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18 Introduction to Electrochemistry

18A Characterizing Oxidation/reduction reactions

redox reactions:

Ce 4+

+

Fe 2+

Ce 3+

+

Fe 3+

oxidizing agent, oxidant (electron acceptor): Ce 4+ + e - Ce 3+ reducing agent, reductant (electron donor): Fe 2+ Fe 3+ + e -

(reduction of Ce 4+ ) (oxidation of Fe 2+ )

MnO 4 -

+

5e -

+ 8H +

Mn 2+

+

4H 2 O

5Fe 2+

5Fe 3+

+

5e -

MnO 4 - + 5Fe 2+ + 8H +

Mn 2+

+

5Fe 3+

+

4H 2 O

18A-1 Comparing Redox Reaction to Acid/Base Reactions

acid 1

A red

+

+

base 2

B ox

base 1

A ox

+

+

B red

acid 2

(acid/base reaction) (oxidation/reduction reaction)

Ex. 18-1

2H +

+

Cd(s)

H 2 (g)

+

Cd 2+

2Ag +

+

H 2 (g)

2Ag(s)

+

2H +

Cd 2+

+

Zn(s)

Cd(s)

+

Zn 2+

What can we deduce regarding the strengths of H + , Ag + , Cd 2+ and Zn 2+ as electron acceptors (or oxidizing agents)?

Ag + > H + > Cd 2+ > Zn 2+

H + > Cd 2+ ,

Ag + > H + , Cd 2+ > Zn 2+

18A-2 Oxidation/Reduction Reaction in Electrochemical Cells

Ag +

+

e -

Ag(s)

Cu 2+

+

Ag(s)

(a)
(a)

+

Cu(s)

Cu(s)

2e -

+

Ag +

Cu 2+

Fig. 18-2 (a) a galvanic cell at open circuit; (b) a galvanic cell doing work; (c)an electrolytic cell

(c) (b)
(c)
(b)

120

18B ELECTROCHEMICAL CELLS

Consists of two conductors ( electrodes ), each of which is immersed in an electrolyte solution.

18B-1 Cathodes and Anodes

cathode : reduction occurs:

Ag +

+

e -

Ag(s)

 

Fe 3+

+

e -

Fe 2+

 

NO 3 -

+

10H +

+

8e -

NH 4 +

+

3H 2 O

Anode : oxidation occurs:

Cu(s)

Cu 2+

+

2e -

2Cl -

Cl 2 (g)

+

2e -

Fe 2+

Fe 3+

+

e -

18B-2 Types of Electrochemical Cells

galvanic (voltaic) cells : store and supply electrical energy proceed spontaneous reaction and produce a flow of electron from the anode to the cathod via an external conductor. electrolytic cells : required an external source of electrical energy

2Ag(s)

+

Cu 2+

2Ag +

+

Cu(s)

18B-3 Representing Cells Schematically

Cu|Cu 2+ (0.0200 M)Ag + (0.0200 M)|Ag

anode

cathode

Cu|CuSO 4 (0.0200 M)AgNO 3 (0.0200 M)|Ag

liquid-junction potential: develop across the interface between two solutions that differ in their electrolyte composition.

18B-4 Currents in Electrochemical Cells

Electricity is carried by movement of anions toward the anode and cations toward the cathode

Fig. 18-3 Movement of charge in a galvanic cell

movement of anions toward the anode and cations toward the cathode Fig. 18-3 Movement of charge

121

18C ELECTRODE POTENTIALS

2Ag +

+

ΔG = –nFE cell

Cu(s) 2Ag(s)

0

ΔG = −

0

nFE

cell

= −RT lnK

eq

+

Cu 2+

(Fig. 18-4a)

R

: the gas constant

T

: the absolute temperature

(a)

(b)

(c)

gas constant T : the absolute temperature (a) (b) (c) (a) the high-resistance voltmeter prevents any
gas constant T : the absolute temperature (a) (b) (c) (a) the high-resistance voltmeter prevents any
gas constant T : the absolute temperature (a) (b) (c) (a) the high-resistance voltmeter prevents any

(a) the high-resistance voltmeter prevents any significant electron flow, and the full open circuit cell potential is measured. For the concentrations shown, this value is + 0.412V

(b) the voltmeter is replaced with a low- resistance current meter and the cell discharges with time until eventually equilibrium is reached.

(c) after equilibruium is reached, the cell potential is again measured with a voltmeter and found to be 0.000V. The concentrations in the cell are now those at equilibrium as shown.

Fig. 18-4 Change in cell potential after passage of current until equilibrium is reached.

122

18C-1 Sign Convention for Cell Potential

An electrode potential is, by definition, a reduction potential.

An oxidation potential is the potential for the half-reaction written in the opposite way. The sign of an oxidation potential is, therefore, opposite that for a reduction potential, but the magnitude is the same.

The IUPAC sign convention is based on the actual sign of the half-cell of interest when it is connected to the standard hydrogen electrode.

Cell potential E cell

E cell = E right – E left

potential E c e l l E cell = E right – E left Fig 18-5

Fig 18-5 Cell potential in the galvanic cell of Fig. 18-4b as a function of time. The current, which is directly related to the cell potential, also decreases with the same time behavior.

18C-2 The Standard Hydrogen Reference Electrode

Standard Hydrogen Electrode (SHE), Normal Hydrogen Electrode

2H + (aq)

Pt, H 2 (p = 1.00 atm)|([H + ] = x M)

+

2e -

H 2 (g)

The potential of the standard hydrogen electrode:

0.000 V at all temp. at p H 2 = 1.00,

a H + = 1.00,

Fig. 18-6 The hydrogen gas electrode.

a H + = 1.00, Fig. 18-6 The hydrogen gas electrode. 18C-3 Defining Electrode Potential and

18C-3 Defining Electrode Potential and Standard Electrode Potential

Electrode potential: the potential of a cell consisting of the electrode of interest acting as a cathode and the standard hydrogen electrode acting as an anode.

E cell = E right – E left = E Ag – E SHE = E Ag – 0.000 = E Ag

Standard electrode potential of a half-reaction Eº:

the activities of the reactants and products are all unity.

half-reaction

Ag +

+

e -

Ag(s)

Pt, H 2 (p = 1.00 atm)|H + ( a H + = 1.00)Ag + (a Ag + = 1.00)|Ag SHEAg + (a Ag + = 1.00)|Ag Standard electrode potential (Eº Ag + /Ag ) = + 0.799 V

123

Fig. 18-7 Measurement of the electrode potential for a Ag electrode. If the silver ion

Fig. 18-7 Measurement of the electrode potential for a Ag electrode. If the silver ion activity in the right-hand compartment is 1.00, the cell potential is the standard electrode potential of the Ag + /Ag half-reaction.

electrode potential of the Ag + /Ag half-reaction. Fig. 18-8 Measurement of the standard electrode potential

Fig. 18-8 Measurement of the standard electrode potential for Cd 2+ + 2e - Cd(s)

Cd 2+ +

Cd 2+ /Cd + = -0.403 V Cd(s) + 2H + Cd 2+ + H 2 (g)

2e -

Cd(s)

Half-Reaction

Standard Electrode Potential, V

Ag + + e - Ag(s) 2H + + 2e - H 2 (g)

Cd 2+ + 2e -

Zn 2+ + 2e - Zn(s)

Cd(s)

+ 0.799

+ 0.000

0.403

0.763

The relative strength of the four ionic species as electron acceptors (oxidizing agents):

Ag + > H + > Cd 2+ > Zn 2+

18C-5 Effect of Concentration on Electrode Potentials: The Nernst Equation

aA

+

bB

+

E = E

o

RT

ln

c d

[C] [D]

⋅⋅⋅

 

n

F

a b

[A] [B]

⋅⋅⋅

+

ne -

cC

+

dD

+

.

Eº = standard electrode potential

R

= gas constant 8.314 J K -1 mol -1

T

= temperature in kelvins

n = no. of moles of e - that appear in the half-reaction

F

= faraday = 96485 C (coulombs)

ln

= natural logarithm = 2.303 log

 

E = E

o

0.0592

c d

[C] [D]

⋅⋅⋅

   
 

n

log

a b

[A] [B]

⋅⋅⋅

Ex. 18-2

(1) Zn 2+

+

2e -

Zn(s)

E

=

E

o

0.0592

1

     

2

log

[Zn

2 +

]

 

(2) Fe 3+

+

e -

Fe 2+

E

=

E

o

0.0592

[Fe

2 +

]

     

1

log

[Fe

3 +

]

124

+

H 2 (g)

E

 

E

o 0.0592

log

P

H

2

=

 

2e -

+

5e -

+

8H +

Mn 2+

+

H 2 O

 

o 0.0592

[Mn

2 +

]

 

E

=

E

log

2

5

-

[MnO ][H

4

+ ]

8

[H

+ ]

2

(3) 2H +

(4) MnO 4 -

(5) AgCl(s) + e -

Ag(s) + Cl -

E = Eº – (0.0592) log [Cl - ]

18C-6 The Standard Electrode Potential, Eº (Table 18-1)

the electron potential when all reactants and products of a half- reaction have unity activity.

1. Eº relative potential (reference electrode: SHE = 0 V)

2. a relative reduction potential

3. the reactants and products are at unit activities

4. Eº independent of the number of moles reactant and product

Fe 3+ +

e -

Fe 2+

5Fe 3+ + 5e - 5Fe 2+

Eº = + 0.771 V

Eº = + 0.771 V

E

=

0.771

1

log

[Fe

2 +

3 +

]

0.0592

[Fe

]

E

=

=

0.771

0.771

0.0592

log

[Fe

2 5

+

]

0.771

0.0592

log(

[Fe

2 +

]

 

=

 

 

5

[Fe

3 5

+

]

5

[Fe

3 +

]

5

×

0.0592

log

[Fe

2

+

]

 

5

[Fe

3

+

]

)

5

5. E: + stronger oxidant than H+, – weaker oxidant than H+

6. Eº: temperature dependent

Systems Involving Precipitates or Complex Ions

Ag +

+

e -

Ag(s)

Ag + /Ag = + 0.799 V

Ag(S 2 O 3 ) 2 3- = + 0.017 V

AgCl(s)

+

e -

Ag(s) + Cl -

AgCl /Ag = + 0.222 V

Ag(S 2 O 3 ) 2 3- +

e -

Ag(s) + 2S 2 O 3 2-

E

=

=

E

E

0

Ag /Ag

+

0

Ag /Ag +

+

0.0592

1

1

log

[Ag

+

]

K

sp

0

Ag /Ag

E

=

+

0.0592log

0.0592log[Cl ]

-

[Cl - ] = 1.00, E= AgCl /Ag

E

0

AgCl/Ag

=

E

0

Ag

+

/Ag

+

0.0592 log1.82

×

10

10

=

0.799

+

(-0.577) - 0.000

=

0.222 V

125

0.0592

[Cl

-

]

log

1

K sp

0.0592 log1.00

Fig. 18-9 Measurement of the standard electrode potential for an Ag/AgCl electrode. Ex. 18-3 Calculate

Fig. 18-9 Measurement of the standard electrode potential for an Ag/AgCl electrode.

Ex. 18-3 Calculate the electrode potential of a silver electrode immersed in a 0.0500 M
Ex. 18-3 Calculate the electrode potential of a silver electrode immersed in a 0.0500 M
solution of NaCl using (a) Eº Ag + = 0.799 V, and (b) Eº AgCl = 0.222 V.
(a) Ag +
+
e -
Ag(s)
+ 0.799
− 10
Ksp
1.82
× 10
− 9
[Ag
+ ] =
=
=
3.64
×
10
M
-
0.0500
[Cl ]
1
E =
0.799
0.0592 log
0.299 V
9 =
3.64
× 10
(b) E = 0.222 – 0.0592 log[Cl - ] = 0.222– 0.0592 log 0.0500 = 0.299 V

18C-7 Limitations to the Use of Standard Electrode Potentials

Use of Concentrations Instead of Activities Effect of Other Equilibria Formal Potentials

The electrode potential when the ratio of analytical concentrations of reactants and products of a half-reaction is exactly 1.00 and the molar concentrations of any other solutes are specified.

Fig.18-10 Measurement of the formal potential of the Ag/Ag + couple in 1M HClO 4 .

solutes are specified. Fig.18-10 Measurement of the formal potential of the Ag/Ag + couple in 1M

126