ELECTROCHEMISTRY

1
Electrolysis: Learning Outcomes

Electrolyte 1. Use Faradays law to calculate amounts of

conductivity, Faradays products formed, amounts of current passed,
law, time elapsed and oxidation state

2. Describe the differences between

Electrochemical cell,
standard electrode
potential and redox
reaction
electrolytic cell and galvanic cell
3. Recognize oxidation and reduction half
reactions
4. Write half reactions and overall cell
reactions
5. Use standard reduction potential to calculate
the standard cell potential, to identify the
cathode and anode, to predict the spontaneity
of a redox reaction

CHM 3010_Electrochemistry 2
Electrolysis: Learning Outcomes

6. Use Nernst equation to relate

electrode potentials and cell potentials
Nernst equation
to different concentrations and partial
pressures

Application of
electrochemistry in
determination of
equilibrium constant
and Gibbs free energy
7. Relate standard cell potential to the
standard Gibbs free energy change and
the equilibrium constant

CHM 3010_Electrochemistry 3
Electrochemistry
Electrochemistry deals with the chemical changes
produced by electric current & with the production
of electricity by chemical reactions
All electrochemical reactions involve the transfer of
electrons oxidation-reduction reactions (redox
reactions)
In most applications the reacting system contained
in a cell, and an electric current enters or exits by
electrodes

CHM 3010_Electrochemistry 4
Electrochemistry
The two parts of the reaction are physically separated.
The oxidation reaction occurs in one cell.
The reduction reaction occurs in the other cell.

There are two types of electrochemical cells:

1. Electrolytic cells are those in which electrical energy
from an external source causes nonspontaneous
chemical reactions to occur
2. Voltaic or galvanic cells are those in which
spontaneous chemical reactions produces electricity &
supply it to an external circuit

CHM 3010_Electrochemistry 5
Figure 21.3 General characteristics of voltaic and electrolytic cells
VOLTAIC CELL ELECTROLYTIC CELL
System
Energydoes
is released
work onfrom
its Surroundings(power
Energy is absorbed tosupply)
drive a
spontaneous
surroundings
redox reaction nonspontaneous redox reaction
do work on system(cell)

Oxidation half-reaction Oxidation half-reaction

X X+ + e- A- A + e-
Reduction half-reaction Reduction half-reaction
Y++ e- Y B++ e- B
Overall (cell) reaction Overall (cell) reaction
X + Y+ X+ + Y; DG < 0 A- + B+ A + B; DG > 0

CHM 3010_Electrochemistry 6
Electrical Conduction
Electric current represents transfer of charge

Charge can be conducted through metals & through

pure liquid electrolytes (i.e. molten salts) or
solutions containing electrolytes

Metals conduct electric currents well in a process

called metallic conduction.
Involves the electron flow with no atomic motion
& no obvious changes in the metal

CHM 3010_Electrochemistry 7
Electrical Conduction
In ionic or electrolytic conduction conduction by
the motion of ions through a solution or a pure liquid
(ionic motion transports the electrons)
Positively charged ions (cations) move toward the
negative electrode
Negatively charged ions (anions) move toward the
positive electrode

Both ionic & metallic conductions occur in

electrochemical cells

CHM 3010_Electrochemistry 8
Electrodes
Electrodes are surfaces on which oxidation or
reduction half-reactions occur

They may or may not participate in the reactions

Electrodes that do not react with the liquids or

products of the electrochemical reactions are called
inert electrodes

Two examples of common inert electrodes are graphite

and platinum.

CHM 3010_Electrochemistry 9
Electrodes
The following identification for electrodes is correct
for either electrolytic or voltaic cells:

The cathode is the electrode at which reduction

occurs as electrons are gained by some species (CR)
The cathode is negative in electrolytic cells and
positive in voltaic cells.

The anode is the electrode at which oxidation

occurs as electrons are lost by some species (AO)
The anode is positive in electrolytic cells and
negative in voltaic cells.

CHM 3010_Electrochemistry 10
 Electrochemical process
When a metal is immersed in a solution containing its ion an
equilibrium exists.
M(s) M+(aq) + e
Oxidation and reduction occur on the electrode surface where
electron is transferred to or from the electrode.
Electrical neutrality of every component of the cell must be
maintained, therefore:

+ + +
i. - -

ii. When oxidation occurs on one electrode,

reduction must occur on the other

Anode electrode where oxidation occurs

Cathode electrode where reduction occurs

CHM 3010_Electrochemistry 11
 Voltaic or galvanic cell
A cell where electrical current is generated from spontaneous chemical
reaction on the electrode surface in the solution.

Zn

1 hour
CuSO4

Spontaneous chemical reaction occurs

Cu2+ + Zn Cu + Zn2+
Energy is produced in form of heat (wasted) and cannot be benefited
or used.

CHM 3010_Electrochemistry 12
Figure 21.4 The spontaneous reaction between zinc and copper(II) ion

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

CHM 3010_Electrochemistry 13
Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
 Electrochemical cell
An electrochemical cell consists of at least two electrodes
connected by a wire and an electrolyte.

Galvano/voltmeter
G Connection
wire
electrodes

electrolyte

CHM 3010_Electrochemistry 14
Voltaic or Galvanic Cells
Voltaic or galvanic cells are electrochemical cells in which a
spontaneous (product-favored) chemical redox reactions
produce electrical energy.
The two halves of the redox reaction are separated,
requiring electron transfer to occur through an external
circuit useful electrical energy is obtained
electrons (from redox reaction) are forced to travel through wires
and creating a potential difference
Examples of voltaic cells include:
Automobile batteries
Flashlights batteries
Computer & calculator batteries

CHM 3010_Electrochemistry 15
A Galvanic Cell: The Copper - Silver Cell

CHM 3010_Electrochemistry 16
 Zn-Cu cell
Daniel cell 2 part of the cell are separated and are connected by wire.

Zn Cu Salt bridge
Zn Cu
ZnSO4
ZnSO4 CuSO4

CuSO4
Porous pot

Zn metal is oxidised to Zn2+ while Cu2+ in the solution is reduced to Cu.

Zn electrode Zn Zn2+ + 2e [O] anode
Cu electrode Cu2+ + 2e Cu [R] cathode
Electron is continuously taken from Cu thus become +ve electrode and
given to Zn thus become ve electrode.
Electron flows from Zn (-ve) to Cu (+ve) giving electric current
(energy).

CHM 3010_Electrochemistry 17
The Construction of Simple Voltaic Cells
Salt bridge
allows the movement of ions to keep the solutions neutral
A tube filled with a solution composed of a salt of ions not
involved in the cell reaction saturated salt/5% agar solution
(sets to the consistency of firm gelatin)
Common salt solutions: KNO3 or KCl
Porous plugs are fitted at each end prevents the salt solution
from pouring out but at the same time allows ion exchanges
with the solutions in half-cells

CHM 3010_Electrochemistry 18
The Construction of Simple Voltaic Cells
Salt bridge serves 3 functions:
Allows electrical contact between the two solutions
Prevents mixing of the electrode solutions
Maintains the electrical neutrality in each half-cell as
ions flow into & out of the salt bridge

A cell in which all reactants & products are in their

thermodynamic standard states (1 M for dissolved species
& 1 atm partial pressure for gases) is called a standard cell

CHM 3010_Electrochemistry 19
 Role of salt bridge
What happen without salt bridge?
The function of salt bridge is to maintain electrical
neutrality in each part of the cell. Made from saturated KCl
or KNO3 etc.
Glass tube
Saturated Saturated
KCl KCl gel
Glass wool

In anode section, oxidation occurs, Zn2+ ion increases and

the ve ion concentration is unchanged. The ve ion from
salt bridge (eg. Cl-) flows into this section to maintain
neutrality.
What about the cathode section?

CHM 3010_Electrochemistry 20
Figure 21.5 A voltaic cell based on the zinc-copper reaction

Oxidation half-reaction Reduction half-reaction

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

Overall (cell) reaction

Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)
Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

CHM 3010_Electrochemistry 21
Figure 21.6 A voltaic cell using inactive electrodes
Oxidation half-reaction Reduction half-reaction
2I-(aq) I2(s) + 2e- MnO4-(aq) + 8H+(aq) + 5e-
Mn2+(aq) + 4H2O(l)

Overall (cell) reaction

2MnO4-(aq) + 16H+(aq) + 10I-(aq) 2Mn2+(aq) + 5I2(s) + 8H2O(l)

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

CHM 3010_Electrochemistry 22
Sample Problem 21.2: Diagramming Voltaic Cells

PROBLEM: 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(NO3)3
solution, another half-cell with an Ag bar in an AgNO3 solution, and
a KNO3 salt bridge. Measurement indicates that the Cr electrode is
negative relative to the Ag electrode.
PLAN: Identify the oxidation and reduction reactions and write each half-
reaction. Associate the (-)(Cr) pole with the anode (oxidation) and the
(+) pole with the cathode (reduction).

SOLUTION: e- Voltmeter

salt bridge
Oxidation half-reaction
Cr K+ Ag
Cr(s) Cr3+(aq) + 3e-

Reduction half-reaction NO3-

Ag+(aq) + e- Ag(s) Cr3+ Ag+

Overall (cell) reaction

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

CHM 3010_Electrochemistry 23
 Cell notation
Represent a cell in written form. The Zn-Cu cell can be represented as:
Zn(s)/Zn2+(aq)//Cu2+(aq)/Cu(s)
or
Zn(s)/ZnSO4(aq)//CuSO4(aq)/Cu(s)

Anode left, cathode right. Metals (or conducting materials) for electrical
terminals at both ends. Phase separation - /. Salt bridge - //. If electrolyte
contain > 1 participating in the reaction they are separated by a coma (,).

Examples:
Cd(s)/Cd2+(aq)//H+(aq)/H2(g)/Pt

Ag/AgCl/Cl-(aq)//Fe3+(aq),Fe2+(aq)/Pt

CHM 3010_Electrochemistry 24
 Notation for a Voltaic Cell
components of components of
anode compartment cathode compartment
(oxidation half-cell) (reduction half-cell)

phase of lower phase of higher phase of higher phase of lower

oxidation state oxidation state oxidation state oxidation state

phase boundary between half-cells

Examples: Zn(s) | Zn2+(aq) || Cu2+(aq) | 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

CHM 3010_Electrochemistry 25
 Why Does a Voltaic Cell Work?

The spontaneous reaction occurs as a result of the different

abilities of materials (such as metals) to give up their electrons
and the ability of the electrons to flow through the circuit.

Ecell > 0 for a spontaneous reaction

1 Volt (V) = 1 Joule (J)/ Coulomb (C)

CHM 3010_Electrochemistry 26
Table 21.1 Voltages of Some Voltaic Cells

Voltaic Cell Voltage (V)

Common alkaline battery 1.5

Lead-acid car battery (6 cells = 12V) 2.0

Calculator battery (mercury) 1.3

Electric eel (~5000 cells in 6-ft eel = 750V) 0.15

Nerve of giant squid (across cell membrane) 0.070

CHM 3010_Electrochemistry 27
 Electromotive force (emf)
A force is needed to move a charge. Total force to move
electron(s) from a ve electrode to a +ve electrode in an
electrochemical cell is termed emf (in volts or V). Emf of a
cell is often called cell potential or Ecell.
emf depends on 3 factors:
Tendency of two half reactions to occur spontaneously.
Electrolyte concentration and gas pressure.
Temperature.
Standard emf - Ecello measured at 25 oC, 1 atm of gas
pressure and 1.0 electrolyte concentration

CHM 3010_Electrochemistry 28
 Electrode and cell potentials
Each ion has tendency to take up electron and undergoes reduction.
However the ability to be reduced is different and ion with higher
ability will succeed while the other undergoing oxidation.
Example Zn-Cu cell, Zn2+ vs Cu2+. Cu2+ has higher ability to gain
electron thus reduced and Zn2+ oxidised.
This tendency is termed electrode (half cell) potential and the different
(+ve value) between two electrode potentials is the cell potential.
Thus
Ecell = Ecathode Eanode
Ecell > 0 so Ecathode > Eanode
Based on cell notation Ecell = Eright - Eleft
Only cell potential can be measured experimentally. The electrode
potential is calculated from the cell potential if the potential for the
other half cell is known.
Ecathode = Ecell + Eanode or Eanode = Ecathode - Ecell

CHM 3010_Electrochemistry 29
Standard hydrogen electrode and
standard electrode potential
An electrode potential is calculated from a cell potential where the
potential of one electrode is known. It is conventionally agreed that the
potential of hydrogen electrode at 25 oC, [H+] = 1 M and PH2 = 1 atm is
0.0000 V.

Example to determine the potential for Cu/Cu2+

Pt/H2(g)/H+(aq)//Cu2+/Cu

The cell potential (from meter) is 0.34 V

Ecello = ECuo EH2o = 0.34 V or ECuo = 0.34 V

By this way a list of electrode (half cell) potentials are obtained. They
are also referred to as standard reduction potentials. See the list in
reference books.

CHM 3010_Electrochemistry 30
 The standard hydrogen
electrode. Hydrogen gas
at 1 atm is passed over
finely divided platinum.
The solution contains
1.00 M hydrogen ion.
The reduction potential is
exactly 0 V at 298 K
(25oC).

CHM 3010_Electrochemistry 31
 Using a hydrogen half-cell, other reduction
potentials can be measured

A galvanic cell
comprised of copper
and hydrogen half-
cells. The reaction is
Cu2+(aq)+H2(g)
Cu(s)+2H+(aq)

Cell notation:
Pt(s), H2(g)|H+(aq)||Cu2+(aq)|Cu(s)

CHM 3010_Electrochemistry 32
 Redox reactions
The reduction potentials table can also be used to determine whether a
redox reaction can occur spontaneously. The strength of a reduction or
oxidation agent depend on the potential value. A substance or an ion
with high reduction potential will be easily reduced thus is a strong
oxidation agent and vice versa.

MnO4-, O3, F2 strong oxidants

Li, K, Na strong reductants

Example: Will the following mixture react spontaneously at standard state?

Zn2+(aq) + Fe2+(aq) ???
(a) Zn2+(aq) + 2e Zn Eo = -0.76 V
(b) Fe3+(aq) + e Fe2+ Eo = 0.77 V
(a)-2(b); Zn2+(aq) + 2Fe2+(aq) Zn(s) + 2Fe3+(aq)

E o
reaction 0.76 (0.77) 1.53
The forward reaction is not spontaneous.

CHM 3010_Electrochemistry 33
 Free energy and Ecell
DG is the maximum work that can be obtained or extracted from a system or process.
DG = wmax
In electrochemical cell
Work (w) = - charge (Q) x emf
= - nF x emf
= - nFEcell
Therefore DG = - nFEcell
For standard state
DGo = - nFEcello
Example: Zn + Cu2+ Zn2+ + Cu Eo = 1.10 V
DGo = - 2 x 96500 x 1.10
= - 212300 J = - 212.3 kJ

Spontaneous
DG = -ve E = +ve
reaction
Nonspontaneou
DG = +ve E = -ve
s reaction

CHM 3010_Electrochemistry 34
 Nernsts equation
For a general reaction
aA + bB eE + fF
The corresponding relation for Gibbs free energy is:

[ E ]e [ F ] f
DG DG RT lno
Therefore [ A]a [ B]b
e f
Or [ E ] [ F ]
nFE nFE o RT ln
[ A]a [ B]b
At 25 oC
[ E ]e [ F ] f Nernsts equation
E E RT ln
o

[ A]a [ B]b

0.0592 [ E ]e [ F ] f
EE o
log
n [ A]a [ B]b
If all species are at unit concentration log Q = 0 and Ecell = Ecello

CHM 3010_Electrochemistry 35
 The Nernst Equation

D = D - (0.059/n)log10(Q)

D, in analogy with DG, indicates the direction

of spontaneous change:
D > 0 reaction goes left to right
D = 0 no net reaction (equilibrium)
D < 0 reaction goes right to left

CHM 3010_Electrochemistry 36
 A Standard Half Reaction

Note that the Nernst equation combines the

tendency of both the oxidation reaction to
proceed and the reduction reaction to
proceed as a pair of coupled reactions. To
establish a scale of reactivity we measure
half reactions against a standard half
reaction:
H2 2H+ + 2e

CHM 3010_Electrochemistry 37
 The Hydrogen Electrode
The hydrogen electrode is the standard
reference electrode for aqueous half-cell
potentials. The half-cell reaction is the
reduction
2 H+(aq) + 2e H2 (g)

The standard potential of this half-cell is

set equal to zero. Potentials measured for
a cell containing the standard hydrogen
electrode will be equal to the half-cell
potential of the other electrode. A table of
standard half-cell potentials may be
obtained from any of the references.

CHM 3010_Electrochemistry 38
 Conventions for (Half-cell Potentials)
1. Assign standard hydrogen electrode a potential of 0.0 V.
2. When half reactions are written as reductions, reactions
that proceed as reductions more readily than H+/H2 are
assigned positive voltages, those that proceed less readily are
assigned negative voltages.
3. If the direction of the half reaction is reversed, the sign of
the standard half cell potential is reversed. If the reaction is
multiplied by some factor, the standard half cell potential
remains unchanged.
4. The value of the half cell potential is a measure of the
tendency of the reaction to proceed from left to right as
written.
CHM 3010_Electrochemistry 39
 Usage of Ecell
Determination of Equilibrium Constant
aA + bB eE + fF

[ E ]e [ F ] f
DG DG RT ln
o

[ A]a [ B]b

DG 0 and K eq
[ E ]e [ F ] f
RT [ A]a [ B]b
E
o
ln K eq
nF
o
The eq const can be calculated from cell or vice
E
versa

CHM 3010_Electrochemistry 40
Figure 21.9 The interrelationship of DG0, E0, and K

DG0 K E0cell Reaction at

DG0 standard-state
conditions
<0 >1 >0 spontaneous
0 1 0 at equilibrium
>0 <1 <0 nonspontaneous
DG0 = -nFEocell
DG0 = -RT lnK

By substituting standard state

values into E0cell, we get

E0cell K E0cell = (0.0592V/n) log K (at 250C)

E0cell = -RT lnK

nF
Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

CHM 3010_Electrochemistry 41
Electrolysis

CHM 3010_Electrochemistry 42
 Electricity can be used to make nonspontaneous
redox reactions to occur
The process is called electrolysis
Electrolysis occurs in an electrolysis or
electrolytic cell
These cells require a source of direct current,
possibly one of the batteries just discussed, to
provide electrical energy

CHM 3010_Electrochemistry 43
Electrolytic Cell Galvanic Cell
Cathode is negative Cathode is positive
(reduction) (reduction)
Anode is positive (oxidation) Anode is negative (oxidation)

In both types of cells oxidation occurs at the anode

and reduction occurs at the cathode
Electrolysis in aqueous solutions often involves
water molecules
This is often unintended and called a competing
reaction

CHM 3010_Electrochemistry 44
 Electrolytic cell
+ -
Battery
Example: Electrolysis of fused NaCl
Anode Cathode

Cl2 released Cl- Na deposit

Na+

Na+ is attracted to ve electrode and reduced while Cl-

attracted fo +ve electrode and oxidised.
Na+(l) + e Na(s) anode
Cl-(l) 1/2Cl2(g) + e cathode

In term of electrode charge

electrolytic cell is different Cell Anode Cathode
from voltaic cell Electrolytic +ve -ve
Voltaic -ve +ve

CHM 3010_Electrochemistry 45
Electrolysis from aqueous solution
Consider electrolysis of aqueous NaCl. The process become complex in the
presence of water as the water itself can be oxidised or reduced.
Cathode H2 is released
Anode O2 is released for dilute NaCl
Cl2 is released for conc. NaCl
Cathode : 2 competing reactions
2H2O + 2e H2 + 2OH- Eo=-0.83 V
Na+ + e Na Eo=-2.71 V
H2O with higher red. potential is reduced.

Anode : 2 competing reactions

2H2O O2 + 4H+ + 4e Eo = -1.23 V
Cl- Cl2 + 2e Eo = -1.36 V

The oxidation potential for H20 is a little higher and since the conc of Cl- is low
H2O is oxidised. However for high conc. NaCl, due to the concentration effect
Cl- is oxidised.

CHM 3010_Electrochemistry 46
 Faradays Law
Faraday relates the amount of substance obtained at the
electrode with the amount of charge transferred during
electrolysis.
Na+ + e Na(s)
Cl- 1/2Cl2 + e
I mole of e is required to deposit 1 mole of Na and
release half mole of Cl2

Charge of 1 e = 1.602 X 10-19 C

Charge of 1 mole of e = 6.022 X 1023 X 1.602X 10-19
96500 C
This is well known as Faradays number, 1 F = 96500 C

CHM 3010_Electrochemistry 47
 Electrolysis of molten
sodium chloride.
The passage of an
electric current through
molten sodium chloride
decomposes the material
into molten sodium and
chlorine gas.
The products must be
kept separated because
they react on contact to
re-form NaCl.

CHM 3010_Electrochemistry 48
A microscopic view of the changes at the anode in the electrolysis
of molten NaCl.
The positive charge of the electrode attracts Cl- ions.
At the surface of the electrode electrons are pulled from the ions
yielding neutral Cl atoms which combine to form Cl2 molecules
that rise to the surface as a gas.

CHM 3010_Electrochemistry 49
 Sodium is a liquid at the melting point of sodium
chloride (801 oC)

Reaction at the cathode:

Na+(l) + e- Na(l)
Reaction at the anode:
2Cl-(l) Cl2(g) + 2e-
Cell reaction:
2Na+(l) + 2Cl-(l) 2Na(l) + Cl2(g)
The electrode polarities are reversed in electrolytic cells
relative to those in galvanic cells

CHM 3010_Electrochemistry 50
 Electrolysis of an
aqueous solution of
potassium sulfate. The
products of the
electrolysis are H2 and O2
gas, not the expected
products solid K and
S2O82-. Why?

Look up the E0 values of all possible electrode reactions

and work out how you may arrive at the statement given
above.
Refer Chemistry: Matter and Its Changes by brady and
Senese (4th Edn) Chp 21.

CHM 3010_Electrochemistry 51
Example
Calculate the mass of Cu (atomic mass = 64) deposited at cathode in
the electrolysis of CuSO4 if 2 A current was flowed for 1 hour.

At cathode Cu2+ + 2e Cu
2 F is required to deposit 1 mole Cu

Charge, Q = i.t = 2 C s-1 X 3600 s = 7200 C

Mole of Cu deposited = 7200/(2 X 96500) = 0.0373 mole

Mass of Cu = 0.0373 X 64 = 2.39 g

CHM 3010_Electrochemistry 52
 Table 21.4 Comparison of Voltaic and Electrolytic Cells
Electrode

Cell Type DG Ecell Name Process Sign

Voltaic <0 >0 Anode Oxidation -

Voltaic <0 >0 Cathode Reduction +

Electrolytic >0 <0 Anode Oxidation +

Electrolytic >0 <0 Cathode Reduction -

CHM 3010_Electrochemistry 53