Electrochemistry

John W. Moore
Conrad L. Stanitski
Peter C. Jurs
http://academic.cengage.com/chemistry/moore

Chapter 18
Electrochemistry and Its
Applications
Stephen C. Foster Mississippi State University

Electrochemistry is the study and use of e- flow in

chemical reactions.
Redox reactions generate (and use) e Those e- can be harnessed (batteries).
Corrosion is an electrochemical reaction.
Applied e- flow:
Can drive reactant-favored reactions toward products.
Rechargeable batteries, electrolysis, and
electroplating

Redox Reactions

Redox Reactions

Oxidation Number Refresher

Pure element = 0.
Monatomic ion = charge of ion.
(ox. numbers in a species) = overall charge.

Oxidation & reduction (Redox) always occur together.

Element
F
Cl, Br, I
H
O

ox. no.
1
1
+1
2

Exceptions?
None
Interhalogens
Metal hydrides = -1
Metal peroxides = -1
Halogen oxides

Redox Reactions

Oxidation = loss of e- = increase in ox. no.

+2 e-

2 HCl(aq) + Mg(s)
+1 -1

H2(g) + MgCl2(aq)

-2

+2 -1

e-

H+ is reduced, Mg is oxidized.

Using Half-Reactions to Understand Redox

Give oxidation numbers for each atom. Identify the oxidizing

and reducing agents:
6 Fe2+ + Cr2O72- + 14 H3O+
6 Fe3+ + 2 Cr3+ + 21 H2O
Species
Fe2+
Cr2O72H3O+
+1
Fe3+
Cr3+
H2O

Reduction = gain of e- = decrease in ox. no.

Redox reactions split into half reactions:

Ox. number
Explanation
+2
charge on ion
O = -2; Cr = +6
O is usually -2; 2(Cr) + 7(-2) = -2
O = -2; H = +1
O is usually -2; H is usually
+3
+3
O = -2; H = +1

Fe2+ Fe3+ oxidation

Cr(+6) Cr3+ reduction

charge on ion
charge on ion
O is usually -2, H is usually +1

Fe2+ = reducing agent

Cr2O72- = oxidizing agent

Using Half-Reactions to Understand Redox

Balancing Redox Equations

Half-reactions may include different numbers of e-:

Redox in acidic or basic solutions are harder

(H2O, H3O+ or OH- are often omitted).

Al3+(aq) + 3 e-

Al(s)

Zn2+(aq) + 2 e-

Zn(s)

e- must balance in the full reaction.

2[ Al(s)
3[ Zn2+(aq) + 2 e2 Al(s) + 3 Zn2+(aq)

Al3+(aq) + 3 e- ]
Zn(s) ]

H3AsO4 + I2

HAsO2 + IO3-

which occurs in aqueous acidic solution.

2 Al3+(aq) + 3 Zn(s)

Balancing Redox Equations in Acidic Solution

H3AsO4 + I2

Balance:

HAsO2 + IO3-

(acidic solution)

(i) What is oxidized? Reduced?

I2 (I = 0) IO3- (I = +5) oxidation
H3AsO4 (As = +5) HAsO2 (As = +3) reduction
(ii) Write unbalanced half-reactions:
H3AsO4 HAsO2
I2 IO3(iii) Balance atoms (except H and O).
H3AsO4 HAsO2
I2 2 IO3-

Balancing Redox Equations in Acidic Solution

(vii) Equalize e- and add.
5 [ H3AsO4 + 2 H+ + 2 e- HAsO2 +2 H2O ]
1[
I2 + 6 H2O 2 IO3- + 12 H+ + 10 e- ]
5 H3AsO4 + 10 H+ + 10 e- + I2 + 6 H2O
2H+
5 HAsO2 + 10 H2O + 2 IO3- + 12 H+ + 10 e4H2O

5 H3AsO4 + I2 5 HAsO2 + 4 H2O + 2 IO3- + 2 H+

(viii) Make H3O+ (H2O + H+). Add H2O if needed.
5 H3AsO4 + I2 5 HAsO2 + 2 H2O + 2 IO3- + 2 H3O+

Balancing Redox Equations in Acidic Solution

(iv) Balance O (add H2O as needed).
H3AsO4 HAsO2 + 2 H2O
I2 + 6 H2O 2 IO3(v) Balance H (add H+ as needed).
H3AsO4 + 2 H+ HAsO2 +2 H2O
I2 + 6 H2O 2 IO3- + 12 H+
(vi) Balance charges (add e- ).
H3AsO4 + 2 H+ + 2 e- HAsO2 +2 H2O
I2 + 6 H2O 2 IO3- + 12 H+ + 10 ezero charge 2(-1) + 12(+1)}
10(-1)
0
=
10
+ -10

Balancing Redox Equations in Basic Solution

Balance the following (basic conditions):
N2 + S2S + N2H4
(i) Oxidized? Reduced?
N2 (N = 0) N2H4 (N = -2) reduction
S2- (S = -2) S (S = 0)
oxidation
(ii) Unbalanced half-reactions:
N2 N2H4

S2- S

(iii) Balance (except H and O).

N2 N2H4

S2- S

Balancing Redox Equations in Basic Solution

Balancing Redox Equations in Basic Solution

(vi) Equalize e- and add.
1 [ N2 + 4 H+ + 4 e- N2H4 ]
2 [ S2- S + 2 e- ]
+
N2 + 4 H + 4 e- + 2 S2- N2H4 + 2 S + 4 eN2 + 4 H+ + 2 S2- N2H4 + 2 S

(iv) Balance O (add H2O as needed).

N2 N2H4
S2- S
(v) Balance H (add H+ as needed).
N2 + 4 H+ N2H4
S2- S

(vii) Make H2O (H+ + OH-). Add OH-.

N2 + 4 H+ + 4 OH- + 2 S2- N2H4 + 2 S + 4 OH-

(vi) Balance charges (add e- ).

N2 + 4 H+ + 4 e- N2H4
S2- S + 2 e-

N2 + 4 H2O + 2 S2- N2H4 + 2 S + 4 OH-

Electrochemical Cells

Electrochemical Cells

Cu2+(aq) + Zn(s) Cu(s) + Zn2+(aq)

e-

e-

Cu2+(aq) + Zn(s) Cu(s) + Zn2+(aq)

Linked oxidation and reduction

reactions.

e-

e-

e- move across an external

conductor.

Also called a voltaic cell or a battery.

battery
A battery is strictly a series of linked voltaic cells.

Electrochemical Cells

Electrodes (anode & cathode)

Allow e- to pass in and out of
solution.
A salt bridge (or porous barrier)
is required...

Anode
(oxidation)

Salt
bridge

Cathode
(reduction)

Electrochemical Cells

Salt bridge
Contains a salt solution (e.g. K2SO4 ).
Ions pass into the cells (restricts bulk flow).
Stops charge buildup.
porous
plug

Zn
SO42Zn2+

SO42- released
as Zn Zn2+

K2SO4

Cu
K+
Cu2+

2 K+ released
as Cu2+ Cu

Electrochemical Cells

Electrochemical Cells

Zinc is removed:
Zn

A compact notation:
Zn2+ + 2 e-

Oxidation at the anode (both vowels).

Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu (s)

anode cell

Zn supplies e-.

cathode cell

Anode has - charge.

Current flows from anode to cathode.

Copper is deposited:
Cu2+ + 2 e-

Cu

Reduction at the cathode (both consonants).

Cu2+ accepts e-.

| = phase boundary.
|| = salt bridge.
Details (e.g. concentration) listed after each species.

Cathode has + charge.

Electrochemical Cells & Voltage

Electrical work

= charge x Ep
= (number of e-) Ep

SI Units
Charge: 1 coulomb (C) = 1 ampere x second = 1 As
Potential:
1 volt (V) = 1 J C-1

Electrochemical Cells & Voltage

Cell voltage varies if conditions vary.
A standard voltage ( E ) occurs if:
All [solute] = 1 M.
or saturated if the solubility < 1 M.

All gases have P = 1 bar.

Voltage depends on cell

chemistry size.

All solids are pure.

Charge depends on nreactants

size.

Electrochemical Cells & Voltage

Electrochemical Cells & Voltage

Standard hydrogen electrode (SHE)

Ecell is positive = product favored reaction

(Ecell < 0 is reactant favored)
favored

Absolute voltages cannot be measured.

Pt | H2(1bar), 1M H3O+ ||

E = 0 V (oxidation & reduction).

They are measured relative to a standard electrode.

2 H3O+(aq, 1M) + 2 e-

H2(g, 1 bar) + 2 H2O ()

Using Standard Cell Potentials

Reduction Half Reaction

E (V)
2 F-(aq)

+2.87

H2O2(aq) + 2 H3O + 2 e- 4 H2O()

+1.77

F2(g) + 2 e-

Electrochemical Cells & Voltage

Cu2+(aq) + 2 eCu(s)
Zn(s)
Zn2+(aq) + 2 e-

reduction
oxidation

MnO4-(aq)+8 H3O+ + 5 e- Mn2+(aq) + 12 H2O() +1.51

Tabulated as
reductions.

Cl2(g) + 2 e-

2 Cl-(aq)

+1.358

Br2(g) + 2 e-

2 Br-(aq)

+1.066

Ag+(aq) + e-

Ag(s)

+0.799

Cu2+(aq) + 2 e-

Cu(s)

+0.337

2 H3O+(aq) + 2 e-

H2(g) + 2 H2O()

Ni2+(aq)

e-

Ni(s)

-0.25

Fe2+(aq) + 2 e-

Fe(s)

-0.44

Zn2+(aq) + 2 e-

Zn(s)

-0.763

Al3+(aq) + 3 e-

Al(s)

-1.66

Li+(aq)

Li(s)

-3.045

+2

e-

0.00

Electrochemical Cells & Voltage

Reaction

Process

Ered (Table)

Zn Zn2+ + 2 e-

oxidation

-0.76 V

+0.76 V

Cu

reduction

+0.34 V

+0.34 V

Cu2+

+2

e-

Ecell = Ecathode - Eanode

Ecell = 0.34 (-0.76) V

The overall voltage:

Ecell = EZn2+, reduction + ECu, oxidation
If an equation is reversed, E -1 x E
Eoxidation = - Ereduction.
E tables are reduction values, so:
Ecell = Ereduction + Eoxidation
Ecell = Ecathode - Eanode

Electrochemical Cells & Voltage

What is E for a Ni(s) | Ni2+|| Ag+ | Ag(s) cell?
Reduction Half Reaction
Ag+(aq)
.
.
.

e-

Ag(s)

E (V)
+0.799
.
.
.

Ni2+(aq) + 2 e- Ni(s)

-0.25

= 1.10 V
Or

Ecell = Eoxid + Ered

= 0.34 + 0.76 V = 1.10 V

Anode written on the left; cathode the right.

E = Ecathode - Eanode = 0.799 (-0.25) V = 1.05 V

Electrochemical Cells & Voltage

Using Standard Cell Potentials

If Ni(s)| Ni2+(aq, 1M) is connected to SHE, the Ni

electrode loses mass over time. Ecell = 0.25 V. Is Ni
oxidized or reduced? What is E for the Ni half cell?

1. Tabulated half-cell E are reductions.

Ni loses mass:
Ni(s) Ni2+(aq) + 2 eNi is oxidized (a
anode).

3. More positive E = easier reduction.

Since:

Ecell = Ecathode - Eanode

0.25 V = ESHE - Eanode = 0 - Eanode
Eanode = -0.25 V

(Note: this is the tabulated reduction value)

2. Reactions can be reversed.

4. Less positive E = easier oxidation (for the reverse

reaction).
5. A left species, will oxidize any right below it.
6. E depends on [reactant] and [product], but not on
nreactant or nproduct (i.e not stoichiometric coefficient).

Using Standard Cell Potentials

Using Standard Cell Potentials

Will Zn(s) react with a 1 M iron(III) solution? If so what

is E for the reaction?

Will Zn react with a 1 M iron(III) solution? If so what is E for the reaction.

Reduction Half Reaction

F2(g) + 2

e-

E (V)

F-(aq)

+2.87

Fe2+(aq)

Fe3+(aq) + e-

Yes!

+2

Zn(s)

e-

E = +0.771 V
E = -1(-0.763 V)

2 Fe3+ + Zn 2 Fe2+ + Zn2+

Ecell = +1.534 V

+0.771

2 H3O+(aq) + 2 e- H2(g) + 2 H2O()

Zn2+(aq)

2 Fe3+ + 2 e- Fe2+
Zn
Zn2+ + 2 e-

+0.0
-0.763

Fe3+ (left) is higher than Zn (right).

Note
2 x (Fe3+ reaction) to balance e-.
E (Fe3+) is not doubled.

Using Standard Cell Potentials

Using Standard Cell Potentials

a) Will Al(s) react with a 1 M tin(IV) solution?

b) Will 1 M Fe2+ react with Sn(s)?

Whats the voltage of: Al(s)|Al3+,1M || Sn2+,1M|Sn(s) ?

Sn4+ + 2 eSn2+ + 2 eFe2+ + 2 eAl3+ + 3 e-

Sn2+ (s)
Sn (s)
Fe (s)
Al (s)

+0.15 V
-0.14 V
-0.44 V
-1.66 V

(a) Yes left (Sn4+) above right (Al).

(b) No left (Fe2+) below right (Sn).

E and Gibbs Free Energy

Product-favored reactions: G < 0.
Spontaneous cell reactions: Ecell > 0.
G = n F E
Ecell
with n = moles of e- transferred,
F = Faraday constant = charge/(mol of e-).
= (e- charge) x (Avogadros number).
= (1.60218 x 10-19 C)(6.02214 x 1023 mol-1).
F = 96,485 C/mol = 96,500 C/mol (3 sig. fig.)

Sn2+ + 2 e- Sn
Al
Al3+ + 3 eBalance e-:
3(Sn2+ + 2 e- Sn)
2(Al
Al3+ + 3 e- )
2+
3 Sn + 2 Al 3 Sn + 2 Al3+

E = -0.14 V
E = -1(-1.66 V)

E = -0.14 V
E = +1.66 V
Ecell = +1.52 V

E and Gibbs Free Energy

Cu2+ + Zn(s) Cu(s) + Zn2+

Ecell = 1.10 V

Spontaneous.
G = nFEcell = 2 mol (96500 C/mol)(1.10 V)
= 2 .12 x105 J

(1 J = 1 C V)

= 212 kJ

G, Ecell, and K
Since:

G, Ecell, and K

G = RT ln K = nFEcell

Determine K for:
Cu2+ + Zn(s) Cu(s) + Zn2+

RT
Ecell = R T ln K = (2.303)
log K
nF
nF

Ecell = 0.0257 V ln K
n

At 298 K:

Ecell = 1.10 V

Ecell = 0.0592 V log K

n
or,

1.10 V =

0.0592 V log K
2
2 mol e

log K = 37.16

0.0592 V
Ecell =
log K
n

K = 1037.16 = 1.5 x 1037

Effect of Concentration on Cell Potential

Effect of Concentration on Cell Potential

E values apply if [solute] = 1 M (or saturated).

What is the voltage for:

Cu2+ + Zn(s) Cu(s) + Zn2+
2+
if [Cu ] = 0.1 M and [Zn2+] = 5.0 M. Ecell = 1.10 V.

Other conditions:
Ecell = Ecell

RT
ln Q
nF

Nernst equation
E = E

At 298 K:
Ecell = Ecell 0.0592 V log Q
n

E = 1.10

Ecell = Ecell 0.0257 V ln Q

n

5.0
0.1

Concentration Cells

Concentration dependence leads to:

Zn | Zn2+ (dilute) || Zn2+ (conc.) | Zn

Ecell 0 V

Zn | Zn2+ (0.01M) || Zn2+ (1M) | Zn

anode = oxidation

0.0592
log
2

= 1.05 V

Concentration Cells

Example

[Zn2+]
0.0592
log
[Cu2+]
2

E = E

E = 0.0

0.010
0.0592
log
1
2

E = 0.0

0.0592
log 10-2
2

cathode = reduction

Zn(s) Zn2+ (0.01M) + 2 eZn2+ (1M) + 2 e- Zn(s)

Zn2+(1M) Zn2+(0.01M)
(net reaction)

[Zn2+]dilute
0.0592
log
[Zn2+]conc
2

E = 0.0592 V

Common Batteries

Primary Batteries
Alkaline Battery:

Primary battery
One time use. Not easily rechargeable

Zn(s) + 2 OH-(aq) ZnO(aq) + H2O() + 2 eMnO2(s) + H2O() + e- MnO(OH)(s) + OH-(aq)

Overall

Secondary battery
Rechargeable battery.

Zn(s) + H2O() + 2 MnO2(s) ZnO(aq) + 2 MnO(OH)(s)

Ecell = 1.54 V when new.

Primary Batteries

Secondary Batteries

Mercury battery

Lead-Acid Battery (high capacity, high current).

Pb(s) + HSO4-(aq) + H2O() PbSO4(s) + H3O+(aq) + 2 ePbO2(s) + 3 H3O+(aq) + HSO4-(aq) + 2 e- PbSO4(s) + 5 H2O
Pb + PbO2(s) + 2 H3O+ + 2 HSO4-(aq) 2 PbSO4(s) + 4 H2O

Net E = +2.041 V
Zn(s) + 2 OH- ZnO(aq) + H2O() + 2 eHgO(s) + H2O() + 2 e- Hg() + 2 OH-(aq)
Zn(s) + HgO(s) Hg() + ZnO(aq)

Insoluble PbSO4 stays on the electrodes

The reaction is reversed by recharging.

Ecell = 1.35 V

Lead-Acid Storage Battery

6 cells in series (12 V).

Secondary Batteries
Nickel-Cadmium (Nicad).
Cd(s) + 2 OH-(aq) Cd(OH)2(s) + 2 e2[NiO(OH)(s) + H2O() + e- Ni(OH)2(s) + OH-(aq)]
Cd(s) + 2 NiO(OH)(s) + 2 H2O Cd(OH)2(s) + 2 Ni(OH)2(s)
Insoluble
(Rechargable)

net: E = +1.299 V

Secondary Batteries

Secondary Batteries

Nickel-metal hydride (NiMH). Doesnt use toxic Cd.

Lithium Ion. Low mass, high energy density.

MH(s) + OH-(aq) M(s) + H2O() + e-

Li(s) (in polymer) Li+ (in polymer) + eLi+ ( in CoO2 ) + e- + CoO2 LiCoO2

NiO(OH)(s) + H2O() + e- Ni(OH)2(s) + OH-(aq)

MH(s) + NiO(OH)(s) M(s) + Ni(OH)2(s)

Ecell =+1.4 V

Li(s) + CoO2(s) LiCoO2(s)

M is a metal alloy in KOH

Ecell = 3.4 V

Fuel Cells

Electrolysis

Convert bond energy into electricity.

Electrolytic cell:
cell Applied voltage forces a reaction to
occur. e.g. electrolysis of molten NaCl:

ProtonProton-Exchange
Membrane (PEM) fuel cell.
H2 2 H+ + 2 e O2 + 2 H+ + 2 e- H2O

V
e-

e-

Pt catalyst

2 Na+ + 2 e- 2Na ()

O2 in

H2 in

Cl2 (g) + 2

+2

Cl-

Cl2 (g) + 2 Na()

H+

gases flow
through
channels

Na+

E = -2.714 V

Cl-

e-

E = -1.358 V
E = -4.072 V

H+

Graphite electrodes.
Pt catalyst coated on both
sides of the membrane.

H2 out

H2O out

Anode

Cathode

Na() and Cl2(g) produced if > 4.1 V is applied.

However, melting NaCl takes lots of energy

H+ exchange
membrane

Electrolysis

Electrolysis

reductions

K+(aq) + e- K(s)

oxidations

Aqueous solutions? Other reactions can occur.

Consider KI(aq):

2 I-(aq) I2(aq) + 2 e-

E = -2.925 V

2 H2O() + 2 e- H2(g) + 2 OH-(aq) E = -0.828 V

E = -0.535 V

6 H2O() O2(g) + 4 H3O+(aq) + 4 e- E = -1.229 V

Eox -1 x Ered

The most positive E half reactions occur

2 H2O + 2 I- H2 + I2 + 2 OH-

Ecell = -1.363 V

Brown = I2 ; Purple = OH- (phenolphthalein)

Electrolysis

Electrolysis

Reduction Half Reaction

Aqueous
oxidation will
not occur.

Aqueous
reduction will
not occur.

F2(g) +2 e-

E (V)
2 F-(aq)

+2.87

4 H2O()

+1.77

2 Cl-(aq)

+1.358

O2(g) + 4 H3O+(aq) + 4 e- 6 H2O()

+1.229

Br2(g) +2 e-

2 Br-(aq)

+1.066

Ag+(aq) + e-

Ag(s)

+0.799

2 H3O+(aq) + 2 e-

H2(g) + 2 H2O()

Ni2+(aq) + 2 e-

Ni(s)

-0.25

Fe2+(aq) + 2 e-

Fe(s)

-0.44

Zn2+(aq) + 2 e-

Zn(s)

-0.763

2 H2O() + 2 e-

H2(g) + 2 OH-(aq)

-0.8277

Al3+(aq) + 3 e-

Al(s)

-1.66

Na+(aq) + e-

Na(s)

-2.714

K+(aq) + e-

K(s)

-2.925

H2O2(aq) + 2 H3O+2

e-

Cl2(g) +2 e-

0.00

Electrolysis of Brine

Summary
Metal ions are reduced if Ered > 0.8 V
Aqueous Na+, K+, Mg2+, Al3+ cannot be reduced.
Anions can be oxidized if Ered < +1.2 V
Aqueous F- cannot be oxidized.
In practice Erequired > E calculated.
Overvoltage is needed
Cl-(aq) can be oxidized to Cl2(g).

Counting Electrons

Chlorine is produced from NaCl(aq) by the chlor-alkali

process.
2 Cl-(aq) Cl2(g) + 2 e2 H2O() + 2 e- 2 OH-(aq) + H2(g)

Cu2+(aq) + 2 e-

Cu(s)

2 mol e- 1 mol Cu.

Also

charge = current x time

1 coulomb = 1 ampere x 1 second
1C=1As

NaOH(aq) is 21- 30% NaOH by weight.

Counting Electrons

Counting Electrons

Determine the mass of Cu plated onto an electrode from

a Cu2+ solution by the application of a 10. A current for
10. minutes.

What is the cost to produce 14. g of Al (mass of a soda

can) by the reduction of Al3+. Assume V = 4.0 V and 1
kWh of electricity costs 10 cents.

Cu2+(aq) + 2 e-

Charge = 10. A x 10. min x (60 s/min) = 6.0 x

6.0 x103 C

Al3+ + 3 e-

Cu(s)
103

1 mol e- 1 mol Cu 63.55 g

= 2.0 g
96500 C 2 mol e- 1 mol Cu

14. g 1 mol Al
26.98 g

e-

3 mol
1 mol Al

Al
96500 C
1 mol e-

= 1.5 x 105 C

1J

Energy used = (1.5 x105 C)(4.0V) 1 C x 1V

1 kWh
3.60 x 106 J

= 0.17 kWh (or 1.7 cents)

10

Corrosion: Product-Favored Reactions

Corrosion: Product-Favored Reactions

Oxidation of metals by the environment.

Iron rusts

Anode:

M(s)

Mn+ + n e-

Cathode: often involve water and/or O2

O2(g) + 2 H2O() + 4 e- 4 OH-(aq)
2 H2O() + 2 e- 2 OH-(aq) + H2(g)

Anode:
2[Fe(s)
Cathode: O2(g) + 2 H2O() + 4 e2 Fe(s) + O2(g) + 2 H2O()

Iron(II) hydroxide is converted to rust by O2 and H2O:

Rust
(Fe2O3xH2O(s); x = 2 - 4)

Anode and cathode must be electrically connected.

(The metal itself acts as the conductor).

Corrosion: Product-Favored Reactions

Fe2+ + 2 e-]
4 OH-(aq)
2 Fe(OH)2(s)

Corrosion Protection
Anodic inhibition

Iron nails corroding:

Blue = Fe2+ indicator
Purple = OH- indicator

Paint or coat the surface.

Form thin metal oxide coat:

2 Fe(s) + 2 Na2CrO4(aq) + 2 H2O()

Fe2O3(s) + Cr2O3(s) + 4 NaOH(aq)

Stress points corrode

quickly.

Insoluble coating;
impervious to O2 and H2O

Cathodic protection Attach a more reactive metal

which will corrode first.

Corrosion Prevention
Iron can also be galvanized (coated with Zn):

Zn(OH)2 (insoluble film) forms on the

surface.
Zn Zn2++ 2 e- E = 0.763 V
Fe Fe2+ + 2 e- E = 0.44 V

11