19 Applications of Standard Electrode Potentials

(1) Calculating thermodynamic cell potentials

(2) Calculating equilibrium constants for redox reactions
(3) Constructing redox titration curves

19A Calculating Potentials of Electrochemical Cells

Ecell = Eright Eleft
Ex. 19-1 Calculate the thermodynamic potential of the following cell and the free
energy change associated with the cell reaction.
Cu|Cu2+(0.0200 M)Ag+(0.0200 M)|Ag
Ag+ + e- Ag(s) E = 0.799 V
Cu2+ + 2e- Cu(s) E = 0.337 V
1
E Ag + /Ag = 0.799 0.0592 log = 0.6984V
0.0200
0.0592 1
E Cu 2 + /Cu = 0.337 log = 0.2867V
2 0.0200
Ecell = EAg+ - ECu2+ = 0.6984 - 0.2867 = + 0.412 V
G for Cu(s) + 2Ag+ Cu2+ + 2Ag(s)
G = -nFEcell = -2 96485 C 0.412 V = -79500J (18.99 Kcal)
Ex. 19-2 Calculate the thermodynamic potential of the cell
Ag|Ag+(0.0200 M)Cu2+(0.0200 M)|Cu
Ecell = ECu2+ - EAg+ = 0.2867 - 0.6984 = 0.412 V
Ex. 19-3 Calculate the potential of the following cell and indicate whether it is
galvanic or electrolytic (see Fig. 19-1).
Pt|UO22+(0.0150 M),U4+(0.200 M), H+(0.0300 M)
Fe2+(0.0100 M), Fe3+(0.0250 M),|Pt
Fe3+ + e- Fe2+ E = 0.771 V
2+ + - 4+
UO2 + 4H + 2e U + 2H2O E = 0.334 V
[Fe 2+ ] 0.0100
E cathode = 0.771 0.0592 log = 0. 771 0.0592 log
[Fe 3+ ] 0.0250
= 0.771-(-0.0236) = 0.7946 V

0.0592 [ U 4+ ] 0.0592 0.200

E anode = 0.334 log 2+ + 4
= 0.334 log
2 [ UO 2 ][H ] 2 0.0150 0.0300 4
= 0.334 - (0.2136) = 0.1204 V

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 Ecell = Ecathode Eanode = 0.7946 0.1204 = +0.674 V
( positive sign galvanic)

Fig. 19-1 Cell for ex. 19-3 Fig. 19-2 Cell without liquid junction for ex. 19-4

Ex. 19-4 Calculate the theoretic potential for

Ag|AgCl(sat'd), HCl(0.0200 M) | H2(0.800 atm), Pt
2H+ + 2e- H2(g) E = 0.000 V

AgCl(s) + e- Ag(s) +Cl- E = 0.222 V

0.0592 0.800
Ecathode = 0.000 log = 0.0977V
2 2
0.0200
Eanode = 0.222 0.0592 log 0.0200 = 0.3226 V
Ecell = 0.0977 0.3226 = 0.420 V
The negative sign means that the cell reaction
2H+ + Ag(s) + Cl- H2(g) + AgCl(s)
is nonspontaneous, and thus the cell is electrolytic.
Ex. 19-5 Calculate the potential for the following cell using (a) concentration and (b)
activities: Zn|ZnSO4(x M), PbSO4(satd)|Pb,
where x = 5.00 10-4, 2.00 10-3, 1.00 10-2 and 5.00 10-2,
(a) In a neutral solution, [SO42-] = cZnSO4 = x = 5.00 10-4,
PbSO4 + 2e- Pb(s) + SO42- E = -0.350 V
Zn2+ + 2e- Zn(s) E = -0.763 V

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 0.0592
E PbSO3/Pb = 0.350 log(5.00 10 4 ) = 0.252V
2
0.0592 1
E Zn 2+ /Zn = 0.763 log = 0.860V
2 5.00 10 4
Ecell = Eright Eleft = -0252 (-0.860) = +0.608 V

(b) Calculate activity coefficient for Zn2+ and SO42-

1
= (5.00 10 4 2 2 + 5.00 10 4 2 2 ) = 2.00 10 3
2
0.51 2 2 2.00 10 3
log SO 2 = = 8.61 10 2 , SO 2- = 0.820, Zn 2 + = 0.825
4
1 + 3.3 0.4 2.00 10 3 4

0.0592
E PbSO 4 /Pb = 0.350 log(0.820 5.00 10 4 ) = 0.250V
2
0.0592 1
E Zn 2 + /Zn = 0.763 log = 0.863V
2 0.825 5.00 10 4
Ecell = Eright Eleft = -0250 (-0.863) = + 0.613 V
Table 19-1 Effect of Ionic Strength on the Potential of a Galvanic Cell

[ZnSO4], M , Ionic E, V, based on E, V, based on E, V, Experimental

Concentration
Strength Activity Values
-4
5.00 10 2.00 10-3 0.608 0.613 0.611
2.00 10-3 8.00 10-3 0.573 0.582 0.583
1.00 10-2 4.00 10-2 0.531 0.550 0.553
2.00 10-2 8.00 10-2 0.513 0.537 0.542
5.00 10-2 2.00 10-1 0.490 0.521 0.529
Ex. 19-6 Calculate the potential required to initiate deposition of Cu from a solution
that is 0.010 M in CuSO4 and contains sufficient H2SO4 to give a pH of 4.00.
O2(g) + 4H+ + 4e- 2H2O E = +1.229 V
2+ -
Cu + 2e Cu(s) E = +0.337 V
0.0592 1
E Cu 2 + /Cu = +0.337 log = +0.278V
2 0.010
0.0592 1 0.0592 1
E O 2 /H 2 O = +1.229 log = 1 .229 log = +0.992V
4 pO2 [H + ]4 4 1 atm 10- 4
Ecell = Eright Eleft = +0.278 0.992 = -0.714 V
The cell reaction Cu2+ + 2H2O O2(g) + 4H+ + Cu(s) is nonspontaneous
and that to cause Cu to be deposited, we must apply a cathode potential more
negative than -0.714 V

129
19B Determining Standard Potentials Experimentally
Ex. 19-7 Pt,H2(1.00 atm)|HCl(3.21510-3 M), AgCl(satd)|Ag E = +0.52053 V
Calculate the E for the half-reaction AgCl(s) + e Ag(s) +Cl-
-

E right = E AgCl
0
0.0592 log( Cl- )(c HCl )
1
p H22
H+ + e- H2(g) Eleft = EH0 + /H 0.0592 log
2
( H + )(cHCl )
Ecell = Eright Eleft
p
1
2
0
= [ E AgCl 0.0592 log( Cl )( HCl )] EH + /H 0.0592 log
0 H 2
2
( H + )(cHCl )

( + )(cHCl )
= E AgCl
0
0.0592 log( Cl )( HCl ) 0.000 0.0592 log H 1
p H22
( H + )( Cl )(cHCl ) 2
Ecell = 0.52053 = E 0
AgCl 0.0592 log 1
p H22
(0.945)(0.939)(3.215 10 3 ) 2
E 0
AgCl = 0.52053 + 0.0592 log 1
= 0.2223 0.222 V
1.00 2

19C Calculating Redox Equilibrium Constants

Cu(s) + 2Ag+ Cu2+ + 2Ag(s) [Cu 2 + ]
K eq =
[Ag + ]2
Cu|Cu2+(x M)Ag+(y M)|Ag
at chemical equilibrium Ecell = 0 = Eright Eleft = EAg ECu
or Eright = Eleft = EAg = ECu
Eox1 = Eox2= Eox3 = Eox4
0.0592 1 0.0592 1
E 0Ag log + 2
= E 0Cu log
2 [Ag ] 2 [Cu 2+ ]
2Ag+ + 2e- 2Ag(s) E = 0.799V
0.0592 1 0.0592 1 0.0592 [Cu 2+ ]
E 0
Ag E 0
Cu = log log = log
2 [ Ag + ]2 2 [Cu 2+ ] 2 [Ag + ]2
0.0592
= log K eq
2

130
 2 (E oAg E oCu ) [Cu 2 + ] n (E oB E oA )
= log = log K eq log K eq =
0.0592 [Ag + ] 2 0.0592
0
G 0 nFE cell 0
n (E oright E oleft )
ln K eq = = at 25C log K eq =
nE cell
=
RT RT 0.0592 0.0592
Ex. 19-8 Calculate the Keq for the reaction Cu(s) + 2Ag+ Cu2+ + 2Ag(s)

[Cu 2 + ] 2 (0.799 0.337)

log K eq = log = = 15.61
[Ag + ]2 0.0592
Keq = antilog 15.61 = 4.1 1015

Ex. 19-9 Calculate the Keq for the reaction 2Fe3+ + 3I- 2Fe2+ + I3-
2Fe3+ + 2e- 2Fe2+ 0.771 V
I3- + 2e- 3I- 0.536 V

0.0592 [Fe 2 + ]2
E = E log
Fe 3+ /Fe 2+ Fe 3+ /Fe 2+ 2 [ Fe3+ ]2

0.0592 [ I - ]3
E - - = E - - log
I 3 /I I 3 /I 2 [ I3- ]
at equilibrium E =E
Fe3+ /Fe 2 + I3- /I -

0.0592 [ Fe 2 + ]2 = 0.0592 [I - ]3
E log E - - log
Fe3+ /Fe 2 + 2 [Fe3+ ]2 I 3 /I 2 [I3- ]

2(E E - )
Fe3+ /Fe 2 + I3 [Fe 2 + ]2 [I - ]3 [Fe 2 + ]2 [I3- ]
= log log = log
0.0592 [Fe3+ ]2 [I3- ] [Fe3+ ]2 [I - ]3

2+ 2 - 2(E 3+ 2 + E - - )
[Fe ] [I3 ] Fe /Fe I3 / I
log =
3+ 2 - 3 0.0592
[Fe ] [I ]

2(E 3+ 2+ E - )
Fe /Fe I3 / I- 2(0.771 0.536)
log K eq = = = 7.94
0.0592 0.0592
Keq = antilog 7.94 = 8.7 107

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Ex. 19-10 Calculate the Keq for the reaction
2MnO4- + 3Mn2+ + 2H2O 5MnO2(s) + 4H+
2MnO4- + 8H+ + 6e- 2MnO2(s) + 4H2O E = 1.695 V
3MnO2(s) + 12H+ + 6e- 3Mn2+ + 6H2O E = 1.23 V
EMnO4-/MnO2 = EMnO2/Mn2+

0.0592 1 0.0592 [Mn 2 + ]3

1.695 - log = 1.23 log log
6 [MnO-4 ]2 [H + ]8 6 [H + ]12
6(1.695 - 1.23) 1 [H + ]12 [H + ]12
= log + log = log
0.0592 [MnO -4 ] 2 [H + ] 8 [Mn 2 + ] 3 [MnO -4 ] 2 [Mn 2 + ] 3 [H + ] 8

[H + ]4
log K eq = log = 47.1
[MnO -4 ]2 [Mn 2 + ]3
Keq = antilog 47.1 = 1 1047

19D Constructing Redox Titration Curves

19D-1 Electrode Potentials during Redox Titrations
Fe2+ + Ce4+ Fe3+ + Ce3+ ECe4+/Ce3+ = EFe3+/Fe2+ = Esystem = EIn
SHECe4+, Ce3+, Fe3+, Fe2+ | Pt
Most end point in oxidation/reduction titrations are based on the rapid changes in
Esystem that occur at or near chemical equivalence.
Before the equivalence point, Esystem calculations are easiest to make using the
Nernst equation for the analyte. Beyond the equivalence point, the Nernst equation
for the titrant is more convenient.
Equivalence-point Potentials
at the equivalence point

o [Ce3+ ] o [Fe 2 + ]
E eq = E 4 + 0.0592 log and E eq = E 3+ 0.0592 log
Ce 4+ Fe 3+
[Ce ] [Fe ]

o o [Ce3+ ][Fe 2 + ]
2E eq = E 4 + + E 3+ 0.0592 log = E o 4 + + E o 3+
Ce Fe [Ce 4 + ][Fe3+ ] Ce Fe

Eo + Eo
3+ 3+ 2+
([Fe ] = [Ce ], [Fe ] = [Ce ]) 4+
E eq = Ce 4 + Fe3+
2

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Ex. 19-11 Obtain an expression for the equivalence-point potential in the titration of
0.0500 M U4+ with 0.1000 M Ce4+. Assume both solutions are 1.0 M in H2SO4.
U4+ + 2Ce4+ + 2H2O UO22+ + 2Ce3+ + 4H+
UO22+ + 4H+ + 2e- U4+ + 2H2O E = 0.334 V
Ce4+ + e- Ce3+ (formal potential) E' = 1.44 V

0.0592 [U 4+ ]
E eq = E 2 + log (a)
UO 2 2 [ UO 22 + ][H + ]4

' 0.0592 [Ce3+ ]

E eq = E 4 + log (b)
Ce 1 4+
[Ce ]

2a + b 3E eq = 2E 2 + + E ' 4 + 0.0592 log [ U 4 + ][Ce3+ ]

UO 2 Ce
[ UO 2 + ][Ce 4 + ][H + ]4 2
at equivalence [U4+] = [Ce4+]/2 and [UO22+] = [Ce3+]/2
2E + E '
UO 22 + Ce 4 + 0.0592 2[Ce 4 + ][Ce3+ ]
E eq = log
3 3 2[Ce3+ ][Ce 4 + ][H + ]4
2E + E '
UO 22 + Ce 4 + 0.0592 1
= log
3 3 [H + ]4 pH dependent

19D-2 The Titration Curves

Titration of 50.00 mL of 0.0500 M Fe2+ with 0.1000 M Ce4+ in a medium that is 1.0
M in H2SO4 at all times.
Ce4+ + Fe2+ Fe3+ + Ce3+
Ce4+ + e- Ce3+ E' = 1.44 V (1M H2SO4)
Fe3+ + e- Fe2+ E' = 0.68 V (1M H2SO4)
Initial Potential
Potential After the Addition of 5.00 mL of Cerium(IV)
5.00 0.100 0.500
[Fe3+ ] = [Ce 4 + ] = [Ce 4 + ]
50.00 + 5.00 55.00
50.00 0.0500 5.00 0.100 2.00
[ Fe 2 + ] = + [Ce 4 + ] = + [Ce 4 + ]
55.00 55.00
[Fe3+] 0.500/55.00 and [Fe2+] 2.00/55.00
0.0592 2.00 / 55.00
E system = +0.68 log = 0.64 V
1 0.500 / 55.00
133
Equilvalence-Point Potential
E 0' + E 0' 3 +
4+ 1.44 + 0.68
E eq = Ce Fe = = 1.06 V
2 2
Potential After the Addition of 25.10 mL of Cerium(IV)
25.00 0.100 2.500
[Ce3+ ] = [Fe2 + ]
75.10 75.10
25.10 0.1000 50.00 0.0500 0.010
[Ce 4 + ] = + [Fe 2 + ]
75.10 75.10
0.0592 [Ce 3+ ] 0.0592 2.500 / 75.10
E = +1.44 log = 1.44 log = 1.30 V
1 [Ce 4 + ] 1 0.010 / 75.10

Table 19-2 Electrde Potential versus SHE in Titrations with 0.100 M Ce4+
Potential, vs, SHE
Reagent Volume, mL
50.00 mL of 0.0500 M Fe2+ 50.00 mL of 0.02500 M U4+
5.00 0.64 0.316
15.00 0.69 0.339
20.00 0.72 0.352
24.00 0.76 0.375
24.90 0.82 0.405
25.00 1.06 Equivalence Point 0.703
25.10 1.30 1.30
26.00 1.36 1.36
30.00 1.40 1.40

Oxidation/reduction curves are independent of the concentration of the

reactants except when the solution is very dilute.

Fig. 19-3 Titration curves for

0.1000M Ce4+ titration.
A: Titration of 50.00 mL of
0.05000 M Fe2+.
B: Titration of 50.00 mL of
0.02500 M U4+.

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19D-3 Effect of Variables on Redox Titration Curves
Reactant concentration
titration curves are usually independent of analyte and reagent conc.
Completeness of the Reaction
completeness of the reaction change in Esystem in the equivalence-point
region

Fig. 19-5
Effect of titrant electrode potential on reaction
completeness. The standard electrode potential
for the analyte (EA0) is 0.200V; starting with
curve A, standard electrode potentials for the
titrant (ET0) are 1.20, 1.00, 0.80, 0.60 and 0.40,
respectively. Both analyte and titrant undergo a
one-electron change.

19E Oxidation/Reduction Indicators

*Specific Indicators: react with one of the participants in the titration to produce a
color.
starch: form a deep blue complex with iodine
KSCN: form a red Fe(III)/thiocyanate complex with Fe(III)
*General Redox Indicators: respond to the potential of the system.
0.0592 [In ]
Inox + ne- Inred 0
E = EIn log red
ox /In red n [In ox ]
a color change Inox Inred
[In red ] 1 [In red ] 0 0.0592
10 E = EIn
[In ox ] 10 [In ox ] n
For a typical indicator to undergo a useful transition in color, the titrant must cause
a change of 0.118/n V in the potential of the system.

For many indicators, n is 2, so a change of 0.059 V is sufficient.

Iron(II) Complexes of Orthophenanthrolines

(phen)3Fe3+ + e- (phen)3Fe2+
pale blue red

135
Table 19-3 Selected Oxidation/Reduction Indicators
Color Transition
Indicator Conditions
Oxidized Reduced Potential, V
5-Nitro-1,10- Pale blue Red-violet +1.25 1M H2SO4
phenanthroline iron(II)
complex
2,3-Diphenylamine Blue-violet Colorless + 1.12 7-10 M H2SO4
dicarboxylic acid
1,10-Phenanthroline Pale blue Red + 1.11 1M H2SO4
iron(II) complex
5-Methyl-1,10- Pale blue Red + 1.02 1M H2SO4
phenanthroline iron(II)
complex
Erioglaucin A Blue-red Yellow-green + 0.98 0.5M H2SO4
Diphenylamine Red-violet Colorless + 0.85 Dilute acid
sulfonic acid
Diphenylamine Violet Colorless + 0.76 Dilute acid
p-Ethoxychrysoidine Yellow Red + 0.76 Dilute acid
Methylene blue Blue Colorless + 0.53 1M acid
Indigo tetrasulfonate Blue Colorless + 0.36 1M acid
Phenosafranine Red Colorless + 0.28 1M acid

N
N
2+
Fe
N
N

3
1,10-phenanthroline
ferroin (phen)3Fe2+

N N
NO2 H3C

N N

5-nitro-1,10- phenanthroline 5-methyl-1,10- phenanthroline

136