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SCE

SCE 3109
3109
Energetics
Energetics in
in Chemistry
Chemistry

Electrochemistry
Course Textbooks

• Brown, T.L., Lemay, H.E. & Bursten, B.E. (2006).


Chemistry –The Central Science. 10th ed. New
Jersey: Prentice Hall.

• McMurry, J. & Fay, R.C. (2008). Chemistry. 4th ed.


New Jersey: Prentice Hall.

Additional reference:
http://www.wwnorton.com/college/chemistry/gilbert/overview/ch17.htm
Redox reactions
• Electrochemistry is the branch of chemistry that deal with
the interconversion of electrical energy and chemical
energy.

• Electrochemical processes are redox (oxidation-


reduction) reactions.

• In redox reactions, electrons are transferred from one


species to another.
Oxidation is loss of electrons.
Reduction is gain of electrons.

• Oxidation and reduction must occur together.


Redox reactions

Oxidation Numbers

In order to keep track of


what loses electrons
and what gains them,
we assign oxidation
numbers.
Redox reactions

Oxidation and Reduction

• A species is oxidized when it loses electrons.


– Here, zinc loses two electrons to go from neutral
zinc metal to the Zn2+ ion.
• A species is reduced when it gains electrons.
– Here, each of the H+ gains an electron and they
combine to form H2.
Redox reactions

Oxidation and Reduction

• What is reduced is the oxidizing agent.


– H+ oxidizes Zn by taking electrons from it.

• What is oxidized is the reducing agent.


– Zn reduces H+ by giving it electrons.
Redox reactions

Half Reactions

• Although oxidation and reduction must take place


simultaneously, it is often convenient to consider them
as separate processes.
Redox reactions

Half Reactions
• Oxidation Half-Reaction: Zn(s) → Zn2+(aq) + 2 e–
• The Zn loses two electrons to form Zn 2+ .
Redox reactions

Half Reactions
• Reduction Half-Reaction: Cu2+(aq) + 2 e– → Cu(s)
• The Cu2+ gains two electrons to form copper.
Redox reactions

Overall: Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)


Redox reactions

Balancing Redox Equations by Methods of Half-


Reaction
• The easiest way to balance the equation of an
oxidation-reduction reaction is via the half-reaction
method.
• This involves treating the oxidation and reduction as
two separate processes, balancing these half
reactions, and then combining them to attain the
balanced equation for the overall reaction.
Redox reactions
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)

Oxidation half-reaction:

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

Reduction half-reaction:

Cu2+(aq) + 2e- Cu(s)


Redox reactions

Half-Reaction Method

1. Assign oxidation numbers to determine what is


oxidized and what is reduced.

2. Write the oxidation and reduction half-reactions.

3. Balance each half-reaction.


a) Balance elements other than H and O.
b) Balance O by adding H2O.
c) Balance H by adding H+.
d) Balance charge by adding electrons.
Redox reactions

Half-Reaction Method

4. Multiply the half-reactions by integers so that the


electrons gained and lost are the same.

5. Add the half-reactions, subtracting things that appear


on both sides.

6. Make sure the equation is balanced according to mass.

7. Make sure the equation is balanced according to


charge.
Redox reactions

Half-Reaction Method

Consider the reaction between MnO4− and C2O42− :

MnO4−(aq) + C2O42−(aq)  Mn2+(aq) + CO2(aq)


Redox reactions

Half-Reaction Method

First, we assign oxidation numbers.

+7 +3 +2 +4

MnO4− + C2O42-  Mn2+ + CO2

Since the manganese goes from +7 to +2, it is reduced.

Since the carbon goes from +3 to +4, it is oxidized.


Redox reactions

Half-Reaction Method

Oxidation Half-Reaction

C2O42−  CO2


To balance the carbon, we add a coefficient of 2:

C2O42−  2 CO2


The oxygen is now balanced as well.
To balance the charge, we must add 2 electrons to the right
side.
C2O42−  2 CO2 + 2 e−
Redox reactions

Half-Reaction Method

Reduction Half-Reaction

MnO4−  Mn2+

The manganese is balanced; to balance the oxygen, we


must add 4 waters to the right side.

MnO4−  Mn2+ + 4 H2O

To balance the hydrogen, we add 8 H+ to the left side.

8 H+ + MnO4−  Mn2+ + 4 H2O


Redox reactions

Half-Reaction Method

Reduction Half-Reaction

8 H+ + MnO4−  Mn2+ + 4 H2O

To balance the charge, we add 5 e− to the left side.

5 e− + 8 H+ + MnO4−  Mn2+ + 4 H2O


Redox reactions

Half-Reaction Method

Combining the Half-Reaction

C2O42−  2 CO2 + 2 e− x5


5 e− + 8 H+ + MnO4−  Mn2+ + 4 H2O x2
Redox reactions

Half-Reaction Method

Combining the Half-Reaction

5 C2O42−  10 CO2 + 10 e−


10 e− + 16 H+ + 2 MnO4−  2 Mn2+ + 8 H2O

16 H+ + 2 MnO4− + 5 C2O42−  2 Mn2+ + 8 H2O + 10 CO2


Redox reactions

Half-Reaction Method

Balancing Redox Equations in Acidic Solution

Complete and balance the following equations using the


method of half-reaction.

a) Cr2O72− (aq) + Cl− (aq) Cr3+ (aq) + Cl2 (g)


b) Cu (s) + NO3− (aq)  Cu2+ (aq) + NO2 (g)
c) Mn2+ (aq) + NaBiO3 (s)  Bi3+ (aq) + MnO4− (aq)
Redox reactions

Half-Reaction Method

Balancing Redox Equations in Basic Solution

• If a reaction occurs in basic solution, we can balance it as


if it occurred in acid.

• Once the equation is balanced, add OH− to each side to


“neutralize”the H+ in the equation and create water in its
place.

• If this produces water on both sides, we have to subtract


water from each side.
EXAMPLE: Brown (Pg: 854)
Voltaic Cells
• In spontaneous oxidation-
reduction (redox) reactions,
electrons are transferred and
energy is released.

• We can use that energy to do


work if we make the electrons
flow through an external
device.

• We call such a setup a voltaic


(or galvanic) cell.
Voltaic Cells
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
Voltaic Cells

• A typical cell looks like


this.

• The oxidation occurs at


the anode.

• The reduction occurs at


the cathode.

• Each of the two


compartments of a
voltaic cell is called a
half-cell.
Voltaic Cells

• Electrons become
available as zinc metal
is oxidized at the anode.

• Then, electrons leave


the anode and flow
through the wire to the
cathode.

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


Voltaic Cells

• As the electrons leave


the anode, the cations
formed dissolve into the
solution in the anode
compartment.

• The zinc electrode


loses mass.

• The concentration of
the Zn2+ solution
increases.
Zn(s) Zn2+(aq) + 2e-
Voltaic Cells

• As the electrons reach


the cathode, cations in
the solution are
attracted to the cathode.

Cu2+(aq) + 2e- Cu(s)


Voltaic Cells

• The electrons are taken


by the cation, and the
neutral metal, Cu, is
deposited on the
cathode.
• The Cu electrode gains
mass.
• The Cu2+ solution
becomes less
concentrated as Cu2+ is
reduced to Cu(s).
Cu2+(aq) + 2e- Cu(s)
Voltaic Cells

• For a voltaic cell to work,


the solutions in the two
half-cells must remain
electrically neutral.
Voltaic Cells

• As Zn is oxidized in the
anode compartment,
Zn2+ ions enter the
solution.

• Thus, there must be


some means for
positive ions to migrate
out of the anode
compartment or for
negative ions to migrate
in to keep the solution
electrically neutral.
Voltaic Cells

• Similarly, the reduction


of Cu2+ at the cathode
removes positive
charges from the
solution, leaving an
excess of negative
charges in that half-cell.

• Thus, positive ions must


migrate into the
compartment or
negative ions must
migrate out.
Voltaic Cells
• Therefore, we use a
porous glass barrier or
a salt bridge to maintain
the electrical neutrality
of the solutions.

• Porous glass barrier


separates the two
compartments, but
allows migration of ions.
Voltaic Cells
• A salt bridge, usually a
U-shaped tube that
contains a salt solution,
such as NaNO3(aq),
whose ions will not
react with other ions in
the cell or with the
electrode materials.

• The salt solution is


often incorporated into
a pasta or gel so that
the salt solution does
not pour out.
Voltaic Cells
• As oxidation and
reduction proceed at
the electrodes, ions
from the salt bridges
migrate to neutralise
charge in the cell
compartment.
– Cations move toward
the cathode.
– Anions move toward
the anode.
Voltaic Cells

• In any voltaic cell the


electrons flow from the
anode through the
external circuit to the
cathode.
• The anode in a voltaic
cell is labeled with a
negative sign and the
cathode with a positive
sign.
Voltaic Cells
Voltaic Cells
Anode half-reaction: Zn(s) Zn2+(aq) + 2e-
Cathode half-reaction: Cu2+(aq) + 2e- Cu(s)

Overall cell reaction: Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)

Shorthand notation for galvanic cell:


Salt bridge
Anode half-cell Cathode half-cell

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

Electron flow
Phase boundary Phase boundary
Example

Write a balanced equation for the overall cell reaction, and


give a brief description of a galvanic cell represented by the
following shorthand notation:

Fe(s) | Fe2+(aq) || Sn2+(aq) | Sn(s)

Solution:

Fe(s) + Sn2+(aq) Fe2+(aq) + Sn(s)


Example

Problem 17.1 (Page 692) (McMurry & Fay)

Design a galvanic cell that uses the redox reaction


2Ag+(aq) + Ni(s) 2Ag(s) + Ni2+(aq)

Identify the anode and cathode half-reactions, and sketch


the experimental setup. Label the anode and cathode,
indicate the direction of electron and ion flow, and identify
the sign of each electrode.
Example

Problem 17.4 (Page 693) (McMurry & Fay)

Consider the following galvanic cell.


Example

Problem 17.4 (Page 693) (McMurry & Fay)


a) Complete the drawing by adding any components
essential for a functioning cell.
b) Label the anode and cathode, and indicate the
direction of ion flow.
c) Write a balanced equation for the cell reaction.
d) Write the shorthand notation for the cell.
Electrochemical Cells

Electrochemical cells are of two basic types:

Galvanic (Voltaic) Cell:


A spontaneous chemical reaction which generates an
electric current.

Electrolytic Cell:
An electric current which drives a nonspontaneous
reaction.
Voltaic Cells

• The redox reaction between Zn


and Cu2+ is spontaneous
regardless of whether they
react directly or in the separate
compartments of a voltaic cell.
Voltaic Cells

• Electrons move through


the external circuit from
zinc anode to the
copper cathode.

• Why do electrons
transfer spontaneously
from Zn anode to Cu
cathode?
Electromotive Force (emf)

• Water only
spontaneously flows
one way in a waterfall.

• Likewise, electrons
only spontaneously
flow one way in a
redox reaction — from
higher to lower
potential energy.
Electromotive Force (emf)
• The potential difference between the anode and cathode
in a cell is called the electromotive force (emf).

• It is also called the cell potential (Ecell) or the cell


voltage.

• The potential difference between the two electrodes of a


voltaic cell provides the driving force that pushes
electrons through the external circuit.

Electromotive Force (emf): The force or electrical potential


that pushes the negatively charged electrons away from the
anode (- electrode) and pulls them toward the cathode (+
electrode).
Electromotive Force (emf)
Cell potential is measured in volts (V).
joule
SI unit of energy
J
1V=1
C

volt
SI unit of electric potential coulomb
Electric charge

1 coulomb is the amount of charge transferred when


a current of 1 ampere flows for 1 second.
Electromotive Force (emf)
• The emf of a paricular voltaic cell depends on the
 specific reaction that occur at the cathode and anode

 the concentrations of reactants and products


 temperature

• Under standard conditions (1 M concentrations for reactants


and products in solution; 1 atm pressure for those that are gases;
solids and liquids in pure form), the emf is called the
standard emf, or the standard cell potential, and is
denoted Eocell.
Standard Cell Potentials
• For the following Zn-Cu voltaic cell, the standard cell
potential at 25°C is +1.10 V.

Zn(s) + Cu2+(aq, 1 M) Zn2+(aq, 1 M) + Cu(s)  = +1.10 V


Ecell

For any cell reaction that


proceeds spontaneously,
such as that in a voltaic
cell, the cell potential will
be positive.
Standard Cell Potentials
• The emf or cell potential of a voltaic cell depends on the
particular cathode and anode half-cells involved.

• The standard cell potential


Ecell  (cathode) − Ered
= Ered  (anode)
Standard Reduction Potentials

Standard
reduction
potentials for
many
electrodes
have been
measured and
tabulated.
Standard Hydrogen Electrode

• The standard reduction potentials (often called half-cell


potentials) are determined from the difference between
two electrodes.

• The reference point is called the standard hydrogen


electrode (S.H.E.) and consists of a platinum electrode in
contact with H2 gas (1 atm) and aqueous H+ ions (1 M).

• The standard hydrogen electrode is assigned an arbitrary


value of exactly 0.00 V.
Standard Reduction Potentials
The standard hydrogen electrode (S.H.E.) has been
chosen to be the reference electrode.
E°cell = 0.34 V
Standard Reduction Potentials
Anode half-reaction: H2(g) 2H1+(aq) + 2e-
Cathode half-reaction: Cu2+(aq) + 2e- Cu(s)

Overall cell reaction: H2(g) + Cu2+(aq) 2H1+(aq) + Cu(s)


Ecell  (cathode) − Ered
= Ered  (anode)

0.34 V = E°red (cathode) ― 0 V

A standard reduction potential can be defined:

Cu2+(aq) + 2e- Cu(s) E°red = 0.34 V


Standard Reduction Potentials
Standard Reduction Potentials

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


Cathode half-reaction: 2H1+(aq) + 2e- H2(g)

Overall cell reaction: 2H1+(aq) + Zn(s) H2(g) + Zn2+(aq)


Ecell  (cathode) − Ered
= Ered  (anode)

0.76 V = 0 V ― Eored (anode)

Eored (anode) = - 0.76 V

As a standard reduction potential:

Zn2+(aq) + 2e- Zn(s) Eored = -0.76 V


Using Standard Cell Potentials

The cell potential at standard conditions can be found


through this equation:


Ecell  (cathode) − Ered
= Ered  (anode)
Using Standard Cell Potentials
• For the oxidation in this cell,

 = −0.76 V
Ered

• For the reduction,

Ered = +0.34 V

Ecell = Ered (cathode) − Ered (anode)


= +0.34 V − (−0.76 V) = +1.10 V
Using Standard Cell Potentials

• When selecting two half-cell reactions the more negative


value will form the oxidation half-cell (anode).
• Consider the reaction between zinc and silver:
Ag+(aq) + e– → Ag(s) E°= 0.80 V
Zn2+(aq) + 2 e– → Zn(s) E°= –0.76 V
• Therefore, zinc forms the oxidation half-cell (anode).

Ecell = Ered (cathode) − Ered (anode)


= +0.80 V − (−0.76 V) = +1.56 V
Using Standard Cell Potentials

Example
• Using data in Appendix E, calculate the standard emf for
a cell that employs the following overall cell reaction:

2Al(s) + 3I2(s) 2Al3+(aq) + 6I― (aq)

Ecell = Ered (cathode) − Ered (anode)

= +0.536 V − (−1.66 V) = +2.196 V


Using Standard Cell Potentials

Example
• Using data in Appendix E, calculate the standard emf for
a cell that employs the following overall cell reaction:

Cr2O72-(aq) + 14H+ (aq) + 6I―(aq) 2Cr3+(aq) + 3I2 (s) + 7H2O

Ecell = Ered (cathode) − Ered (anode)

= +1.33 V − (0.536 V) = +0.794 V


Using Standard Cell Potentials

Example
• A voltaic cell is based on the half reactions:

In+(aq) In3+(aq) + 2e-


Br2(l) + 2e- 2Br―(aq)

The standard emf for this cell is 1.46 V. Using data in


Appendix E, calculate Eored for the reduction of In3+ to In+.
Ecell = Ered (cathode) − Ered (anode)

1.46 V = +1.065 V − Eored (anode)


Eored (anode) = - 0.395 V
Using Standard Cell Potentials

Example

• A voltaic cell is based on the following two standard


half reactions:
Cd2+(aq) + 2e- Cd(s)
Sn2+(aq) + 2e- Sn(s)
By using data in Appendix E, determine
a) the half-reactions that occur at the cathode and
the anode
b) the standard cell potential.
Using Standard Cell Potentials

Solution:

a) Anode: Cd(s) Cd2+(aq) + 2e-


Cathode: Sn2+(aq) + 2e- Sn(s)

b) Ecell = Ered (cathode) − Ered (anode)

= (- 0.136 V) − (- 0.403 V) = 0.267 V


Using Standard Cell Potentials

Example

• A voltaic cell is based on Co2+/Co half-cell and an


AgCl/Ag half-cell.
a) Write the half-reaction occurs at the anode?
b) What is the standard cell potential?

Answers: (a) Co  Co2+ + 2e-


(b) + 0.499 V
Using Standard Cell Potentials

Zn(s) Zn2+(aq) + 2e- E° = -(-0.76 V)


Cu2+(aq) + 2e- Cu(s) E° = 0.34 V

Zn(s) + Cu2+(aq) Zn2+(g) + Cu(s) E° = 1.10 V

2 x [Ag1+(aq) + e- Ag(s)] E° = 0.80 V


Cu(s) Cu2+(aq) + 2e- E° = -0.34 V

2Ag(s) + Cu2+(aq) 2Ag2+(g) + Cu(s) E° = 0.46 V

Half-cell potentials are intensive properties.


Using Standard Cell Potentials

Example

a) What is the standard emf of an electrochemical cell


made of a Cd electrode in a 1.0 M Cd(NO3)2 solution
and a Cr electrode in a 1.0 M Cr(NO3)3 solution?

b) What is the standard emf of an electrochemical cell


made of a Mg electrode in a 1.0 M Mg(NO3)2 solution
and a Ag electrode in a 1.0 M AgNO3 solution?

Answer: (a) +0.337 V (b) +3.169 V


Using Standard Cell Potentials

Predicting whether a redox reaction is spontaneous

Using the standard reduction potentials listed in Appendix


E, determine whether the following reactions are
spontaneous under standard conditions.
(a) Cu(s) + 2H+(aq) Cu2+(aq) + H2(g)
(b) Cu2+(aq) + H2(g) Cu(s) + 2H+(aq)

(c) Cl2(g) + 2I-(aq) 2Cl-(aq) + I2(s)


Using Standard Cell Potentials

Solution: (a) Cu(s) + 2H+(aq) Cu2+(aq) + H2(g)

In this reaction, Cu is oxidized to Cu2+ and H+ is reduced to


H2 .

Reduction: 2H+(aq) + 2e- H2(g) Eored = 0 V

Oxidation: Cu(s) Cu2+(aq) + 2e- Eored = +0.34 V

E  = Ered (cathode) − Ered (anode)


= 0 V − (0.34 V) = -0.34 V
Because EO is negative, the reaction is not spontaneous in the
direction written.
Using Standard Cell Potentials

Solution: (b) Cu2+(aq) + H2(g) Cu(s) + 2H+(aq)

In this reaction, H2 is oxidized to H+ and Cu2+ is reduced to


Cu.

Reduction: Cu2+(aq) + 2e- Cu(s) Eored = +0.34 V

Oxidation: H2(g) 2H+(aq) + 2e- Eored = 0 V

E  = Ered (cathode) − Ered (anode)


= 0.34 V − (0 V) = 0.34 V
Because EO is positive, the reaction is spontaneous and could be
used to build a voltaic cell.
Using Standard Cell Potentials

Solution: (c) Cl2(g) + 2I-(aq) 2Cl-(aq) + I2(s)

Reduction: Cl2(g) + 2e- 2Cl-(aq) Eored = +1.36 V

Oxidation: 2I-(aq) I2(s) + 2e- Eored = +0.54 V

E  = Ered (cathode) − Ered (anode)


= 1.36 V − (0.54 V) = +0.82 V
Because EO is positive, the reaction is spontaneous and could be
used to build a voltaic cell.
Using Standard Cell Potentials

Predicting whether a redox reaction is spontaneous

Practice Exercise: Brown (Pg 869)


McMurry & Fay (Pg 701)(Problem 17.8)
Oxidizing and Reducing Agents

• The strongest oxidizers


have the most positive
reduction potentials.

• The strongest reducers


have the most negative
reduction potentials.
Oxidizing and Reducing Agents
Oxidizing and Reducing Agents

Example:

a) Rank the following ions in order of increasing strength


as oxidizing agents: NO3- (aq), Ag+ (aq), Cr2O72- (aq).

Answer: Ag+ < NO3- < Cr2O72-

b) Rank the following species from the strongest to the


weakest reducing agent: I- (aq), Fe (s), Al (s).

Answer: Al (s) > Fe (s) > I- (aq)


Oxidizing and Reducing Agents

Example:

c) Arrange the following oxidizing agents in order of


increasing strength under standard-state conditions:
Br2(aq), Fe3+ (aq), Cr2O72- (aq).

Answer: Fe3+ < Br2 < Cr2O72-

d) Arrange the following reducing agents in order of


increasing strength under standard-state conditions :
Al(s), Na(s), Zn(s).

Answer: Zn < Al < Na


Oxidizing and Reducing Agents

The greater the difference


between the two, the
greater the voltage of the
cell.
Oxidizing and Reducing Agents
Consider the following table of standard reduction potentials:

a) Which substance is the strongest reducing agent? Which is


the strongest oxidizing agent?
b) Which substances can be oxidized by B2+? Which can be
reduced by C?
c) Write a balanced equation for the overall cell reaction that
delivers the highest voltage, and calculate Eo for the reaction.
Oxidizing and Reducing Agents
Answers:

(a) D is the strongest reducing agent.


A3+ is the strongest oxidizing agent.

(b) B2+ can oxidize C and D.


C can reduce A3+ and B2+.

(c) A3+ + 2D  A+ + 2 D+
2.85 V
Free Energy & Redox Reactions

• Two quantitative measures of the tendency for a


chemical reaction to occur:
(a) the cell potential, E (elecrochemical quantity)
(b) the free-energy change, G (themochemical quantity)

• The change in Gibbs free energy, G, is a measure of


the spontaneity of a process that occurs at constant
temperature and pressure.
Free Energy & Redox Reactions

• The relationship between emf, E and the free-energy


change, G is
G = −nFE

where n is the number of moles of electrons transferred,


and F is a constant, the Faraday.

Note:
Faraday’ s constant is the quantity of electrical charge on one
mole of electrons.
1 F = 96,485 C/mol = 96,485 J/V-mol
Free Energy & Redox Reactions

• G for a redox reaction can be found by using the


equation
G = −nFE
If the free-energy change, G, for a reaction is negative,
the reaction is spontaneous.
The greater the negative value of G, the greater the
tendency for the reaction to occur.

The unit of G is J/mol.


Note: A positive value of E and a negative value of G
both indicate that a reaction is spontaneous.
Free Energy & Redox Reactions

For a constant-temperature process:


The change of Gibbs free energy (ΔG)

G = −nFE

G < 0 The reaction is spontaneous in the forward direction.


G > 0 The reaction is nonspontaneous as written. The
reaction is spontaneous in the reverse direction.
G = 0 The reaction is at equilibrium.
Free Energy & Redox Reactions

• Under standard conditions,

G = −nFE
Free Energy & Redox Reactions
The standard cell potential at 25 °C is 1.10 V for the
reaction:
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
Calculate the standard free-energy change for this reaction
at 25 °C.

G° = -nFE°
96,485 J
= -(2) (1.10 V)
V mol

G° = -212267 J/mol = -212.267 kJ/mol


Free Energy & Redox Reactions
Example:
The standard cell potential at 25 °C is 0.92 V for the
reaction:
Al(s) + Cr3+(aq) Al3+(aq) + Cr(s)

What is the standard free-energy change for this reaction at


25 °C?

Answer: -270 kJ/mol


Free Energy & Redox Reactions
Example:
Calculate the standard free-energy change for the following
reaction at 25°C:
3Ca(s) + 2Al3+(1 M) 3Ca2+(1 M) + 2Al(s)

Solution: G° = -nFE° Eo = ?

Answer: 7 x 102 kJ/mol

Comment: The positive value of ΔG° tell us that the reaction is not
spontaneous under standard-state conditions at 25°C.
Cell EMF Under Nonstandard
Conditions
• Suppose we start a reaction in solution with all the
reactants in their standard states (that is, all at 1 M
concentration.

• As soon as the reaction starts, the standard-state


condition no longer exists for the reactants or the
products because their concentrations are different from
1 M.

• Under nonstantard-state conditions, we must use G


rather than G to predict the direction of the reaction.
Cell EMF Under Nonstandard
Conditions
• The relationship between G and G is

G = G°+ RT ln Q

R is the gas constant (8.314 J/K •mol)

T is the absolute temperature (K)

Q is the reaction quotient


Cell EMF Under Nonstandard
Conditions
Example:
The standard free-energy change for the reaction
N2(g) + 3H2(g) 2NH3(g)

is -33.2 kJ/mol at 25°C.

In certain experiment, the initial pressures are PH2 = 0.250


atm, PN2 = 0.870 atm, and PNH3 = 12.9 atm.

Calculate ΔG for the reaction at these pressure, and


predict the direction of reaction?
Cell EMF Under Nonstandard
Conditions
Solution:

G = G°+ RT ln Q
(PNH3)2
= G°+ RT ln
(PH2)3 (PN2)
(12.9)2
= -33.2 x 103 J/mol + (8.314 J/Kmol)(298 K) ln
(0.250)3 (0.870)
= -9.9 x 103 J/mol

= -9.9 kJ/mol

Because ΔG is negative, the net reaction proceed from left to right.


Cell EMF Under Nonstandard
Conditions
• The emf generated under nonstandard conditions can be
calculated by using an equation first derived by Walter
Nernst (1864-1941), a German chemist who established
many of the theoretical foundations of electrochemistry.
Nernst Equation
G = G + RT ln Q

Using: G = -nFE and G° = -nFE°

This mean −nFE = −nFE + RT ln Q

Dividing both sides by −nF, we get the Nernst equation:


RT
E = E − nF ln Q

or, using base-10 logarithms,

2.303 RT
E = E − nF log Q
Nernst Equation

At room temperature (298 K),

2.303 RT
F = 0.0592 V

Thus the equation becomes

0.0592
E = E − n log Q
Nernst Equation
Example
Consider a galvanic cell that uses the reaction:

Cu(s) + 2Fe3+(aq) Cu2+(aq) + 2Fe2+(aq)

What is the potential of a cell at 25 °C that has the


following ion concentrations?

[Fe3+] = 1.0 x 10-4 M [Cu2+] = 0.25 M [Fe2+] = 0.20 M


Nernst Equation
Solution
0.0592 V
E = E° - log Q
n

Calculate E°:

Cu(s) Cu2+(aq) + 2e- Eored = 0.34 V


Fe3+(aq) + e- Fe2+(aq) Eored = 0.77 V

E°cell = 0.77 V –(0.34 V) = 0.43 V


Nernst Equation
Solution
0.0592 V
E = E° - log Q
n
Calculate E:
0.0592 V [Cu2+][Fe2+]2
E = Eo - log
n [Fe3+]2

0.0592 V (0.25)(0.20)2
= 0.43 V - log
2 (1.0 x 10-4)2

E = 0.25 V
Nernst Equation
Example
Calculate the emf at 298 K generated by the cell:
Cr2O72- (aq) + 14H+(aq) + 6I-(aq) 2Cr3+(aq) + 3I2(s) + 7H2O(l)

when [Cr2O72- ] = 2.0 M, [H+] = 1.0 M, [I-] = 1.0 M, [Cr3+] =


1.0 x 10-5 M.

Answer: E = 0.89 V
Nernst Equation
Why the emf of a voltaic cell drops as the cell discharges?
Consider the following reaction:

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

The standard cell potential


at 25 °C is 1.10 V.
E°cell = 1.10 V
Nernst Equation
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)

As the voltaic cell is discharged, the reactants are


consumed and the products are generated, so the
concentrations of these substances change.
The emf produced under non-standard conditions at 298
K:
0.0592 V
E = E° - log Q
n
0.0592 V [Zn2+]
= 1.10 V - log
2 [Cu2+]
Nernst Equation
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)

0.0592 V [Zn2+]
E = 1.10 V - log
2 [Cu2+]

As the cell operates, the concentration of reactant (Cu2+)


decreases and the concentration of product (Zn2+)
increases relative to standard conditions.
Thus, the emf decreases.

For example, when [Cu2+] is 0.05 M and [Zn2+] is 2.0 M,

E = 1.05 V
Nernst Equation
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)

0.0592 V [Zn2+]
E = 1.10 V - log
2 [Cu2+]

As reactants are converted to products, the value of E


decreases, eventually reaching E = 0 (the cell is “dead”).
Because G = −nFE, it follows that G = 0 when E = 0.

Recall thet a system is at equilibrium when G = 0.


Thus, when E = 0, the cell reaction has reached
equilibrium and no net reaction is occurring.
Concentration Cells
EXAMPLE

• Calculate the emf of the following concentration cell:


Ni(s) | Ni2+(0.001 M) || Ni2+(1.00 M) | Ni(s)

Anode: Ni(s) Ni2+(0.001 M) + 2e-


Cathode: Ni2+(1.00 M) + 2e- Ni(s)

Overall: Ni2+(1.00 M) Ni2+(0.001 M)


Ecell  (cathode) − Ered
= Ered  (anode)
= -0.28 V –(-0.28 V) = 0 V
Concentration Cells
Overall: Ni2+(1.00 M) Ni2+(0.001 M)

0.0592 V 0.001
E=0- log
n 1.00

= 0 –(- 0.0888) = +0.0888 V

The concentration cell generates an emf of 0.0888 V even


though E°= 0.
The difference in concentration provides the driving force
for the cell.
Concentration Cells

• The Nernst equation implies that a cell could be created


that has the same substance at both electrodes.

• For such a cell, Ecell would be 0, but Q would not.
• Therefore, as long as the concentrations are
different, E will not be 0.
• When the concentrations in the two compartments become
the same, the value of Q = 1 and E = 0.
Equilibrium Constants

RT
G = G + RT ln Q E = E − nF ln Q

At Equilibrium At Equilibrium

G = 0 Q=K E=0 Q=K

0 = G0 + RT lnK RT
0 = E − nF ln K
G0 =  RT lnK
RT
E°= ln K
nF
Equilibrium Constants

G0 =  RT lnK
Equilibrium Constants

Three methods to determine equilibrium constants:


[C]c[D]d
1. K from concentration data: K=
[A]a[B]b

-G°
2. K from thermochemical data: ln K =
RT

RT
3. K from electrochemical data: E°= ln K
nF
or
nFE°
ln K =
RT
Equilibrium Constants
Equilibrium Constants

Example:

The equilibrium constant for the reaction


Sr(s) + Mg2+(aq) Sr2+ (aq) + Mg (s)
is 2.69 x 1012 at 25°C. Calculate E° for a cell made up of
Sr/Sr2+ and Mg/Mg2+ half-cells.

Solution: RT
E°= ln K
nF

Answer: 0.368 V
Equilibrium Constants

Example:

Calculate equilibrium constant for the following reaction at


25°C:
Sn(s) + 2Cu2+(aq) Sn2+ (aq) + 2Cu+ (aq)

Solution: RT
E°= ln K Eo ?
nF

Answer: 6.5 x 109


Equilibrium Constants

Example:

Calculate ΔGo for the following process at 25°C:


AgCl (s) Ag+ (aq) + Cl- (aq)
The Ksp of silver chloride is 1.6 x 10-10.
Equilibrium Constants

Solution:

Ksp = [Ag+][Cl-] = 1.6 x 10-10

Go =  RT lnK

Go =  (8.314 J/Kmol)(298 K) ln 1.6 x 10-10


= 5.6 x 10-4 J/mol
= 56 kJ/mol
Equilibrium Constants

Example:

Calculate ΔG o and Kc for the following reaction at 25°C:


Mg(s) + Pb2+(aq) Mg2+(aq) + Pb(s)

Answer: -432 kJ/mol, 5 x 1075


Applications of Oxidation-
Reduction Reactions
Batteries
Batteries, which consist of one or more voltaic cells, are
used widely as self-contained power sources.
Batteries
Lead Storage Battery
Batteries
Lead Storage Battery
Anode: Pb(s) + HSO41-(aq) PbSO4(s) + H1+(aq) + 2e-

Cathode: PbO2(s) + 3H1+(aq) + HSO41-(aq) + 2e- PbSO4(s) + 2H2O(l)

Overall: Pb(s) + PbO2(s) + 2H1+(aq) + 2HSO41-(aq) 2PbSO4(s) + 2H2O(l)


Batteries
Lead Storage Battery

Because the reaction product, solid PbSO4, adheres to


the surface of the electrodes, a “run-down”lead storage
battery can be recharged by using an external sources of
direct current to drive the cell reaction in the reverse,
nonspontsneous direction.

In an automobile, the battery is continuously recharged by


a device called an alternator, which is driven by the
engine.
Batteries
Lead Storage Battery

A lead storage battery typically provides good service for


several years, but eventually the spongy PbSO4 deposits
on the electrodes turn into hard, crystalline form that can’
t
be converted back to Pb and PbO2.

Then it’
s n longer possible to recharge the battery, and it
must be replaced.
Batteries
Dry-Cell Batteries
Leclanchécell
Batteries
Dry-Cell Batteries
Leclanchécell
Anode: Zn(s) Zn2+(aq) + 2e-

Cathode: 2MnO2(s) + 2NH41+(aq) + 2e- Mn2O3(s) + 2NH3(aq)+ H2O(l)


Batteries
Dry-Cell Batteries
Alkaline cell
Anode: Zn(s) + 2OH1-(aq) ZnO(s) + H2O(l) + 2e-
Cathode: 2MnO2(s) + H2O(l) + 2e- Mn2O3(s) + 2OH1-(aq)

The alkaline dry cell is a modified version of the Leclanchécell in


which the acidic NH4Cl electrolyte of the Leclanchécell is
replaced by a basic electrolyte, either NaOH or KOH.
Batteries
Alkaline Batteries
Batteries
Dry-Cell Batteries

Corrosion of the zinc anode is a significant side reaction


under acidic conditions because zinc reacts with H+(aq) to
give Zn2+(aq) and H2(g).

Under basic conditions, however, the cell has a longer life


because zinc corrodes more slowly.
Batteries

Mercury Batteries
Batteries
Nickel-Cadmium (“ni-cad”) Batteries
Anode: Cd(s) + 2OH1-(aq) Cd(OH)2(s) + 2e-
Cathode: NiO(OH)(s) + H2O(l) + e- Ni(OH)2(s) + OH1-(aq)
Batteries
Nickel-Metal Hydride (“NiMH”) Batteries
Anode: MHab(s) + OH1-(aq) M(s) + H2O(l) + e-
Cathode: NiO(OH)(s) + H2O(l) + e- Ni(OH)2(s) + OH1-(aq)

Overall: MHab(s) + NiO(OH)(s) M(s) + Ni(OH)2(s)


Batteries
Lithium and Lithium Ion Batteries
Lithium
Anode: xLi(s) xLi1+(soln) + xe-
Cathode: MnO2(s) + xLi1+(soln) + xe- LixMnO2(s)

Lithium Ion

Anode: LixC6(s) xLi1+(soln) + 6C(s) + xe-


Cathode: Li1-xCoO2(s) + xLi1+(soln) + xe- LiCoO2(s)
Batteries
Lithium Ion Batteries
Fuel Cells

A fuel cell is a galvanic cell in which one of the reactants


is a fuel such as hydrogen or methanol.

A fuel cell differs from an ordinary battery in that the


reactants are not contained within the cell but instead are
continuously supplied from an external reservoir.
Fuel Cells
Hydrogen-Oxygen Fuel Cell
Fuel Cells
Hydrogen-Oxygen Fuel Cell

Anode: 2H2(g) + 4OH1-(aq) 4H2O(l) + 4e-


Cathode: O2(g) + 2H2O(l) + 4e- 4OH1-(aq)

Overall: 2H2(g) + O2(s) 2H2O(l)


Corrosion
Corrosion
Corrosion
Prevention of Corrosion
• Iron is often covered with a coat of paint or another metal
such as tin, chromium or zinc to protect its surface
against corrosion.
• Covering the surface with paint or tin simply a means of
preventing oxygen and water from reaching the iron
surface.
• If the coating is broken and the iron is exposed to
oxygen and water, corrosion will begin.
• Galvanized iron, which is iron coated with a thin layer of
zinc, uses the principles of electrochemistry to protect
the iron from corrosion even after the surface coat is
broken.
Corrosion
Prevention of Corrosion
1. Galvanization: The coating of iron with zinc.
As the potentials indicate, zinc is oxidized more easily
than iron:
Fe2+(aq) + 2e- Fe(s) E°red = -0.45 V
Zn2+(aq) + 2e- Zn(s) E°red = -0.76 V

When some of the iron is oxidized (rust), the process


would be reversed immediately because zinc can
reduce Fe2+ to Fe.
Corrosion
Prevention of Corrosion
1. Galvanization: The coating of iron with zinc.

As long as the zinc and iron are in contact, the zinc protects the
iron from oxidation even if the zinc layer becomes scratched.
Corrosion
Prevention of Corrosion
2. Cathodic Protection: Instead of coating the entire
surface of the first metal with a second metal, the
second metal is placed in electrical contact with the
first metal:
Anode: Mg(s) Mg2+(aq) + 2e-
Cathode: O2(g) + 4H1+(aq) + 4e- 2H2O(l)

Attaching a magnesium stake to iron will corrode the


magnesium instead of the iron. Magnesium acts as a
sacrificial anode.
Electrochemical Cells

Electrochemical cells are of two basic types:

Galvanic (Voltaic) Cell:


A spontaneous chemical reaction which generates an
electric current.

Electrolytic Cell:
An electric current is used to drives a nonspontaneous
reaction.

The processes occurring in voltaic (galvanic) and


electrolytic cells are the reverse of each other.
Electrolysis and Electrolytic Cells

Electrolysis: The process of using an electric current to


bring about chemical change.
Electrolysis and Electrolytic Cells
Electrolysis of Water
• Water in a beaker under atmospheric
conditions (1 atm and 25°C) will not
spontaneously decompose to form H2 and
O2.

• However, this reaction can be induced in a


electrolytic cell.

• The electrolytic cell consists of a pair of


electrodes made of a non-reactive metal,
such as platinum, immersed in water.
Electrolysis and Electrolytic Cells
Electrolysis of Water
• When the electrodes are connected to the battery,
nothing happens because there are not enough ions in
pure water to carry much of an electric current.
(Remember that at 25°C, pure water has only 1 x 10-7
M OH- ions.)

• The reaction is occurs readily in a 0.1 M H2SO4 solution


because there are a sufficient number of ions to conduct
electricity.
Electrolysis and Electrolytic Cells
Electrolysis of Water
Electrolysis and Electrolytic Cells
Electrolysis of Water
Anode: 2H2O(l) O2(g) + 4H+(aq) + 4e-
Cathode: 4H2O(l) + 4e- 2H2(g) + 4OH-(aq)

Overall: 6H2O(l) 2H2(g) + O2(g) + 4H+(aq) + 4OH-(aq)

If the anode and cathode solutions are mixed, the H+ and


OH- ions react to form water:
4H+ (aq) + 4OH-(aq) 4H2O(l)

The net electrolysis reaction is therefore the decomposition


of water:
2H2O(l) 2H2(g) + O2(g)
Electrolysis and Electrolytic Cells
Electrolysis of Molten Sodium Chloride

Cathode:

The negative electrode attracts Na+ cations, which combine


with the electrons supplied by the battery and are thereby
reduced to liquid sodium metal.
Electrolysis and Electrolytic Cells
Electrolysis of Molten Sodium Chloride

Cathode:

The positive electrode attracts Cl- anions, which replenish


the electrons removed by the battery and are thereby
oxidized to chlorine gas.
Electrolysis and Electrolytic Cells
Electrolysis of Molten Sodium Chloride

Cathode:

The signs of the electrodes are opposite for galvanic and


electrolytic cell.
Electrolysis and Electrolytic Cells
Electrolysis of Molten Sodium Chloride

Anode: 2Cl-(l) Cl2(g) + 2e-


Cathode: 2Na+(l) + 2e- 2Na(l)

Overall: 2Na+(l) + 2Cl-(l) 2Na(l) + Cl2(g)

As in a galvanic cell, the anode is the electrode where


oxidation take place, and the cathode is the electrode
where reduction take place.
Electrolysis and Electrolytic Cells

Example
Metallic potassium was first prepared by Humphrey Davy in
1807 by electrolysis of molten potassium hydroxide:

a) Label the anode and


cathode, and show the
direction of ion flow.
b) Write balanced
equations for the anode,
cathode and overall cell
reactions.
Electrolysis and Electrolytic Cells

Answer:

Cathode Anode
Electrolysis and Electrolytic Cells

Answer:

Anode: 4OH-(l) O2(g) + 2H2O(l) + 4e-


Cathode: 4K+(l) + 4e- 4K(l)

Overall: 4K+(l) + 4OH-(l) 4K(l) + O2(g) + 2H2O(l)


Electrolysis and Electrolytic Cells
Electrolysis of Aqueous Sodium Chloride
• When an aqueous salt solution is electrolyzed, the
electrode reactions may differ from those for electrolysis
of the molten salt because water may be involved.
Electrolysis and Electrolytic Cells
Electrolysis of Aqueous Sodium Chloride
• The anode half-reaction might be:

2Cl-(aq) Cl2(g) + 2e- E°red = 1.36 V

2H2O(l) O2(g) + 4H+(aq) + 4e- E°red = 1.23 V

• Both E°red are not very different, but the values do


suggest that H2O should be preferentially oxidized at the
anode.
• However, by experiment the observed product at the
anode is Cl2 because of a phenomenon called
overvoltage.
Electrolysis and Electrolytic Cells
Electrolysis of Aqueous Sodium Chloride
• In studying electrolytic processes, we sometimes find
that the voltage required for a reaction is always higher
than the electrode potential indicates.
• The additional voltage required is the overvoltage.

• The additional voltage for O2 formation is quite high (can


be as large as 1 V). Therefore, under normal operating
conditions Cl2 gas is actually formed at the anode
instead of O2.
Electrolysis and Electrolytic Cells
Electrolysis of Aqueous Sodium Chloride
• The cathode half-reaction might be:
Na+(aq) + e- Na(s) E°red = -2.71 V

2H2O(l) + 2e- H2(g) + 2OH-(aq) E°red = -0.83 V

Water is reduced preferentially because the standard


reduction potential is much less negative.
Electrolysis and Electrolytic Cells
Electrolysis of Aqueous Sodium Chloride

Anode: 2Cl-(aq) Cl2(g) + 2e- E°red = 1.36 V


Cathode: 2H2O(l) + 2e- H2(g) + 2OH-(aq) E°red = -0.83 V

Overall: 2Cl-(l) + 2H2O(l) Cl2(g) + H2(g) + 2OH-(aq)

• The minimum potential required to force this


nonspontaneous reaction to occur under standard-state
conditions is 2.19 V plus the overvoltage.
• Na+ acts as a spectator ion and is not involved in the
electrode reactions. Thus NaCl solution is converted to
NaOH solution as the electrolysis proceeds.
Electrolysis and Electrolytic Cells
Electrolysis of Aqueous Sodium Chloride

• The useful by-product NaOH can be obtained by


evaporating the aqueous solution at the end of electrolysis.
Electrolysis and Electrolytic Cells

Example
Predict the half-cell reactions that occur when aqueous
solutions of the following salts are electrolyzed in a cell
with inert electrodes. What is the overall cell reaction in
each case?
(a) LiCl (b) CuSO4 (c) K2SO4
Electrolysis and Electrolytic Cells

Answer (a) LiCl


The anode half-reaction might be:

2Cl-(aq) Cl2(g) + 2e- E°red = 1.36 V

2H2O(l) O2(g) + 4H+(aq) + 4e- E°red = 1.23 V

The cathode half-reaction might be:


Li+(aq) + e- Li(s) E°red = -3.05 V

2H2O(l) + 2e- H2(g) + 2OH-(aq) E°red = -0.83 V


Electrolysis and Electrolytic Cells

Answer (a) LiCl

Anode: 2Cl-(aq) Cl2(g) + 2e-


Cathode: 2H2O(l) + 2e- H2(g) + 2OH-(aq)

Overall: 2Cl-(l) + 2H2O(l) Cl2(g) + H2(g) + 2OH-(aq)


Electrolysis and Electrolytic Cells

Answer (b) CuSO4


The anode half-reaction:

2SO42-(aq) S2O82-(aq) + 2e- E°red = 2.01 V

2H2O(l) O2(g) + 4H+(aq) + 4e- E°red = 1.23 V

The cathode half-reaction might be:


Cu2+(aq) + 2e- Cu(s) E°red = +0.34 V

2H2O(l) + 2e- H2(g) + 2OH-(aq) E°red = -0.83 V


Electrolysis and Electrolytic Cells

Answer (b) CuSO4

Anode: 2H2O(l) O2(g) + 4H+(aq) + 4e-


Cathode: Cu2+(aq) + 2e- Cu(s)

Overall: 2Cu2+(aq) + 2H2O(l) 2Cu(s) + O2(g) + 4H+(aq)


Electrolysis and Electrolytic Cells

Answer (c) K2SO4


The anode half-reaction:

2SO42-(aq) S2O82-(aq) + 2e- E°red = 2.01 V

2H2O(l) O2(g) + 4H+(aq) + 4e- E°red = 1.23 V

The cathode half-reaction might be:


K+(aq) + e- K(s) E°red = -2.93 V

2H2O(l) + 2e- H2(g) + 2OH-(aq) E°red = -0.83 V


Electrolysis and Electrolytic Cells

Answer (c) K2SO4

Anode: 2H2O(l) O2(g) + 4H+(aq) + 4e-


Cathode: 2H2O(l) + 2e- H2(g) + 2OH-(aq) x2

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


Electrolysis and Electrolytic Cells

Example
An aqueous solution of Mg(NO3)2 is electrolyzed. What
are the products at the anode and cathode?

Answer:

Anode, O2; Cathode, H2


Electrolysis and Electrolytic Cells

Solution
The anode half-reaction:
• nitrate ions migrate to the anode but because they are
too stable to be oxidised.

2H2O(l) O2(g) + 4H+(aq) + 4e- E°red = 1.23 V

The cathode half-reaction might be:


Mg2+(aq) + 2e- Mg(s) E°red = -2.37 V

2H2O(l) + 2e- H2(g) + 2OH-(aq) E°red = -0.83 V


Electrolysis and Electrolytic Cells

Factors that affects the electrolysis products of an aqueous


ionic solutions:
1. Due to the over-voltage from O2 formation, ions like I-,
Br-, and Cl- are oxidised when compare to water
molecules.

2. Oxoanions like SO42-, CO32-, NO3-, PO43- are not


oxidised by water molecule because the central non-
metal of these oxoanions (eg. S, C, N and P) is
already in its highest oxidation state. Water is oxidised
to O2 and H+.
Commercial Applications of
Electrolysis
Commercial Applications of
Electrolysis
• Extraction of metal (Na, Al)
• Manufacture of chemicals (Cl2, NaOH)
• Purification metal
• Electroplating
• Electroplating plastic
• Anodizing
• Effluent treatment
Commercial Applications of
Electrolysis
Down’s Cell for the Production of Sodium Metal
Commercial Applications of
Electrolysis
Down’s Cell for the Production of Sodium Metal
• Sodium metal is produced commercially in a Downs cell
by electrolysis of a molten mixture of sodium chloride
and calcium chloride.

• The presence of CaCl2 allows the cell to be operated at


a lower temperature because the melting point of the
NaCl-CaCl2 mixture (about 580°C) is depressed well
below that of pure NaCl (801°C).
Commercial Applications of
Electrolysis
Down’s Cell for the Production of Sodium Metal

• The liquid sodium produced at the cylindrical steel


cathode is less dense than the molten salt and thus
floats to the top part of the cell. Where it is drown off into
a suitable container.
Commercial Applications of
Electrolysis
Down’s Cell for the Production of Sodium Metal

• Chlorine gas forms at the graphite anode, which is


separated from the cathode by an iron screen to keep
the highly reactive sodium and chlorine away from each
other.
Commercial Applications of
Electrolysis
Hall-Heroult Process for the Production of Aluminum
Commercial Applications of
Electrolysis
Hall-Heroult Process for the Production of Aluminum
• The Hall-Heroult process involves electrolysis of a
molten mixture of aluminium oxide (Al2O3) and cryolite
(Na3AlF6) at about 1000°C in a cell with graphite
electrodes.

• Electrolysis of pure Al2O3 is impractical because it melts


at a very high temperature (2045°C).
Commercial Applications of
Electrolysis
Hall-Heroult Process for the Production of Aluminum
Commercial Applications of
Electrolysis
A Membrane Cell for Electrolytic Production of Cl2 and NaOH
Commercial Applications of
Electrolysis
Production of Cl2 and NaOH
• Chlorine is used in water and sewage treatment, as a
bleaching agent in manufacturing paper, and in the
manufacture of plastics such as polyvinyl chloride (PVC).

• Sodium hydroxide is employed in making paper, textiles,


soaps and detergents.
Commercial Applications of
Electrolysis
A Membrane Cell for Electrolytic Production of Cl2 and NaOH

A saturated aqueous solution of sodium chloride flows into


the anode compartment, where Cl- is oxidized to Cl2 gas.
Commercial Applications of
Electrolysis
A Membrane Cell for Electrolytic Production of Cl2 and NaOH

Water enters the cathode compartment, where it is


converted to H2 gas OH- ions.
Commercial Applications of
Electrolysis
A Membrane Cell for Electrolytic Production of Cl2 and NaOH

Between the anode and cathode compartments is a special


plastic membrane that is permeable to cations but not to anions
or water.
Commercial Applications of
Electrolysis
A Membrane Cell for Electrolytic Production of Cl2 and NaOH

The membrane keeps the Cl2 and OH- ions apart but allows a
current of Na+ ions to flow into cathode compartment, thus
maintaining electrical neutrality in both compartments.
Commercial Applications of
Electrolysis
A Membrane Cell for Electrolytic Production of Cl2 and NaOH

The Na+ and OH- ions flow out of the cathode compartment as
an aqueous solution of NaOH.
Commercial Applications of
Electrolysis
Electrorefining of copper metal
• The purification of a metal by means of electrolysis is
called electrorefining.

• For example, impure copper obtained from ores is


converted to pure copper in an electrolytic cell that has
impure copper as the anode and pure copper as the
cathode.
Commercial Applications of
Electrolysis
Electrorefining of copper metal
Commercial Applications of
Electrolysis
Electrorefining of copper metal
• At the impure Cu anode:
Copper is oxidized along with more easily oxidized
metallic impurities such as Zn and Fe.
Less easily oxidized impurities such as Ag, Au and Pt fall
to the bottom of the cell as anode mud.

• At the pure Cu cathode:

Cu2+ ions are reduced to pure copper metal.

Less easily reduced metal ions (Zn2+, Fe2+ and so forth)


remain in the solution.
Commercial Applications of
Electrolysis
Electrorefining of copper metal

M(s) M2+(aq) + 2e-


Cu2+(aq) + 2e- Cu(s)
(M = Cu, Zn, Fe)
Commercial Applications of
Electrolysis
Electroreplating
• Closely related to electrorefining is electroplating, the
coating of one metal on the surface of another using
electrolysis.

• For example, steel automobile bumpers are sometimes


plated with chromium to protect them from corrosion,
and silver-plating is commonly used to make items of
fine table service.

• The object to be plated is carefully cleaned and then


set up as the cathode of an electrolytic cell that contains
a solution of ions of the metal to be deposited.
Commercial Applications of
Electrolysis
Electroreplating

Problem 17.21 (McMurry & Fay, page 722)

Sketch an electrolytic cell suitable for electroplating a


silver spoon. Describe the electrodes and the electrolyte,
label the anode and cathode, and indicate the direction
of electron and ion flow. Write balanced equations for
anode and cathode half-reactions. What is the overall
cell reaction?
Commercial Applications of
Electrolysis
Electroplating plastic

• Plastics can be metallized though, through numerous


plating processes.

• The parts must be perfectly clean from any oil, grease


or any plastic injection mold compounds. If the parts
are not cleaned properly, the metal will peel off over
time from the plated plastic part.
Commercial Applications of
Electrolysis
Electroplating plastic

• Then process the plastic part in a very aggressive


chromic/sulfuric acid bath to etch the plastic surface
(make small pits on the surface).

• Then place the plastic part in a palladium chloride bath


to place metal particles in the previous pits made on
the plastic surface.

• After this palladium metal deposition, one can


electroplate the part with copper metal and then
chrome plate or many other various metals such as
nickel or gold.
Commercial Applications of
Electrolysis
Electroplating plastic

• By definition, electroplating requires that an electric


current flow between the part being plated and the
chemical solution.

• If the part is non-conductive then an electric current


cannot flow. How can one plate nonconductive
materials like plastic?
Commercial Applications of
Electrolysis
Electroplating plastic
• The answer is "electroless" plating. It is a way to coat
one metal with another without passing current.
• Electroless plating is applied first to get a conductive
surface, then the electroless plated parts are
electroplated.
In the elecroless plating process, chemical baths are
used to deposit metal coatings but do not need
electricity.
After an electroless coating is produced, a normal
electroplating bath can be used to make the coating
even thicker.
Commercial Applications of
Electrolysis
Electroplating plastic

• Many automotive parts, including grilles and all


manner of decorative trim have been plated plastic.
Commercial Applications of
Electrolysis
Anodizing

• Anodizing is an electrolytic process used to increase


the thickness of the natural oxide layer on the surface
of metal parts.

• The process is called "anodizing" because the part to


be treated forms the anode electrode of an electrical
circuit.
Commercial Applications of
Electrolysis
Anodizing

• Anodizing is an operation performed mainly on


aluminium. The effect is to develop an oxide coating
on the aluminium. Again, this is a conversion coating:
the surface is converted from aluminium to aluminium
oxide.

• Unlike plating, the part to be coated is connected to


the anode - not the cathode.

• The part is immersed in a dilute solution of sulfuric acid,


current is passed, and the part is anodized an oxide
coating forms.
Commercial Applications of
Electrolysis
Anodizing
• The oxide coating is harder and more corrosion
resistant than bare aluminium.
• Some aluminum pots and pans are anodized, and door
and window frames are often anodized.
• The most common anodizing processes, for example
sulfuric acid on aluminium, produce a porous surface
which can accept dyes easily. The number of dye
colors is almost endless; however, the colors produced
tend to vary according to the base alloy.
Commercial Applications of
Electrolysis
Anodizing

These inexpensive decorative carabiners have an anodized


aluminium surface that has been dyed and are made in many
colors.
Commercial Applications of
Electrolysis
Effluent treatment

• Electrolytic effluent treatment is based on the anodic


dissolution of metals, which form their hydroxides, and
the pollutants are removed by sorption (absorption and
adsorption) , coagulation, and other processes
occurring in the space between the electrodes.

Reference: Malkin, V.P. (2003). Industrial Ecology: Electrolytic


Effluent Treatment. Chemical and Petroleum Engineering. 39(1–2):
46-50.
Commercial Applications of
Electrolysis
Effluent treatment

• Basic processes in removing heavy-metal ions by


electrocoagulation from industrial effluents:
– the hydroxides of these metals are formed by the alkali
produced at the cathode, where hydrogen is formed and
excess of hydroxyl ions is formed in the cathode layer;

– the heavy-metal hydroxides coprecipitate with the


coagulant (e.g. iron hydroxides) formed by electrolytic
oxidation of an appropriate anode material (e.g. iron);

– the heavy-metal ions are sorbed on the coagulant.


Quantitative Aspects of
Electrolysis
Quantitative Aspects of
Electrolysis
• The stoichiometry of a half-reaction shows how many
electrons are needed to achieve an electrolytic process.

Na+(aq) + e- Na(s)
(One mole of electrons are required to produce 1 mol of Na from
Na+ .)
Al3+(aq) + 3e- Al(s)
(Three mole of electrons are required to produce 1 mol of Al
from Al3+ .)
Quantitative Aspects of
Electrolysis
• To find out how many moles of electrons pass through a
cell in a particular experiment, we need to measure the
electric current and the time that the current flows.

• The number of coulombs of charges passed through the


cell:
Charge(C) = Current(A) x Time(s)

• Because the charge on 1 mol of electrons is 96,485 C,


the number of moles of electrons passed through the cell
is
Moles of e- = Charge(C) x 1 mol e -

96,485 C
Quantitative Aspects of
Electrolysis

Charge(C) = Current(A) x Time(s)

1 mol e-
Moles of e- = Charge(C) x
96,485 C

Faraday constant
Quantitative Aspects of
Electrolysis
Example

Calculate the mass of aluminium produced in 1.00 h by


the electrolysis of molten AlCl3 if the electrical current is
10.0 A.
Charge(C) = Current(A) x Time(s)
= (10.0 A) x (3600 s) = 3.60 x 104 C

Moles of e- 1 mol e-
= Charge(C) x
96,485 C

= (3.60 x 104 C) 1 mol e-

96,485 C
= 0.373 mol e-
Quantitative Aspects of
Electrolysis
Moles of e- = 0.373 mol e-

Al3+(aq) + 3e- Al(s)


From the half-reaction equation, three mole of electrons are
required to produce 1 mol of Al from Al3+ .
Therefore, 0.373 mole of electrons will produce mol of
Al.

Moles of Al =

Mass of Al = 3.36 g
Quantitative Aspects of
Electrolysis
Example

A constant current of 30.0 A is passed through an


aqueous solution of NaCl for a time of 1.00 h. How many
grams of NaOH and how many liters of Cl2 gas are
produced at STP?

Answer: 12.5 L
Quantitative Aspects of
Electrolysis
• Faraday's 1st Law of Electrolysis - The mass of a
substance altered at an electrode during electrolysis is
directly proportional to the quantity of electric charge
passed through the circuit.

• Faraday's 2nd Law of Electrolysis - For a given


quantity of electricity (electric charge), the mass of an
elemental material altered at an electrode is directly
proportional to the element's equivalent mass. The
equivalent mass of a substance is its molar mass divided
by the number of electrons transferred per ion.
Quantitative Aspects of
Electrolysis
• Faraday's laws can be summarized by

n
where
m is the mass of the substance liberated at an electrode
Q is the total electric charge passed through the substance
F = 96,485 C mol-1 is the Faraday constant
M is the molar mass of the substance
n is the number of electrons transferred per ion
Quantitative Aspects of
Electrolysis

n
• Note that M / n is the same as the equivalent mass of the
substance altered.
• For Faraday's first law, M, F, and n are constants, so that
the larger the value of Q the larger m will be.
• For Faraday's second law, Q, F, and n are constants, so
that the larger the value of M / n (equivalent weight) the
larger m will be.
Quantitative Aspects of
Electrolysis
• In the simple case of constant-current electrolysis, Q = It
leading to

n
Electrical Work

• We have seen that a positive value of E is associated


with a negative value for the free-energy change and,
thus, with a spontaneous process.
• For any spontaneous process, ΔG is a measure of the
maximum useful work, wmax, that can be extracted from
the process:
ΔG = wmax

• Because ΔG = -nFE,
The maximum amount of useful electrical work produced
by a voltaic cell:
wmax = -nFE
Electrical Work

wmax = -nFE

• The cell emf, E is a positive number for a voltaic cell, so


wmax will be a negative number for a voltaic cell.

• The negative value for wmax means that a voltaic cell


does work on its surroudings.
(Remember that work done by a system on its surroundings is
indicated by a negative sign for w.)
Electrical Work

• In an electrolytic cell we use an external source of


energy to bring about a nonspontaneous electrochemical
process.
• In this case, ΔG is positive and Ecell is negative.

• To force the process to occur, we need to apply an


external potential, Eext, which must be larger in
magnitude than Ecell:
Eext > -Ecell

For example, if a nonspontaneous process has Ecell = -0.9 V,


then the external potential Eext must be greater than 0.9 V in
order for the process to occur.
Electrical Work

• When an external potential Eext is applied to a cell, the


surroundings are doing work on the system.

• The work performed in an electrolytic cell:


w = nFEext

Note:
a) The work will be a positive number because the
suroundings are doing work on the system.
b) The quantity n is the number of mole of electrons forced
into the system by the external potential.
c) nF is the total electrical charge supplied to the system by
the external source of electricity.
Electrical Work

• Electrical work can be expressed in energy units of


watts times time.

The watt (W) is a unit of electrical power (that is, the rate of
energy expenditure).
1 W = 1 J/s

Thus, a watt-second is a joule.

• The unit employed by electrical utilities is the kilo-watt-


hour (kWh), which equals 3.6 x 106 J.

3600 s 1 J/s
1 kWh = (1000 W)(1 hr) = 3.6 x 106 J
1 hr 1W
Electrical Work

SUMMARY

• The maximum amount of electrical work produced by a


voltaic cell is given by the product of the total charge
delivered, nF, and the emf, E:

wmax = -nFE

• The work performed in an electrolysis:

w = nFEext

where Eext is the applied external potential.


Electrical Work

EXAMPLE
A voltaic cell is based on the reaction
Sn(s) + I2(s) Sn2+(aq) + 2I-(aq)

Under standard conditions, what is the maximum electrical


work, in joule, that the cell can accomplish if 75.0 g of Sn is
consumed?

wmax = -nFE

Answer: -8.19 x 104 J


Electrical Work

SOLUTION
wmax = -nFE

E = 0.672 V

75.0 g
n= x 2 = 1.26 mol
118.71 g mol
96,485 J
wmax = -nFE = - (1.26 mol) (0.672 V)
V mol
= -8.19 x 104 J

Note: The (-) sign indicates that work is done by the cell.
Electrical Work

EXAMPLE
A voltaic cell is based on the reaction
Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)

Under standard conditions, what is the maximum electrical


work, in joule, that the cell can accomplish if 50.0 g of copper
is plated out?

Answer: -1.67 x 105 J


Electrical Work

EXAMPLE
• Calculate the number of kilowatt-hours of electricity
required to produce 1.0 x 103 kg of aluminium by
electrolysis of Al3+ if the applied voltage is 4.50 V.

w = nFEext

n=? w=?

3.6 x 106 J = 1 kWh

_______ J = ? kWh
Electrical Work

SOLUTION
w = nFEext

(1.0 x 103)(1000) g
n= x3 = 1.1 x 105 mol
27 g/mol
96,485 J
w = nFEext = (1.1 x 105 mol) (4.50 V)
V mol

= 4.82 x 1010 J

4.82 x 1010 J
Kilowatt-hours = x 1 kWh = 1.34 x 104 kWh
3.6 x 106 J
Electrical Work

EXAMPLE
• Calculate the number of kilowatt-hours of electricity
required to produce 1.00 kg of Mg from electrolysis of
molten MgCl2 if the applied emf is 5.00 V.

Answer: 11.0 kWh


Key Concept Summary