Electroqumica

21-1

Key Points About Redox Reactions

Oxidation (electron loss) always accompanies reduction

(electron gain).
The oxidizing agent is reduced, and the reducing agent is
oxidized.
The number of electrons gained by the oxidizing agent
always equals the number lost by the reducing agent.

21-2

Oxidation & Reduction

oxidation is the process that occurs when
oxidation number of an element increases
element loses electrons
compound adds oxygen
compound loses hydrogen
half-reaction has electrons as products

reduction is the process that occurs when

21-3

oxidation number of an element decreases

element gains electrons
compound loses oxygen
compound gains hydrogen
half-reactions have electrons as reactants

Rules for Assigning an Oxidation Number (O.N.)

General rules
1. For an atom in its elemental form (Na, O 2, Cl2, etc.): O.N. = 0
2. For a monoatomic ion: O.N. = ion charge
3. The sum of O.N. values for the atoms in a compound equals zero. The
sum of O.N. values for the atoms in a polyatomic ion equals the ions charge.
Rules for specific atoms or periodic table groups
1. For Group 1A(1):

O.N. = +1 in all compounds

2. For Group 2A(2):

O.N. = +2 in all compounds

3. For hydrogen:

O.N. = +1 in combination with nonmetals

4. For fluorine:

O.N. = -1 in combination with metals and boron

5. For oxygen:

O.N. = -1 in peroxides
O.N. = -2 in all other compounds(except with F)
O.N. = -1 in combination with metals, nonmetals
(except O), and other halogens lower in the group

6. For Group 7A(17):

21-4

Highest and lowest

oxidation numbers of
reactive main-group
elements.

21-5

Sample Problem 4.6

PROBLEM:

PLAN:

Determining the Oxidation Number of an Element

Determine the oxidation number (O.N.) of each element in these

compounds:
(a) zinc chloride (b) sulfur trioxide (c) nitric acid

The O.N.s of the ions in a polyatomic ion add up to the charge of the
ion and the O.N.s of the ions in the compound add up to zero.

SOLUTION:
(a) ZnCl2. The O.N. for zinc is +2 and that for chloride is -1.
(b) SO3. Each oxygen is an oxide with an O.N. of -2. Therefore the
O.N. of sulfur must be +6.
(c) HNO3. H has an O.N. of +1 and each oxygen is -2. Therefore
the N must have an O.N. of +5.

21-6

A summary of terminology for

oxidation-reduction (redox) reactions.
e-

21-7

transfer
Y
or shift of
electrons

X loses electron(s)

Y gains electron(s)

X is oxidized

Y is reduced

X is the reducing agent

Y is the oxidizing agent

X increases its
oxidation number

Y decreases its
oxidation number

OPRA

Sample Problem 4.7

Recognizing Oxidizing and Reducing Agents

PROBLEM: Identify the oxidizing agent and reducing agent in each of the following:
(a) 2Al(s) + 3H2SO4(aq)

Al2(SO4)3(aq) + 3H2(g)

(b) PbO(s) + CO(g)

(c) 2H2(g) + O2(g)

Pb(s) + CO2(g)
2H2O(g)

PLAN: Assign an O.N. for each atom and see which atom gained and which atom
lost electrons in going from reactants to products.
An increase in O.N. means the species was oxidized (and is the
reducing agent) and a decrease in O.N. means the species was reduced
(is the oxidizing agent).
SOLUTION:

+1 +6 -2

(a) 2Al(s) + 3H2SO4(aq)

+3 +6 -2

Al2(SO4)3(aq) + 3H2(g)

The O.N. of Al increases; it is oxidized; it is the reducing agent.

The O.N. of H decreases; it is reduced; H 2SO4 is the oxidizing agent.

21-8

Sample Problem 4.7

continued

+2 -2

Recognizing Oxidizing and Reducing Agents

+2 -2

(b) PbO(s) + CO(g)

+4 -2

Pb(s) + CO2(g)

The O.N. of C increases; it is oxidized; CO is the reducing agent.

The O.N. of Pb decreases; it is reduced; PbO is the oxidizing agent.
0

(c) 2H2(g) + O2(g)

+1 -2

2H2O(g)

The O.N. of H increases; it is oxidized; it is the reducing agent.

The O.N. of O decreases; it is reduced; it is the oxidizing agent.

21-9

A redox titration.

21-10

Sample Problem 4.9

Finding an Unknown Concentration by a Redox

Titration

PROBLEM:

Calcium ion (Ca 2+) is required for blood to clot and for many other
cell processes. An abnormal Ca 2+ concentration is indicative of
disease. To measure the Ca 2+ concentration, 1.00mL of human
blood was treated with Na2C2O4 solution. The resulting CaC 2O4
precipitate was filtered and dissolved in dilute H 2SO4. This solution
required 2.05mL of 4.88x10 -4M KMnO4 to reach the end point. The
unbalanced equation is
KMnO4(aq) + CaC2O4(s) + H2SO4(aq)
MnSO4(aq) + K2SO4(aq) + CaSO4(s) + CO2(g) + H2O(l)
(a) Calculate the amount (mol) of Ca 2+.
(b) Calculate the amount (mol) of Ca 2+ ion concentration expressed
in units of mg Ca2+/100mL blood.

PLAN:
(a)

volume of KMnO4 soln

multiply by M
mol of KMnO4

mol of CaC2O4
molar ratio

21-11

mol of Ca2+
ratio of elements in formula

Sample Problem 4.9

Finding an Unknown Concentration by a Redox

Titration

2KMnO4(aq) + 5CaC2O4(s) + 8H2SO4(aq)

2MnSO4(aq) + K2SO4(aq) + 5CaSO4(s) + 10CO2(g) + 8H2O(l)
continued
2.05mL soln

SOLUTION:
L
4.88x10-4mol KMnO4
103 mL

1.00x10-6mol KMnO4

= 1.00x10-6mol KMnO4

L
5mol CaC2O4

= 2.50x10-6 mol CaC2O4

2mol KMnO4
2.50x10-6 mol CaC2O4
PLAN:
(b)

= 2.50x10-6 mol Ca2+

1mol CaC2O4
mol Ca /1mL blood
SOLUTION:
multiply by 100
2.50x10-6 mol Ca2+ x100 =2.50x10-4 mol Ca2+
1mL blood
100mL blood
mol Ca2+/100mL blood
2+

multiply by M
g Ca2+/100mL blood
10-3g = 1mg

21-12

1mol Ca2+

mg Ca2+/100mL blood

2.50x10-4 mol Ca2+ 40.08g Ca2+

100mL blood
mol Ca2+

mg
10-3g

=10.0mg Ca2+/100mL blood

A summary of redox terminology.

Zn(s) + 2H+(aq)

Zn2+(aq) + H2(g)

OXIDATION
One reactant loses electrons.

Zn loses electrons.

Reducing agent is oxidized.

Zn is the reducing
agent and becomes
oxidized.

Oxidation number increases.

The oxidation number

of Zn increases from
x to +2.

REDUCTION
Other reactant gains
electrons.
Oxidizing agent is reduced.

Hydrogen ion gains

electrons.
Hydrogen ion is the oxidizing agent
and becomes reduced.

Oxidation number decreases. The oxidation number of H

decreases from +1 to 0.

21-13

Half-Reaction Method for Balancing Redox Reactions

Summary: This method divides the overall redox reaction into
oxidation and reduction half-reactions.
Each reaction is balanced for mass (atoms) and charge.
One or both are multiplied by some integer to make the number of
electrons gained and lost equal.
The half-reactions are then recombined to give the balanced redox
equation.

Advantages:
The separation of half-reactions reflects actual physical
separations in electrochemical cells.
The half-reactions are easier to balance especially if they
involve acid or base.
It is usually not necessary to assign oxidation numbers to
those species not undergoing change.

21-14

1. Identifica reaccin
redox

6. Balancear cargas
con electrones

2. Divide en medias
reacciones

7. Igualar electrones

3. Balancea tomos
diferentes a O y H

8. Sumar las medias

reacciones

5. Balancea H con
H+
21-15

Para balancear en
medio bsico

4. Balancea O con
molculas de agua

9. Aadir OH- por cada H+

10. Cancelar las molculas
de agua que se encuentren
a ambos lados

Balancing Redox Reactions in Acidic Solution

Cr2O72-(aq) + I-(aq)

Cr3+(aq) + I2(aq)

1. Divide the reaction into half-reactions Determine the O.N.s for the species undergoing redox.

+6
-1
2Cr2O7 (aq) + I-(aq)
Cr2O72I-

Cr3+
I2

+3
0
3+
Cr (aq) + I2(aq)
Cr is going from +6 to +3
I is going from -1 to 0

2. Balance atoms and charges in each half-reaction 14H+(aq) + Cr2O72net: +12

6e- + 14H+(aq) + Cr2O72-

21-16

2 Cr3+
net: +6
2 Cr3+

+ 7H2O(l)
Add 6e- to left.
+ 7H2O(l)

Balancing Redox Reactions in Acidic Solution

6e- + 14H+(aq) + Cr2O72-

2 Cr3+

2 I-

I2

continued

+ 7H2O(l)

+ 2e-

Cr(+6) is the oxidizing agent and I(-1) is the reducing agent.

3. Multiply each half-reaction by an integer, if necessary 2 I-

I2 + 2e-

X3

4. Add the half-reactions together 6e- + 14H+ + Cr2O726 I14H+(aq) + Cr2O72-(aq) + 6 I-(aq)

2 Cr3+

3 I2 + 6e2Cr3+(aq) + 3I2(s)

Do a final check on atoms and charges.

21-17

+ 7H2O(l)

+ 7H2O(l)

Balancing Redox Reactions in Basic Solution

Balance the reaction in acid and then add OH - so as to neutralize
the H+ ions.
14H+(aq) + Cr2O72-(aq) + 6 I-(aq)

2Cr3+(aq) + 3I2(s)

+ 14OH-(aq)
14H2O + Cr2O72- + 6 I-

+ 14OH-(aq)
2Cr3+ + 3I2

+ 7H2O + 14OH-

Reconcile the number of water molecules.

7H2O + Cr2O72- + 6 I-

2Cr3+ + 3I2

Do a final check on atoms and charges.

21-18

+ 7H2O(l)

+ 14OH-

Sample Problem 21.1:

PROBLEM:

Balancing Redox Reactions by the Half-Reaction

Method

Permanganate ion is a strong oxidizing agent, and its deep purple

color makes it useful as an indicator in redox titrations. It reacts in
basic solution with the oxalate ion to form carbonate ion and solid
mangaese dioxide. Balance the skeleton ionic reaction that occurs
between NaMnO4 and Na2C2O4 in basic solution:
MnO4-(aq) + C2O42-(aq)

PLAN:

MnO2(s) + CO32-(aq)

Proceed in acidic solution and then neutralize with base.

SOLUTION:
MnO4+7
MnO44H+ + MnO4+3e-

21-19

MnO2
+4
MnO2
MnO2 + 2H2O

C2O42+3
C2O42C2O42- + 2H2O

CO32+4
2CO322CO32- + 4H+
+2e-

Sample Problem 21.1:

Balancing Redox Reactions by the Half-Reaction

Method

continued:
4H+ + MnO4- +3e-

MnO2+ 2H2O

C2O42- + 2H2O

2CO32- + 4H+ + 2e-

4H+ + MnO4- +3e-

MnO2+ 2H2O

C2O42- + 2H2O

2CO32- + 4H+ + 2eX3

X2
8H+ + 2MnO4- +6e-

2MnO2+ 4H2O
8H+ + 2MnO4- +6e-

2MnO2+ 4H2O

3C2O42- + 6H2O

6CO32- + 12H+ + 6e-

2MnO2-(aq) + 3C2O42-(aq) + 2H2O(l)

+ 4OH2MnO2-(aq) + 3C2O42-(aq) + 4OH-(aq)

21-20

3C2O42- + 6H2O

6CO32- + 12H+ + 6e-

2MnO2(s) + 6CO32-(aq) + 4H+(aq)

+ 4OH2MnO2(s) + 6CO32-(aq) + 2H2O(l)

Electrochemical Cells

electrochemistry is the study of redox reactions

that produce or require an electric current
the conversion between chemical energy and
electrical energy is carried out in an
electrochemical cell
spontaneous redox reactions take place in a
voltaic cell
aka galvanic cells

nonspontaneous redox reactions can be made to

occur in an electrolytic cell by the addition of
electrical energy
21-21

Electrochemical Cells
oxidation and reduction reactions kept separate
half-cells

electron flow through a wire along with ion flow

through a solution constitutes an electric circuit
requires a conductive solid (metal or graphite)
electrode to allow the transfer of electrons
through external circuit

ion exchange between the two halves of the system

electrolyte

21-22

General characteristics of voltaic and electrolytic cells.

VOLTAIC CELL
System
Energydoes
is released
work on
from
its
spontaneous
surroundings
redox reaction

Oxidation half-reaction
X
X+ + e-

21-23

ELECTROLYTIC CELL
Surroundings(power
Energy is absorbed tosupply)
drive a
nonspontaneous
redox reaction
do work on system(cell)

Oxidation half-reaction
AA + e-

Reduction half-reaction
Y++ e- Y

Reduction half-reaction
B++ eB

Overall (cell) reaction

X + Y+
X+ + Y; G < 0

Overall (cell) reaction

A- + B+
A + B; G > 0

Aniones a Anodo y Cationes a Catodo

The spontaneous reaction between zinc and copper(II) ion.

Zn(s) + Cu2+(aq)

21-24

Zn2+(aq) + Cu(s)

A voltaic cell based on the zinc-copper reaction.

Oxidation half-reaction
Zn(s)
Zn2+(aq) + 2e-

Reduction half-reaction
Cu2+(aq) + 2eCu(s)
Overall (cell) reaction
Zn(s) + Cu2+(aq)
Zn2+(aq) + Cu(s)

The system generate electrical energy if the half reactions are

21-25 physically seperated and connected by an external circuit

A voltaic cell using inactive electrodes.

Oxidation half-reaction
2I-(aq)
I2(s) + 2e-

Reduction half-reaction
MnO4-(aq) + 8H+(aq) + 5eMn2+(aq) + 4H2O(l)

Inactive electrodes:
electrodes they
conduct
electrons into or out the
half-cells
but cannot take part in the
half-reaction.
Most commonly are
graphite (C) or
platinum (Pt)
Overall (cell) reaction
2MnO4-(aq) + 16H+(aq) + 10I-(aq)
2Mn2+(aq) + 5I2(s) + 8H2O(l)

21-26

Features in the diagram

Components of the half-cells: electrode materials,
electrolyte ions, and other substances involved in the
reaction
Electrode name (anode and cathode) and charge.
Each half-reaction with its half-cell and the overall
cell reaction
Direction of the electron flow in the external circuit
Nature of ions and direction of ion flow in the salt
bridge.
21-27

Cell Notation
shorthand description of Voltaic cell
electrode | electrolyte || electrolyte | electrode
oxidation half-cell on left, reduction half-cell on
the right
single | = phase barrier
if multiple electrolytes in same phase, a comma is
used rather than |
often use an inert electrode

double line || = salt bridge

21-28

Tro, Chemistry: A Molecular Approach

28

Notation for a Voltaic Cell

components of
anode compartment

components of
cathode compartment

(oxidation half-cell)

(reduction half-cell)

phase of lower phase of higher

oxidation state oxidation state

phase of higher
oxidation state

phase of lower
oxidation state

phase boundary between half-cells

Examples:

Zn(s) | Zn2+(aq) (1 M) || Cu2+(aq) (1M) | Cu (s)

Zn(s)

Zn2+(aq) + 2e-

Cu2+(aq) + 2e-

Cu(s)

graphite | I-(aq) | I2(s) || H+(aq), MnO4-(aq), Mn2+(aq) | graphite

inert electrode

21-29

Sample Problem 21.2:

PROBLEM:

PLAN:

Diagramming Voltaic Cells

Diagram, show balanced equations, and write the notation for a

voltaic cell that consists of one half-cell with a Cr bar in a Cr(NO 3)3
solution, another half-cell with an Ag bar in an AgNO 3 solution, and
a KNO3 salt bridge. Measurement indicates that the Cr electrode is
negative relative to the Ag electrode.

Identify the oxidation and reduction reactions and write each halfreaction. Associate the (-)(Cr) pole with the anode (oxidation) and
the (+) pole with the cathode (reduction).

SOLUTION:

Voltmeter

e-

salt bridge

Oxidation half-reaction
Cr(s)
Cr3+(aq) + 3e-

Cr

Ag

NO3-

Reduction half-reaction
Ag+(aq) + eAg(s)

Cr3+

Ag+

Overall (cell) reaction

Cr(s) + 3Ag+(aq)
Cr3+(aq) + 3Ag(s)

21-30

Cr(s) | Cr3+(aq) || Ag+(aq) | Ag(s)

Current and Voltage

the number of electrons that flow through the system per
second is the current

unit = Ampere
1 A of current = 1 Coulomb of charge flowing by each second
1 A = 6.242 x 1018 electrons/second
Electrode surface area dictates the number of electrons that can
flow

the difference in potential energy between the reactants

and products is the potential difference

21-31

unit = Volt
1 V of force = 1 J of energy/Coulomb of charge
the voltage needed to drive electrons through the external circuit
amount of force pushing the electrons through the wire is called
the electromotive force, emf

Cell Potential

the difference in potential energy between the

anode the cathode in a voltaic cell is called the
cell potential
the cell potential depends on the relative ease
with which the oxidizing agent is reduced at the
cathode and the reducing agent is oxidized at the
anode
the cell potential under standard conditions is
called the standard emf, Ecell
25C, 1 atm for gases, 1 M concentration of solution
sum of the cell potentials for the half-reactions
21-32

Standard Cell Potentials

Standard cell potential (E ocell)- the potential measured at
specified temperature (usually 298 K) with no current
flowing and all components in their standard states: 1
atm for gases, 1 M for solutions, the pure solid for
electrodes.
Standard Electrode (Half-cell) Potential (E ohalf-cell) is
the potential associated with a given half-reaction
when all the components are in their standard states.
By convention, a standard electrode potential always
refers to the half-reaction written as a reduction.
reduction
21-33

Zn(s) | Zn2+(aq) (1 M) || Cu2+(aq) (1M) | Cu (s)

Zn2+(aq) + 2eCu2+(aq) + 2e-

Zn(s)
Cu2+(aq) + 2eCu2+(aq) + Zn(s)

Zn(s)
Cu(s)

Eozinc (Eoanode)
Eocopper (Eocathode)

Zn2+(aq) + 2eCu(s)
Cu(s) + Zn2+(aq)

The standard cell potential is the difference between the

standard electrode potential of the cathode (reduction) halfcell and the standard electrode potential of the anode
(oxidation) half-cell:
Eocell = Eocathode 21-34

Eoanode

Determining an unknown E 0half-cell with the standard reference

(hydrogen) electrode.

Oxidation half-reaction
Zn(s) Zn2+(aq) + 2e-

Overall (cell) reaction

Zn(s) + 2H3O+(aq) Zn2+(aq) + H2(g) + 2H2O(l)

21-35

0.76

= 0.00 -

Reduction half-reaction
2H3O+(aq) + 2eH2(g) + 2H2O(l)

E0hydrogen = 0.00V

Eoanode

Sample Problem 21.3:

PROBLEM:

Calculating an Unknown E 0half-cell from E0cell

A voltaic cell houses the reaction between aqueous bromine and

zinc metal:
Br2(aq) + Zn(s)
Zn2+(aq) + 2Br-(aq)
E0cell = 1.83V

Calculate E0bromine given E0zinc = -0.76V

PLAN:

The reaction is spontaneous as written since the E 0cell is (+). Zinc is

being oxidized and is the anode. Therefore the E 0bromine can be found
using E0cell = E0cathode - E0anode.

SOLUTION:

anode: Zn(s)

Zn2+(aq) + 2e-

E0Zn as Zn2+(aq) + 2e-

E = +0.76
Zn(s) is -0.76V

E0cell = E0cathode - E0anode = 1.83 = E0bromine - (-0.76)

E0bromine = 1.86 - 0.76 = 1.07 V

21-36

Relative Strengths of Oxidizing and

Reducing Agents
The more positive the Eo value, the more readily
the reaction (as written) occurs.
A strong oxidizing agent forms a weak reducing
agent, and vice versa

21-37

Selected Standard Electrode Potentials (298K)

Half-Reaction

+2.87
+1.36
+1.23
+0.96
+0.80
+0.77
+0.40
+0.34
0.00
-0.23
-0.44
-0.83
-2.71
-3.05

strength of reducing agent

strength of oxidizing agent

21-38

F2(g) + 2e-
2F-(aq)
Cl2(g) + 2e- 2Cl-(aq)
MnO2(g) + 4H+(aq) + 2e- Mn2+(aq) + 2H2O(l)
NO3-(aq) + 4H+(aq) + 3e- NO(g) + 2H2O(l)
Ag+(aq) + e- Ag(s)
Fe3+(g) + e- Fe2+(aq)
O2(g) + 2H2O(l) + 4e- 4OH-(aq)
Cu2+(aq) + 2e- Cu(s)
2H+(aq) + 2e- H2(g)
N2(g) + 5H+(aq) + 4e- N2H5+(aq)
Fe2+(aq) + 2e- Fe(s)
2H2O(l) + 2e- H2(g) + 2OH-(aq)
Na+(aq) + e- Na(s)
Li+(aq) + e- Li(s)

E0(V)

Writing Spontaneous Redox Reactions

By convention, electrode potentials are written as

reductions.
When pairing two half-cells, you must reverse one
reduction half-cell to produce an oxidation half-cell.

The reduction half-cell potential and the oxidation

half-cell potential are substituted to obtain the E0cell.
Eocell = Eocathode - Eoanode
21-39

When writing a spontaneous redox reaction, the

left side (reactants) must contain the stronger
oxidizing and reducing agents.
Changing the balancing coefficients of a halfreaction does not change its Eo value
Example:

Zn(s)

Cu2+(aq)

stronger
stronger oxidizing
reducing agent
agent

21-40

Zn2+(aq)

+ Cu(s)

weaker oxidizing weaker reducing

agent
agent

Sample Problem 21.4: Writing Spontaneous Redox Reactions and Ranking

Oxidizing and Reducing Agents by Strength
PROBLEM: (a) Combine the following three half-reactions into three balanced
equations (A, B, and C) for spontaneous reactions, and calculate
E0cell for each.
(b) Rank the relative strengths of the oxidizing and reducing agents:
(1) NO3-(aq) + 4H+(aq) + 3e(2) N2(g) + 5H+(aq) + 4e(3) MnO2(s) +4H+(aq) + 2ePLAN:

NO(g) + 2H2O(l)
N2H5+(aq)
Mn2+(aq) + 2H2O(l)

E0 = 0.96V
E0 = -0.23V
E0 = 1.23V

Put the equations together in varying combinations so as to produce

(+) E0cell for the combination. Since the reactions are written as
reductions, remember that as you reverse one reaction for an
oxidation, reverse the sign of E 0. Balance the number of electrons
gained and lost without changing the E 0.
In ranking the strengths, compare the combinations in terms of E 0cell.

21-41

Sample Problem 21.4: Writing Spontaneous Redox Reactions and Ranking

Oxidizing and Reducing Agents by Strength
continued (2 of 4)
SOLUTION:
(a)

(1) NO3-(aq) + 4H+(aq) + 3e-

Rev (2) N2H5+(aq)

N2(g) + 5H+(aq) + 4e-

(1) NO3 (aq) + 4H (aq) + 3e

-

(2) N2H5+(aq)
(A)

(B) 2NO(g) + 3MnO2(s) + 4H+(aq)

21-42

X4

E0cell = 1.19V

X3

4NO(g) + 3N2(g) + 8H2O(l)

E0 = -0.96V

Mn2+(aq) + 2H2O(l)

NO3-(aq) + 4H+(aq) + 3e-

(3) MnO2(s) +4H+(aq) + 2e-

E0 = 0.96V
E0 = +0.23V

NO3-(aq) + 4H+(aq) + 3e-

(3) MnO2(s) +4H+(aq) + 2e(1) NO(g) + 2H2O(l)

NO(g) + 2H2O(l)

N2(g) + 5H+(aq) + 4e-

4NO3-(aq) + 3N2H5+(aq) + H+(aq)

Rev (1) NO(g) + 2H2O(l)

NO(g) + 2H2O(l)

Mn2+(aq) + 2H2O(l)

E0 = 1.23V
X2

E0cell = 0.27V

X3

2NO3-(aq) + 3Mn3+(aq) + 2H2O(l)

Sample Problem 21.4: Writing Spontaneous Redox Reactions and Ranking

Oxidizing and Reducing Agents by Strength
continued (3 of 4)
Rev (2) N2H5+(aq)

N2(g) + 5H+(aq) + 4e-

(3) MnO2(s) +4H+(aq) + 2e(2) N2H5+(aq)

E0 = +0.23V

Mn2+(aq) + 2H2O(l)

E0 = 1.23V
E0cell = 1.46V

N2(g) + 5H+(aq) + 4e-

(3) MnO2(s) +4H+(aq) + 2e(C) N2H5+(aq) + 2MnO2(s) + 3H+(aq)

Mn2+(aq) + 2H2O(l)

X2

N2(g) + 2Mn2+(aq) + 4H2O(l)

(b) Ranking oxidizing and reducing agents within each equation:

(A): oxidizing agents: NO 3- > N2

reducing agents: N2H5+ > NO

(B): oxidizing agents: MnO 2 > NO3-

reducing agents: NO > Mn2+

(C): oxidizing agents: MnO 2 > N2

reducing agents: N2H5+ > Mn2+

21-43

Sample Problem 21.4: Writing Spontaneous Redox Reactions and Ranking

Oxidizing and Reducing Agents by Strength
continued (4 of 4)
A comparison of the relative strengths of oxidizing and reducing
agents produces the overall ranking of
Oxidizing agents: MnO 2 > NO3- > N2
Reducing agents: N2H5+ > NO > Mn2+

21-44

G = -wmax = charge x (-Ecell)

G = -n F Ecell
In the standard state -

G0 = -n F E0cell
G0 = - RT ln K
E0cell = RT ln K
nF
21-45

The interrelationship of G0, E0, and K.

G0

G0 = -nFEocell

G0

E0cell

Reaction at
standard-state
conditions

<0

>1

>0

spontaneous

at equilibrium

>0

<1

<0

nonspontaneous

G0 = -RT lnK
By substituting standard state
values into E0cell, we get
E0cell

21-46

E0cell = -RT lnK

nF

E0cell = (0.0592 V)
n

log K (at 298 K)

Sample Problem 21.5:

PROBLEM:

Calculating K and G0 from E0cell

Lead can displace silver from solution:

Pb(s) + 2Ag+(aq)
Pb2+(aq) + 2Ag(s)
As a consequence, silver is a valuable by-product in the industrial extraction
of lead from its ore. Calculate K and G0 at 298 K for this reaction.
PLAN: Break the reaction into half-reactions, find the E 0 for each half-reaction
and then the E0cell. Substitute into the equations found on slide
SOLUTION:

2X
E0cell =
log K =

21-47

Pb2+(aq) + 2eAg+(aq) + e-

Pb(s)
Ag(s)

E0 = -0.13V
E0 = 0.80V

Pb(s)
Pb2+(aq) + 2eAg+(aq) + eAg(s)

0.0592V
n
n x E0cell

log K

0.0592V

(2)(0.93V)
0.0592V

E0 = 0.13V
E0 = 0.80V
E0cell = 0.93V

G0 = -nFE0cell = -(2)(96.5kJ/mol*V)(0.93V)
K = 2.6x1031

G0 = -1.8x102kJ/mol rxn

The Effect of Concentration on Cell Potential:

Nernst Equation

G = G0 + RT ln Q
-nF Ecell = -nF Ecell + RT ln Q
Ecell = E

cell

RT
nF

ln Q

0.0592
Ecell = E cell n
0

21-48

log Q

Electrolytic cells
Electrical energy from an external source drives
a non-spontaneous reaction.
A non-spontaneous reaction occurs by
supplying from an external source an electric
potential greater than Eocell

21-49

The tin-copper reaction as the basis of a voltaic and an electrolytic cell.

voltaic cell
Oxidation half-reaction
Sn(s) Sn2+(aq) + 2eReduction half-reaction
Cu2+(aq) + 2eCu(s)
Overall (cell) reaction
Sn(s) + Cu2+(aq) Sn2+(aq) + Cu(s)

21-50

electrolytic cell
Oxidation half-reaction
Cu(s)
Cu2+(aq) + 2eReduction half-reaction
Sn2+(aq) + 2eSn(s)
Overall (cell) reaction
Sn(s) + Cu2+(aq) Sn2+(aq) + Cu(s)

Comparison of Voltaic and Electrolytic Cells

Electrode
Cell Type

Ecell

Name

Process

Sign

Voltaic

<0

>0

Anode

Oxidation

Voltaic

<0

>0

Cathode

Reduction

Electrolytic

>0

<0

Anode

Oxidation

Electrolytic

>0

<0

Cathode

Reduction

21-51

The electrolysis of water.

Electrolysis the
splitting of a
substance by the
input of electrical
energy, is often used
to decompose a
compound into its
elements.

Reduction half-reaction
2H2O(l) + 4e2H2(g) + 2OH-(aq)

21-52

Overall (cell) reaction

2H2O(l)
H2(g) + O2(g)

Oxidation half-reaction
2H2O(l) 4H+(aq) + O2(g) + 4e-

Electrolysis of pure molten salts

The cation will be reduced amd the anion
oxidized.
2 Cl- (l) --> Cl2(g) + 2e- [anode, oxidation]
Ca2+ (l) + 2 e- --> Ca(s) [cathode, reduction]
Ca2+ (l) + 2 Cl- (l) --> Cl2(g) + Ca(s)

21-53

Electrolysis of Mixed Molten Salts

The more easily oxidized species (stronger reducing
agent) reacts at the anode, and the more easily reduced
species (stronger oxidizing agent) reacts at the cathode.
We cannot use tabulated E o values. We rely on our
knowledge of periodic atomic trends to predict which
of the ions present gains or loses electrons more easily.

21-54

Sample Problem 21.8:

PROBLEM:

Predicting the Electrolysis Products of a Molten

Salt Mixture

A chemical engineer melts a naturally occurring mixture of NaBr

and MgCl2 and decomposes it in an electrolytic cell. Predict the
substance formed at each electrode, and write balanced halfreactions and the overall cell reaction.

PLAN:
Consider the metal and nonmetal components of each compound and
then determine which will recover electrons(be reduced; strength as an oxidizing
agent) better. This is the converse to which of the elements will lose electrons
more easily (lower ionization energy).
SOLUTION: Possible oxidizing agents: Na +, Mg2+
Possible reducing agents: Br -, ClNa, the element, is to the left of Mg in the periodic table, therefore the IE of Mg
is higher than that of Na. So Mg2+ will more easily gain electrons and is the
stronger oxidizing agent.
Br, as an element, has a lower IE than does Cl, and therefore will give up
electrons as Br- more easily than will Cl -.
Mg2+(l) + 2Br-(l)
cathode

21-55

anode

Mg(s) + Br2(g)

Electrolysis of Aqueous Solutions

Complicated by more than one possible oxidation and reduction
possible cathode reactions
reduction of cation to metal
reduction of water to H 2
2 H2O + 2 e-1 H2 + 2 OH-1
E = -0.83 v @ stand. cond.
E = -0.41 v @ pH 7
possible anode reactions
oxidation of anion to element
oxidation of H 2O to O2
2 H2O O2 + 4e-1 + 4H+1
E = -1.23 v @ stand. cond.
E = -0.82 v @ pH 7
oxidation of electrode
particularly Cu
graphite doesnt oxidize

half-reactions with the least negative, or more positive, half-cell

potential.
unless overvoltage changes the conditions

21-56

Electrolysis of NaI(aq)
with Inert Electrodes
possible oxidations
2 I-1 I2 + 2 e-1
E = 0.54 v
2 H2O O2 + 4e-1 + 4H+1 E = 0.82 v
possible reductions
Na+1 + 1e-1 Na0
E = 2.71 v
2 H2O + 2 e-1 H2 + 2 OH-1 E = 0.41 v

overall reaction
2 I(aq) + 2 H2O(l) I2(aq) + H2(g) + 2 OH-1(aq)
21-57

Stochiometry of Electrolysis
Faraday's law of electrolysis the amount of substance
produced at each electrode is directly proportional to the
quantity of charge flowing through the cell.

How much material will form as a result of a given

quantity of charge?
How much charge is needed to produce a given
amount of material?
21-58

To apply Faraday's Law

Balance the half-reaction to find the number of
moles of electrons needed per mole of product.
Use the Faraday constant (F = 9.65 x 104 C/mol e-)
to find corresponding charge.
Use molar mass to find the charge needed for a
given mass of product.
21-59

 Charge cannot be measure directly.

Current is related with charge. Current unit is
ampere (A) 1 ampere = 1 coulomb/second
Current x time = charge

21-60

A summary diagram for the stoichiometry of electrolysis.

MASS (g)
of substance
oxidized or
reduced

AMOUNT (MOL)
of substance
oxidized or
reduced

M(g/mol)

How long does it take to produce

3.0 g of Cl2(g) by electrolysis of
aqueous NaCl using power supply
with a current of 12 A?
2 Cl-(ac)
CURRENT (A)

21-61

balanced
half-reaction

AMOUNT (MOL)
of electrons
transferred

Cl2(g) + 2etime(s)

Faraday
constant
(C/mol e-)
CHARGE (C)

Sample Problem 21.10:

PROBLEM:

PLAN:

Applying the Relationship Among Current, Time,

and Amount of Substance

A technician is plating a faucet with 0.86 g of Cr from an electrolytic

bath containing aqueous Cr2(SO4)3. If 12.5 min is allowed for the
plating, what current is needed?

mass of Cr needed

SOLUTION:

Cr3+(aq) + 3e-

Cr(s)

divide by M
mol of Cr needed
3mol e-/mol Cr
mol of e- transferred

0.86g (mol Cr) (3 mol e-)

= 0.050 mol e-

(52.00 gCr) (mol Cr)

0.050 mol e- (9.65x104 C/mol e-) = 4.8x103 C

9.65x104C/mol echarge (C)

divide by time
current (A)

21-62

4.8x103 C

(min)

12.5 min

(60s)

= 6.4C/s = 6.4 A

Ejercicios
El nmero de oxidacin de fsforo en fosfato de
aluminio AlPO4
El nmero de oxidacin de nitrgeno en N2O4
El nmero de oxidacin de azufre en S2O82 El nmero de oxidacin de oro en AuBr2
El nmero de oxidacin de arsnico en H 3AsO3

21-63

Ejercicios
Balancea en medio cido
Cr2O72-(aq) + C2O42-(aq)

Cr 3+(aq) + CO2(g)

MnO4-(aq) + Br -(aq)

MnO2(s) + BrO3-(aq)

I2(s) + OCl-(aq)
Mn(s) + HNO3(aq)

21-64

IO3-(aq) + Cl-(aq)
Mn2+(aq) + NO2(g)

Ejercicios

Balance la siguiente reaccin redox que toma lugar

en un solucin acdica. Identifica el agente oxidante y
reductor.
FeO42- (aq) + Ti2+ (aq) Fe3+ (aq) + TiO2 (s)

Balance la siguiente reaccin redox que toma lugar en

un solucin bsica. Identifica el agente oxidante y
reductor.
SeO42- (aq) + S2O42- (aq) SeO3 2- (aq) + SO32- (aq)
21-65

Ejercicios

Una celda electroqumica es construda de una media celda de

con alambre de plata que es colocado en 1.00 M de una
solucin acuosa de AgNO3 y la otra media celda consiste de un
electrodo de cinc en una solucin de 1.00 M de Zn(NO 3)2
tambin.
Escribe la ecuacin balanceada para la reaccin espontnea
que ocurre en una celda bajo estas condiciones.
Cul es el Eo de la celda?
Cul es la K y el Go de la celda?
Escribe esta celda en notacin lineal
Cul es el E de la celda a 25.0 oC cuando la [Ag+] = 0.50 m
y [Zn2+] = 1.00 M?

21-66

Ejercicios
Determina el potencial de reaccin para lo
siguiente:
Oxidacin: Cu(s) --> Cu2+(ac, 0.010M) + 2e Reduccin: MnO4-(ac, 2.0M) + 4 H+(ac, 1M) +3e- -->
MnO2 (s) + 2 H2O(l)

21-67

Respuestas
5+, 4+, 7+, 2+, 3+
Cr2O72-(aq) + 3 C2O42-(aq) + 14 H+ (aq) 2 Cr3+(aq) + 6 CO2(g) + 7 H2O (l)
2 MnO4-(aq) + Br-(aq) + 2 H+ (aq) 2 MnO2(s) + BrO3-(aq) + H2O (l)
2 I2(s) + 5 OCl-(aq) + H2O (l) 4 IO3-(aq) + 5 Cl-(aq) + 2 H+ (aq)
Mn(s) + 2 HNO3(aq) + 2 H+ (aq) Mn2+(aq) + 2 NO2(g) + 2 H2O (l)
2 FeO42- (aq) + 3 Ti2+ (aq) + 4 H+ (aq) 2 Fe3+ (aq) + 3 TiO2 (s) + 2 H2O (l) ; AO FeO42- , AR - Ti2+
SeO42- (aq) + S2O42- (aq) + 2 OH- (aq) SeO3 2- (aq) + 2 SO32- (aq) + H2O (l) ; AO
SeO42- , AR - S2O42-

,1.56V, 5.0 x 1052, 3.01 x 105 J, ZnZn2+Ag+Ag, 1.54V

1.36 V
21-68

Sample Problem 21.7:

PROBLEM:

PLAN:

Calculating the Potential of a Concentration Cell

A concentration cell consists of two Ag/Ag + half-cells. In half-cell A,

electrode A dips into 0.0100M AgNO 3; in half-cell B, electrode B
dips into 4.0x10 -4M AgNO3. What is the cell potential at 298 K?
Which electrode has a positive charge?

E0cell will be zero since the half-cell potentials are equal. E cell is
calculated from the Nernst equation with half-cell A (higher [Ag +])
having Ag+ being reduced and plating out, and in half-cell B Ag(s)
will be oxidized to Ag+.

SOLUTION: Ag+(aq, 0.010M) half-cell A

Ecell = E0cell -

0.0592V
1

log

Ag +(aq, 4.0x10-4M) half-cell B

[Ag+]dilute
[Ag+]concentrated

Ecell = 0 V -0.0592 log 4.0x10 -2

= 0.0828V

Half-cell A is the cathode and has the positive electrode.

21-69

A concentration cell based on the Cu/Cu 2+ half-reaction.

Oxidation half-reaction
Cu(s)
Cu2+(aq, 0.1M) + 2e-

Reduction half-reaction
Cu2+(aq, 1.0M) + 2eCu(s)

Overall (cell) reaction

Cu2+(aq,1.0M)
Cu2+(aq, 0.1M)

21-70

When Q < 1 and thus [reactant] > [product], ln Q < 0, so

Ecell > E0cell

When Q = 1 and thus [reactant] = [product], ln Q = 0, so

Ecell = E0cell

When Q >1 and thus [reactant] < [product], ln Q > 0, so

Ecell < E0cell

21-71

Sample Problem 21.6:

Using the Nernst Equation to Calculate E cell

PROBLEM: In a test of a new reference electrode, a chemist constructs a

voltaic cell consisting of a Zn/Zn 2+ half-cell and an H2/H+ half-cell under the
following conditions:
[Zn2+] = 0.010M
[H+] = 2.5M
P H = 0.30atm
2

Calculate Ecell at 298 K.

PLAN: Find E0cell and Q in order to use the Nernst equation.
SOLUTION: Determining E 0cell :
2H+(aq) + 2e-

H2(g)

E0 = 0.00V

Zn2+(aq) + 2e-

Zn(s)

E0 = -0.76V

Zn2+(aq) + 2e-

E0 = +0.76V

Zn(s)
Ecell = E0cell -

0.0592V
n

log Q

Ecell = 0.76 - (0.0592/2)log(4.8x10 -4) =

21-72

Q=

P x [Zn2+]
H2

[H+]2
Q=

(0.30)(0.010)
(2.5)2

Q = 4.8x10-4
0.86V

The laboratory measurement of pH.

Pt
Glass
electrode

Reference
(calomel)
electrode

Hg
Paste of
Hg2Cl2 in
Hg
AgCl on
Ag on Pt
1M HCl

Thin glass
membrane

21-73

KCl
solution

Porous ceramic
plugs

Some Ions Measured with Ion-Specific Electrodes

21-74

Species Detected

Typical Sample

NH3/NH4+

Industrial wastewater, seawater

CO2/HCO3-

Blood, groundwater

F-

Drinking water, urine, soil, industrial stack gases

Br-

Grain, plant tissue

I-

Milk, pharmaceuticals

NO3-

Soil, fertilizer, drinking water

K+

Blood serum, soil, wine

H+

Laboratory solutions, soil, natural waters

Alkaline Battery

21-75

Mercury and Silver (Button) Batteries

21-76

Lithium battery.

21-77

Lead-acid battery.

21-78

Figure 21.17

21-79

Nickel-metal hydride (Ni-MH) battery

Figure 21.18

21-80

Lithium-ion battery.

Figure 21.19

21-81

Fuel cell.

Figure 21.20

21-82

The corrosion of iron.

Figure 21.21

21-83

Enhanced corrosion at sea.

Figure 21.22

The effect of metal-metal contact on the corrosion of iron.

faster corrosion

21-84

cathodic protection

Figure 21.23

The use of sacrificial anodes to prevent iron corrosion.

21-85

Sample Problem 4.8

Balancing Redox Equations by the Oxidation

Number Method

PROBLEM: Use the oxidation number method to balance the following equations:
(a) Cu(s) + HNO3(aq)
(b) PbS(s) + O2(g)
SOLUTION:

+1 +5 -2

(a) Cu(s) + HNO3(aq)

Cu(NO3)2(aq) + NO2(g) + H2O(l)

PbO(s) + SO2(g)
+2 +5 -2

+4 -2

+1 -2

Cu(NO3)2(aq) + NO2(g) + H2O(l)

O.N. of Cu increases because it loses 2e -; it is oxidized and is the reducing agent.

O.N. of N decreases because it gains1e-; it is reduced and is the oxidizing agent.
loses 2eCu(s) + HNO3(aq)

balance other ions

Cu(NO3)2(aq) + NO2(g) + H2O(l)
gains 1e-

x2 to balance e-

balance unchanged polyatomic ions

21-86

Sample Problem 4.8

Balancing Redox Equations by the Oxidation

Number Method

continued
Cu(s) + 4
2 HNO3(aq)

Cu(NO3)2(aq) + 2NO2(g) + 2H2O(l)

2
+2 -2

(b) PbS(s) + O2(g)

+2 -2

+4 -2

PbO(s) + SO2(g)

loses 6ePbS(s) + 3/2 O2(g)

PbO(s) + SO2(g)

gains 2e- per O; need 3/2 O2 to make 3O2total of a 6e- exchange

Multiply by 2 to have whole number coefficients.
2PbS(s) + 3O2(g)

21-87

2PbO(s) + 2SO2(g)