmol V(OH ) 4 consumed   50.00 L  0.314 mmol V(OH ) 4
mL

3 0.0832 mmol V2 (SO 4 ) 3 2 mmol V 3

mmol V consumed    25.00 L
mL mmol V2 (SO 4 ) 3
 4.16 mmol V 3
2 2 mmol VO 2 3
mmol VO formed  0.314 mmol V  3
 0.628 mmol VO 2
mmol V
 
mmol V(OH ) 4 remaining  4.16  0.314  3.85 mmol V(OH ) 4

 3.85 / 75.00 
E P t  0.359  0.0592 log    0.359  0.165  0.194 V
2 
 0.628 / 75.000.100 

18-18 (a)

0.0592  1.00 
E Ni  0.250  log    0.250  0.030   0.280 V anode
2  0.0943 

(b)

EAg  0.151  0.0592 log 0.0922  0.151  (0.061)   0.090 V anode

(c)

0.0592  1.00 
  1.229  0.226  1.003 V cathode
EO2  1.229  log
4  780 / 7601.50  10 4  
4
 

(d)

0.0592  0.0944 
E P t  0.154  log    0.154  ( 0.017)  0.171 V cathode
2  0.350 
Fundamentals of Analytical Chemistry: 8th ed. Chapter 18

(e)

 0.1439 2 
E Ag  0.017  0.0592 log    0.017  0.026   0.009 V anode

 0.00753 

18-19 (a)

0.0592  1.00 
ECu  0.337  log    0.337  0.031  0.306 V cathode
2  0.0897 

(b)

EPt  0.185  0.0592 log 0.1214  0.185  (0.054)   0.131 V anode

(c)

0.0592  0.984 
  0.00  0.237   0.237 V anode
E P t  0.00  log
2  1.00  10 4  
2
 

 0.1628 
(d) E P t  0.771  0.0592 log    0.771  0.015  0.756 V cathode
 0.0906 

(e)

 0.0699 2 
E Ag  0.31  0.0592 log    0.31  ( 0.073)   0.24 V anode

 0.0827 

18-20 2Ag   2e  

2Ag ( s ) E o  0.779

2
[ Ag  ]2 [SO 3 ]  1.5  10 14  K sp
0.0592  [SO 3 ] 
2
0.0592  1 
E  0.799  log  
 2 
 0.799  log
2  [Ag ]  2  K 
 sp 

2
When [SO32-] =1.00, E = Eo for Ag 2SO3 ( s )  2e  

2Ag ( s )  SO3 .

Thus,

0.0592  1.00  0.0592  1.00 

E  0.799  log  0.799  log  14 
 0.799  0.409  0.390 V
2 K  2  1.5  10 
 sp 
Fundamentals of Analytical Chemistry: 8th ed. Chapter 18

18-21 2 Ni 2  4e  

2 Ni( s ) E o  0.250

4
[ Ni 2 ]2 [ P2 O 7 ]  1.7  10 13  K sp
0.0592  [ P2 O 7 ] 
4
0.0592  1 
E  0.250  log    0.250  log
4 2 2
 [ Ni ]  4  K 
 sp 

4
When [P2O74-] =1.00, E = Eo for Ni 2 P2 O 7 ( s )  4e  

2 Ni( s )  P2 O 7 .

Thus,

0.0592  1.00  0.0592  1.00 

E  0.250  log  0.150  log  13 
4    1.7  10 
 K sp  4
 0.250  0.189   0.439 V

18-22 2Tl  2e  

2Tl( s ) E o  0.336

[Tl ]2 [S 2 ]  6  10 22  K sp
0.0592  1  0.0592  [S 2 ] 
E  0.336  log   2   0.336  log
2  [Tl ]  2  K 
 sp 

When [S2-] =1.00, E = Eo for Tl2S( s )  2e  


2Tl( s )  S2 .

Thus,

0.0592  1.00  0.0592  1.00 

E  0.336  log  0.336  log   22 
2  K  2  6  10 
 sp 
 0.336  0.628   0.96 V

18-23 3Pb3  6e  

3Pb( s ) E o  0.126

2
[ Pb2 ]3 [AsO 4 ]2  4.1  10 36  K sp
0.0592  [ AsO 4 ]2 
2
0.0592  1 
E  0.126  log    0.126  log
6 2 3
 [ Pb ]  6  K sp 
 

When [AsO42-] =1.00, E = Eo for Pb3 AsO 4 2 ( s )  4e  

2

3Pb( s )  2AsO 4 .
Fundamentals of Analytical Chemistry: 8th ed. Chapter 18

Thus,

0.0592  1.00  0.0592  1.00 

E  0.126  log  0.126  log  36 
6 K  6  4.1  10 
 sp 
 0.126  0.349   0.475 V

0.0592  1 
18-24 E  0.763  log  2

2  [Zn ] 

[ZnY 2 ]
 3.2  1016
[Zn 2 ][ Y 4 ]

0.0592  [ Y 4 ]3.2  1016  

E  0.763  log  
2  [ZnY 2 ] 

When [Y4-] = [ZnY2-] = 1.00, E  E o ZnY2

0.0592  1.00 3.2  1016  

E  0.763  log    0.763  0.489   1.25 V
2  1.00 

18-25

3 [ FeY  ] 2 [ FeY 2 ]
[ Fe ]  4 and [ Fe ]  4
[ Y ]1.3  1025  [ Y ]2.1  1014 

 [ Fe 2 ] 
E  0.771  0.0592 log  3 

 [ Fe ] 
 [ FeY 2 ]1.3  10 25  
 0.771  0.0592 log  
 [ FeY ]2.1  10  
 14 

When [FeY2-] = [FeY-] = 1.00, E  E o FeY

 1.00 1.3  10 25  
E  0.771  0.0592 log    0.771  0.64  0.13 V
 1.00 2.1  10  
14 

18-26

 2
 [Cu( NH 3 ) 2 ] [Cu( NH 3 ) 2 ]
[Cu ]  and [Cu 2 ] 
[ NH 3 ] 7.2  10 
2 10
[ NH 3 ]2 5.62  1011 
Fundamentals of Analytical Chemistry: 8th ed. Chapter 18

 [Cu  ] 
E  0.153  0.0592 log  2 

 [Cu ] 
 [Cu( NH 3 ) 2  ]5.62  1011  
 0.153  0.0592 log  
 [Cu( NH 3 ) 2 ]7.2  10  
2 10 

When [Cu(NH3)2+] = [Cu(NH3)22+] = 1.00, E  E o Cu ( NH3 )22 

 1.00 5.62  1011  

E  0.153  0.0592 log    0.153  0.053  0.100 V
 1.00 7.2  10  
10 

A B C D
3+ 2+
1 18-27 Fe /Fe half-cell potentials
2
Note: We use the Nernst
equation in column C to
3 Eo, V 0.771 calculate the potentials from
o
4 We also assume 25 C E=Eo-0.0592log([Fe2+]/[Fe3+])
5 [Fe3+]/[Fe2+] [Fe2+]/[Fe3+] E,V
6 0.001 1000.00 0.593
7 0.0025 400.00 0.617
8 0.005 200.00 0.635
9 0.0075 133.33 0.645
10 0.01 100.00 0.653
11 0.025 40.00 0.676
12 0.05 20.00 0.694
13 0.075 13.33 0.704
14 0.100 10.00 0.712
15 0.250 4.00 0.735
16 0.500 2.00 0.753
17 0.750 1.33 0.764
18 1.00 1.00 0.771
19 1.25 0.800 0.777
20 1.50 0.667 0.781
21 1.75 0.571 0.785
22 2.50 0.400 0.795
23 5.00 0.200 0.812
24 10.00 0.100 0.830
25 25.00 0.040 0.854
26 75.00 0.013 0.882
27 100.00 0.010 0.889
28 Spreadsheet Documentation
29 B6=1/A6
30 C6=$B$3-0.0592*LOG10(B6)
Fundamentals of Analytical Chemistry: 8th ed. Chapter 18

18-28

A B C D
4+ 3+
1 18-28 Ce /Ce half-cell potentials
2
Note: We use the Nernst
equation in column C to
3 Eo, V 1.7 calculate the potentials from
o
4 We also assume1 M HClO4 25 C E=Eo-(0.0592)log([Ce3+]/[Ce4+])
5 [Ce4+]/[Ce3+] [Ce3+]/[Ce4+] E,V
6 0.001 1000.00 1.522
7 0.0025 400.00 1.546
8 0.005 200.00 1.564
9 0.0075 133.33 1.574
10 0.01 100.00 1.582
11 0.025 40.00 1.605
12 0.05 20.00 1.623
13 0.075 13.33 1.633
14 0.100 10.00 1.641
15 0.250 4.00 1.664
16 0.500 2.00 1.682
17 0.750 1.33 1.693
18 1.00 1.00 1.700
19 1.25 0.800 1.706
20 1.50 0.667 1.710
21 1.75 0.571 1.714
22 2.50 0.400 1.724
23 5.00 0.200 1.741
24 10.00 0.100 1.759
25 25.00 0.040 1.783
26 75.00 0.013 1.811
27 100.00 0.010 1.818
28 Spreadsheet Documentation
29 B6=1/A6
30 C6=$B$3-0.0592*LOG10(B6)
Fundamentals of Analytical Chemistry: 8th ed. Chapter 18

Plot for Probelm 18-27

0.950
0.900
0.850
0.800
E, V

0.750
0.700
0.650
0.600
0.550
0 20 40 60 80 100 120
[Fe3+]/[Fe2+]

Plot of Problem 18-28

1.850

1.800

1.750

1.700
E, V

1.650

1.600

1.550

1.500
0 20 40 60 80 100 120
4+ 3+
[Ce ]/[Ce ]
Fundamentals of Analytical Chemistry: 8th ed. Chapter 18

18-29

A B C D E F
1 18-29 Plots for Problems 18-27, 18-28 and log ratio
2
3 Eo, V (Fe3+) 0.771 Note: We calculate the logarithm of
4 Eo, V (Ce4+) 1.7 concentration ratio in column B.
5 [Fe3+]/[Fe2+] Log([Fe3+]/[Fe2+] E,V [Ce4+]/[Ce3+] Log([Ce4+]/[Ce3+] E,V
6 0.001 ) -3.00 0.593 0.001 ) -3.00 1.52
7 0.0025 -2.60 0.617 0.0025 -2.60 1.55
8 0.005 -2.30 0.635 0.005 -2.30 1.56
9 0.0075 -2.12 0.645 0.0075 -2.12 1.57
10 0.01 -2.00 0.653 0.01 -2.00 1.58
11 0.025 -1.60 0.676 0.025 -1.60 1.61
12 0.05 -1.30 0.694 0.05 -1.30 1.62
13 0.075 -1.12 0.704 0.075 -1.12 1.63
14 0.100 -1.00 0.712 0.100 -1.00 1.64
15 0.250 -0.60 0.735 0.250 -0.60 1.66
16 0.500 -0.30 0.753 0.500 -0.30 1.68
17 0.750 -0.12 0.764 0.750 -0.12 1.69
18 1.00 0.00 0.771 1.00 0.00 1.70
19 1.25 0.10 0.777 1.25 0.10 1.71
20 1.50 0.18 0.781 1.50 0.18 1.71
21 1.75 0.24 0.785 1.75 0.24 1.71
22 2.50 0.40 0.795 2.50 0.40 1.72
23 5.00 0.70 0.812 5.00 0.70 1.74
24 10.00 1.00 0.830 10.00 1.00 1.76
25 25.00 1.40 0.854 25.00 1.40 1.78
26 75.00 1.88 0.882 75.00 1.88 1.81
27 100.00 2.00 0.889 100.00 2.00 1.82
28 Spreadsheet Documentation
29 B6=LOG10(A6) E6=LOG10(D6)
30 C6=$B$3+0.0592*LOG10(A6) F6=$B$4+0.0592*LOG10(D6)
Fundamentals of Analytical Chemistry: 8th ed. Chapter 18

A plot of potential versus logarithm of the concentration ratio is a straight line.

Plot of Problem 18-27

0.950
0.900
0.850
0.800
0.750
E, V

0.700
0.650
0.600
0.550
0.500
-4.00 -3.00 -2.00 -1.00 0.00 1.00 2.00 3.00
3+ 2+
Log([Fe ]/[Fe ])

Plot of Problem 18-28

1.85

1.80

1.75

1.70
E, V

1.65

1.60

1.55

1.50
-4.00 -3.00 -2.00 -1.00 0.00 1.00 2.00 3.00
Log([Ce4+]/[Ce3+])