Chapter 19

Electrochemistry
Brady and Senese
5th Edition

Index
19.1 Galvanic cells use redox reactions to generate electricity
19.2 Cell potentials can be related to reduction potentials
19.3 Standard reduction potentials can predict spontaneous re
actions
19.4 Cell potentials are related to free energy changes
19.5 Concentrations in a galvanic cell affect the cell potential
19.6 Electrolysis uses electrical energy to cause chemical reac
tions
19.7 Stoichiometry of electrochemical reactions involves elect
ric current and time
19.8 Practical applications of electrochemistry
2

Galvanic Reactions
Are spontaneous redox reactions
Release energy as heat if no resistance is met
May be separated into compartments to harness
energy as a battery

19.1 Galvanic cells use redox reactions to generate electricity

Anatomy of a Galvanic Cell

Cells (compartments containing reactants for each
half-reaction)
Electrodes to conduct current through the solution.
Salt bridge to offset ion movement
Supporting electrolyte

19.1 Galvanic cells use redox reactions to generate electricity

Electrochemical Cells
In all cells, electrons transfer between the cathode
(the reduction half-cell) and the anode (the
oxidation half-cell)
Electrical current is conducted through the passage
of electrons and ions
To prevent charge buildup,
a salt bridge allows ions
to move between the
cells

19.1 Galvanic cells use redox reactions to generate electricity

Your Turn
Towards which compartment will electrons flow in
an electrochemical cell?
A. Toward the cathode
B. Toward the anode
C. It depends on the reaction

19.1 Galvanic cells use redox reactions to generate electricity

Your Turn
Through which components of the cell will ions not
flow?
A. The electrodes
B. The solution
C. The salt bridge

19.1 Galvanic cells use redox reactions to generate electricity

Standard Cell Notation (Line Cell Notation)

Cell reactions separated by || that represents the salt
bridge
Electrodes appear at the outsides
Reaction electrolytes in inner section
Phases separated with |
Species in the same state separated with ,
Concentrations shown in ( )

19.1 Galvanic cells use redox reactions to generate electricity

Learning Check
Balance and identify the cathode and anode
CrO3(s) + MnO2(s) MnO4-(aq) + Cr3+(aq) (basic)

CrO3 + 3H2O + 3e- Cr3+ + 6OHMnO2 + 4OH- MnO4- + 2H2O + 3eCrO3(s) + MnO2(s) + H2O MnO4-(aq) + Cr3+(aq) +
2OH-(aq)
Cathode: CrO3
Anode: MnO2
19.1 Galvanic cells use redox reactions to generate electricity

Learning Check:
Balance and identify the cathode and anode
H2O2(aq) + CO2(g) H2C2O4(aq) + O2(g) (acidic)
H2O2 O2 + 2H+ + 2e2H+ + 2e- + 2CO2 H2C2O4

(acidic)

H2O2(aq) + 2CO2(g) H2C2O4(aq) + O2(g) (acidic)

Cathodic reaction: 2H+ + 2e- + 2CO2 H2C2O4
Anodic reaction: H2O2 O2 + 2H+ + 2e19.1 Galvanic cells use redox reactions to generate electricity

10

Learning Check
Where there are no conductive metals involved in a
process, an inert electrode is used.
C(gr) and Pt are often used. Write the standard cell
notation for the reactions
CrO3(s) + MnO2(s) MnO4-(aq) + Cr3+(aq) (basic)
H2O2(aq) + CO2(g) H2C2O4(aq) + O2(g) (acidic)
C(gr);MnO2(s) | MnO4-(aq) || CrO3(s) | Cr3+(aq) | C
C(gr)|H2O2(aq), H+(aq) | O2(g) || CO2(g) | H2C2O4(aq), H+(aq) | C(gr)

19.1 Galvanic cells use redox reactions to generate electricity

11

Your Turn!
In the reaction MnO2(s) + 2H+(aq) Mn2+(aq) + H2O2(aq)
which is the correct standard cell notation?
A. Pt, MnO2(s)|H+(aq), Mn2+(aq)||H2O|H2O2(aq), H+(aq)|Pt
B. Pt|H2O2(aq), H+(aq)|H2O||H+(aq), Mn2+(aq)|MnO2(s)Pt
C. Both are correct
D. Neither is correct

19.1 Galvanic cells use redox reactions to generate electricity

12

Electrical Potential
Every substance has the potential to gain
electrons, or be reduced in oxidation state
The relative ease of gaining electrons is termed the
reduction potential, and is symbolized Ered
If the matter being observed is in standard state
then E is termed the standard reduction potential
and is symbolized as Ered
Units are Volt 1 V = 1 J C-1

19.2 Cell potentials can be related to reduction potentials

13

Standard Reduction Potentials (Ered)

Ered are tabulated for nearly

every known substance

A high value of Ered (Ered > 0)
means that the substance is easily
reduced
Ered is a relative number,
arbitrarily determined
All substances are compared to
H+, which has a Ered of 0.00 V

19.2 Cell potentials can be related to reduction potentials

14

Cell Potentials
The standard cell potential is calculated as:
Ecell = Ecathode - Eanode

If the cell is non-standard:

Ecell = Ecathode - Eanode

In spontaneous redox reactions, the cathode

portion of the reaction has a higher
reduction potential than that of the anode
(Ecathode > Eanode)
19.2 Cell potentials can be related to reduction potentials

15

Your Turn
Given the two half reactions, what would be Ecell for
the reaction:
Ni(s) + H2O2(aq) + 2H+(aq) 2H2O + Ni2+(aq)
A.
B.
C.
D.

1.52 V
-1.52 V
2.02 V
-2.02 V

Reaction

Ecell

Ni2+ + 2e- Ni

-0.25

H2O2 + 2H+ + 2e- 2H2O

19.2 Cell potentials can be related to reduction potentials

1.77

16

Recognizing the Cathode

Given the cell reaction, the
cathode is the substance that is
reduced (gains electrons)
The anode is the substance that
creates electrons
LEO the lion says GER
the loss of electrons is oxidation and
the gain of electrons is reduction

Spontaneously, the cathode has the

most + Ered of the choices, and the
anode has the most Ered.
19.2 Cell potentials can be related to reduction potentials

17

Predicting Cells in a Spontaneous Reaction

Cathode (Gains e-)

Anode (Loses e-)

Usually a non-metal or a cation.

On the Ered table, these

substances have large, + values.
Water can be a cathode

Appears on the left side of the

reduction table

The cathode reaction occurs as

it appears on the reduction
table

Usually a metal or an anion.

On the Ered table, these have
large, - values.
Water can be an anode
Appears on the right side of the
reduction table.
The anode reaction occurs in
the reverse direction from that
which appears on the reduction
chart

19.3 Standard reduction potentials can predict spontaneous reactions

18

Learning Check
Calculate Ecell. Which are spontaneous?
Cu(s) + Ag+(aq) Cu2+(aq) + Ag(s)
[0.80 - 0.34] V = 0.46 V

Pb + Cu2+ Pb2+ + Cu
[0.34 - (-0.13)] V = 0.47 V

Cr2O72-(aq) + MnO2(s) MnO4-(aq) + Cr3+(aq)

[1.33-1.695] V = -0.365 V
Cu2+/Cu

0.34 V

Cr2O72-/Cr3+

1.33 V

Ag+/Ag

0.80 V

MnO4-/MnO2 1.695 V

Pb2+/Pb

-0.13 V

19.3 Standard reduction potentials can predict spontaneous reactions

19

Your Turn
Which of the following is not spontaneous?
A. Ni2+ + Pb Pb2+ + Ni
B. Ni + Pb2+ Pb + Ni2+
C. Zn + Pb2+ Pb + Zn2+
D. All are spontaneous
Ered
Ni2+ + 2e- Ni
Zn2+ + 2e- Zn
Pb2+ + 2e- Pb
19.3 Standard reduction potentials can predict spontaneous reactions

-0.25
-0.76
-0.13
20

The Thermodynamics of Electrochemistry

Because reduction potential was an arbitrarily
defined value, it has no direct physical meaning
It can be related to the free energy of a system,
however as: G = -nFcell
n = the number of moles of electrons
transferred in the process
F = Faradays Constant, 96,500 C/mol e If the system is not standard, G can be defined
as: G = -nFcell
19.4 Cell potentials are related to free energy changes

21

Learning Check
Calculate G in kJ. Which are spontaneous under standard
conditions?
Cu(s) + Ag+(aq) Cu2+(aq) + Ag(s)
G = -2 mol 96,500 C mol-1 0.46 J C-1 = -88.8 kJ
Pb + Cu2+ Pb2+ + Cu
G = -2 mol 96,500 C mol-1 0.47 J C-1 = -80.7 kJ
Cr2O72-(aq) + MnO2(s) MnO4-(aq) + Cr3+(aq)
G = -6 mol 96,500 C mol-1 (-0.365 J C-1) = 211 kJ
Not spontaneous
Cu2+/Cu 0.34 V

Cr2O72-/Cr

1.33 V

Ag+/Ag 0.80 V

MnO4-/MnO2

1.695 V

Pb2+/Pb -0.13 V
19.4 Cell potentials are related to free energy changes

22

Your Turn
Given that G = 65.3 kJ , what is the value for Ecell
for the reaction Cu2+(aq) + Hg(l) Hg2+(aq) + Cu(s)?
A. 6.53 V
B. .+0.338 V
C. -0.338 V
D. -0.676 V
E. None of these

19.4 Cell potentials are related to free energy changes

23

Relating E to the Equilibrium Constant

Many redox reactions are reversible, thus the whole
cell reactions have equilibrium constants, K
G= nFE
and, G= RT ln K
thus,

RT ln K
E
nF
o

K e

nFE
RT

19.4 Cell potentials are related to free energy changes

24

Learning Check:
Calculate K for the following cells.
Cu(s) + Ag+(aq) Cu2+(aq) + Ag(s)

nFE
RT

2 mol 96,500 C mol-1 0.46 J C-1

-1
-1

8.314
J
mol
K

298.15
K

Pb(s) + Cu2+(aq) Pb2+(aq) + Cu(s)

nFE
RT

E = 0.46 V

3.58 1015

E = 0.47 V

2 mol 96,500 C mol-1 0.47 J C-1

-1
-1

8.314 J mol K 298.15 K

e

19.4 Cell potentials are related to free energy changes

7.8 1015
25

Learning Check (Cont.)

Cr2O72-(aq) + MnO2(s) MnO4-(aq) + Cr3+(aq) E = 0.365 V

nFE
RT

6 mol 96,500 C mol-1 0.365 J C-1

-1
-1

8.314 J mol K 298.15 K

19.4 Cell potentials are related to free energy changes

1.1 1037

26

Your Turn!
What is the value of K for the reaction at 298.15 K:
Ecell = 4.33 V
3PbO2 + 4Al 3Pb + 2Al2O3
A.

2 mol 96,500 C mol-1 4.33 J C -1

-1
-1

8.314 J mol K 298.15 K

B.

3 mol 96,500 C mol-1 4.33 J C -1

-1
-1

8.314 J mol K 298.15 K

C.

6 mol 96,500 C mol-1 4.33 J C -1

-1
-1

8.314 J mol K 298.15 K

1
1

12
mol

96500
Cmol

4
.
33
JC

1 1

8
.
314
Jmol
K

298
.
15
K

D. None of the above

19.4 Cell potentials are related to free energy changes

27

The Nernst Equation

For non- standard

G = G + RT ln Q

conditions,
Substituting for the free nFE = nFE + RT ln Q
energy, G, terms gives us
Dividing by nF, we get
o RT
the Nernst Equation
EE
ln Q
nF
When the temperature is
298 K and ln is converted
o 0.0592 log Q
to log,
EE
n
19.5 Concentrations in a galvanic cell affect the cell potential

28

Learning Check: Calculate Ecell

Al3+/Al -1.66 V

Zn2+/Zn -0.76 V

Al|Al3+(aq) (0.5 M)||Zn2+(aq) (0.2 M)|Zn

Eo ( 0.76 ( 1.66))
0.0592
[0.5]2
E 0.90 V
log
0.885 V
3
6
[0.2]

Al|Al3+(aq) (0.5 M)||Zn2+(aq) (1 M)|Zn

Eo (0.76 (1.66)) 0.90 V

0.0592
[0.5]2
E 0.90
log
0.906 V
3
6
[1]
19.5 Concentrations in a galvanic cell affect the cell potential

29

Learning Check
Al|Al3+(aq) (0.5 M)||Al3+(aq) (0.2 M)|Al Al3+/Al -1.662 V

E o (1.66 (1.66)) 0 V
0.0592
[0.5]
E 0
log
7.85 103 V
3
[0.2]
Al|Al3+(aq) (0.5 M, 25 C )||Al3+(aq) (0.5 M, 50 C )|Al
8.314 (323 K)
1
ln
1.6664 V
3 96,500
[0.5]
8.314 (298 K)
1
E (-1.66)
ln
1.6659 V
3 96,500
[0.5]
Ecell Ecathode Eanode 0.0005 V
E (-1.66)

19.5 Concentrations in a galvanic cell affect the cell potential

30

Learning Check: Find the Unknown

Cr|Cr3+(?? M) ||Ni2+(0.5 M)|Ni
Ecell = +0.494 V

0.0592
[x]2
0.494 (0.25 (0.74))
log
6
[0.5]3

0.222 M = x

Pt|H2(1atm)| H+(? ?pH)||H+(1 M)|H2(1 atm)|Pt

Ecell = 0.000571 V

0.0592
[x]2
0.000571 (0.00 0.00)
log 2
2
[1]

0.978 M = x; pH = 0.00965
H+/H2

0.00 V

Cr3+/Cr

-0.74 V

Ni2+/Ni

-0.25 V

Cu2+/Cu

0.34 V

19.5 Concentrations in a galvanic cell affect the cell potential

31

Your Turn
Consider the reaction shown. What is the value of Ecell?
Pb SO42-(0.1 M) PbSO4 Ni2+(0.2 M) Ni
A.
B.
C.
D.

0.998 V
-0.998 V
-0.101 V
None of these

Ecell

0.060 V

0.0592
1
(0.25 (0.36))
log
2
[0.1][0.2]

Ni2+ Ni -0.25 V

PbSO4 Pb

-0.36 V

19.5 Concentrations in a galvanic cell affect the cell potential

32

Learning Check
Consider the following reaction. Is favored at high or low
temperatures?
Pt|H2(1 atm)|H+(pH = 4)||Cu2+(0.1 M)|Cu

Eo (0.34 0.00)
8.314 T
[0.0001]2
E 0.34
ln
2 96,500
[0.1]2

When Q < 1, reaction is favored at

higher temperature
19.5 Concentrations in a galvanic cell affect the cell potential

33

Electrolytic Reactions: A Refinement

Some reactions are not favored as written
(Ecath < Eanode), yet we would like them to occur
To do this, we apply electrical potential to the
system which exceeds the energy need, and we
remove any possible competing reactions
Since these reactions are not favored, they are
not likely to short out
These reactions can often be performed in one
container, without resistance
19.6 Electrolysis uses electrical energy to cause chemical reactions

34

Electrolysis vs. Electrolytic vs. Galvanic

Note that electrolysis means the application of
electricity
Electrolytic means that the particular reaction
is not spontaneous
Electrolytic Cell

Galvanic Cell

Cathode is negative (reduction)

Anode is positive (oxidation)
Non-spontaneous
Requires a battery

Cathode is positive (reduction)

Anode is negative (oxidation)
Spontaneous
Is a battery

19.6 Electrolysis uses electrical energy to cause chemical reactions

35

Learning Check
In the electrolysis of aqueous K2SO4 The products of the
electrolysis are H2 and O2 gas, not the expected products solid
K and S2O82-. Why?
Cathode

Anode

K+ + e- K -2.92 V
H2O + 2e- H2 + OH- -0.83 V

SO42- S2O82- + 2e- +2.01 V

2H2O O2 + 4H+ + 2e- +1.23 V

Water competes

19.6 Electrolysis uses electrical energy to cause chemical reactions

36

Learning Check
Predict the likely products of the following, when an
electrode is dipped into:
A solution of NaCl
H2(g), O2(g)
Molten NaCl

Cl2(g), Na(l)

A solution of HCl

H2(g), O2(g)

19.6 Electrolysis uses electrical energy to cause chemical reactions

37

Your Turn
An electrode is dipped into an aqueous solution
containing K+(aq) , NO3-(aq), H2O(l) and Cl2(aq).
Which is the cathode?
A. K+(aq)
B. NO3-(aq)
C. H2O(l)
D. Cl2(aq)

4H2O + 2e- 2H2 + O2

NO3- + 3H+ + 3e- HNO2+ H2O
K+ + e- K
Cl2 + 2e- 2Cl-

19.6 Electrolysis uses electrical energy to cause chemical reactions

Ered
-0.83
0.94
-2.92
1.36
38

The Kinetics of Electrolysis

Faradays Equation: q = It = nF
q = charge (coulombs, C)
I = current (Amperes, A, or C/s)
t = time (s)
n = moles of electrons transferred in the process
F = Faradays constant (96,500 C mol-1)
Using units tell us how these quantities are related

19.7 Stoichiometry of electrochemical reactions involves electric current and time

39

Electroplating
In Faradays equation, we use the number of
moles of electrons transferred, ne
Because we cant see electrons, we gauge this by
the amount of metal deposited or lost
Using the half-reaction and stoichiometry, we can
relate the metal to the number of moles of
electrons
moles metal
mass metal

MM metal

coefficient e

ne
coefficient m

19.7 Stoichiometry of electrochemical reactions involves electric current and time

40

Learning Check
What current must be supplied to deposit 3.00 g Au from a
solution of AuCl3 in 200.0 s?
1 mol Au 3 mol e- 96,500 C
3.00 g Au

4410 C = I 200.0 s
196.97 g 1 mol Au
mol e

22.1 A
How much time (in s) does it take to plate 10.2 g of Ag+
using a 0.1 mA power source?
1mol Ag 1 mol e- 96,500 C
10 3 A
10.2 g Ag

0.1 mA
t
107.87 g 1 mol Ag
mA
mol e

t = 9 107 s

19.7 Stoichiometry of electrochemical reactions involves electric current and time

41

Your Turn
In Chrome Plating, Cr3+ is plated as Cr. How long will the
process take if 1.50 g Cr (MM = 52.00) are required and
the current is 50 mA?
A. 1.2 106 s
B. 4.1 105 s
C. 6.5 107 s
D. 1.7 105 s
Ered
Cr3+ +3e- Cr(s)

-0.744 V

19.7 Stoichiometry of electrochemical reactions involves electric current and time

42

Batteries - Galvanic Cells

Primary Cell

Secondary Cell

Non-rechargeable
Alkaline dry cell

Rechargeable
Pb storage Battery

19.8 Practical applications of electrochemistry

43

Important Properties of Batteries

Shelf-life, rate of energy output
Energy density (the ratio of available energy to
battery volume)
Specific energy (the ratio of available energy to
weight)

19.8 Practical applications of electrochemistry

44

Lithium Batteries
Lithium can be used in batteries with high
specific energy (because of its low mass) and
high energy density (because of its very (-) Ered)
Can be either non-rechargeable (primary cells) or
rechargeable (secondary cells)

19.8 Practical applications of electrochemistry

45

Lithium Ion Cells (2)

Dont actually involve true oxidation and
reduction
Li+ ions can slip between layers of atoms in solids
such as graphite intercalation
The Li+ ion battery is based on the transport of Li+
ions

19.8 Practical applications of electrochemistry

46

Hydrogen Fuel Cell

Clean burning
No electrode loss
Easily replenished
High operational
temperature
Highly efficient

19.8 Practical applications of electrochemistry

47

Application: Refining
Al2O3 is electrolyzed in cryolite, AlF6.

19.8 Practical applications of electrochemistry

48

Purification of Copper

19.8 Practical applications of electrochemistry

49

Application: Production of NaOH

19.8 Practical applications of electrochemistry

50