Concentration Cell

1
 Nernst Equation Simplified

At 25 C (298 K) the Nernst Equation is

simplified this way:

0.0591
EE  0
log( Q)
n

2
 Equilibrium Constants and Cell
Potential
At equilibrium, forward and reverse
reactions occur at equal rates, therefore:
1. The battery is “dead”
2. The cell potential, E, is zero volts

Modifying the Nernst Equation (at 25 C):

0.0592
0 volts  E 
0
log( K )
n

3
 Calculating an Equilibrium Constant
from a Cell Potential

Zn + Cu2+  Zn2+ + Cu E0 = + 1.10 V

0.0591
0 volts 1.10  log( K )
2
(1.10)( 2)
 log( K )
0.0591
37.2  log( K )

10 37.2  K 1.58 x10 37

4
 ???
Concentratio
n Cell
Both sides have
the same
components but
at different
concentrations.

Step 1: Determine which side undergoes

oxidation, and which side undergoes reduction.

5
 ???
Concentration
Cell
Both sides have
Anode Cathode the same
components but
at different
concentrations.

The 1.0 M Zn2+ must decrease in concentration, and

the 0.10 M Zn2+ must increase in concentration
Zn2+ (1.0M) + 2e-  Zn (reduction)
Zn  Zn2+ (0.10M) + 2e- (oxidation)
Zn2+ (1.0M)  Zn2+ (0.10M)
6
 ???
Concentration
Cell
Both sides have
Anode Cathode the same
components but
at different
concentrations.

Spontaneous: e- move from anode to cathode

(+Voltage)
Use Le Chatelier: Increasing [Zn2+ (1.0M)] forces
the reverse to take place
Therefore, Decreasing the Ecell

7
 ???
Concentration Cell Concentration
Cell
Both sides have
Anode Cathode the same
components but
at different
concentrations.

Step 2: Calculate cell potential using the Nernst

Equation (assuming 25 C).
Zn2+ (1.0M)  Zn2+ (0.10M)
0.0591
EE  0
log( Q)
n
8
 Nernst Calculations

Zn2+ (1.0M)  Zn2+ (0.10M)

0.0591
EE 0
log( Q)
n
E  0.0 Volts
0
(0.10)
n2 Q
(1.0)
0.0591 0.10
E  0.0  log( )  0.030Volts
2 1.0
9
 Electrolytic
Processes
Electrolytic
processes are
NOT spontaneous.
They have:

A negative A positive free

cell potential, (-E0) energy change, (+G)

10
 Electrolysis of Water

In acidic solution

Anode rxn: 2H 2 O  O2  4H   4e  -1.23 V

Cathode rxn: 4 H 2 O  4e   2 H 2  4OH  -0.83 V
-2.06 V
2H 2O  2H 2  O2

11
 Electroplating
of Silver
Anode reaction:
Ag  Ag+ + e-
Cathode reaction:
Ag+ + e-  Ag
Electroplating requirements:
1. Solution of the plating metal
2. Anode made of the plating metal
3. Cathode with the object to be plated
4. Source of current
12
 A couple of important relationships to remember:

C = coulomb = charge transported by a steady current of

one ampere in one second
C = amp x sec

F = C/n then C = nF

If you know the moles of e- generated, then you use

stoichiometry to determine moles of the metal that are
deposited.

13
 Example #1
Assume that 1.50amps of current flow through a solution
containing silver ions for 15.0 minutes. The voltage is such that
silver is deposited at the cathode. How many grams of silver
metal are deposited? Ag+ + e- Ag
Hint: C = amp x sec
C = 1.50 amp x (15min x 60sec/min)
C = 1.35 x 103 C
Hint: C = nF therefore n = C/F
n = 1.35 x 103 C / 9.65 x 104
n = 1.40 x 10-2 mole e- therefore 1.40 x 10-2 mole Ag
= 1.51g Ag are deposited
14
 Example #2
One ½ reaction occurring in the lead storage battery
is:
Pb + SO42- PbSO4 + 2e-
If the battery delivers 1.50 amps and if its lead
electrode contains 454g of Pb, how long can current
flow?
Hint: convert to mole Pb
454g = 2.19mol Pb which means 4.38 mole e- are
produced
C = nF = 4.38 (9.65 x 104)
C = 4.23 x 105 C
Hint: C = amp x sec
4.23 x 105 = 1.50amp x time
15 Time = 2.82 x 105sec = 78.3 hours
 The Nernst Equation

Consider a galvanic cell that uses the reaction:

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

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

following ion concentrations?

[Fe3+] = 1.0 × 104 M[Cu2+] = 0.25 M [Fe2+] = 0.20 M

16 ‫אלקטרוכימיה‬-15
16
 The Nernst Equation

0.0592 V
E = E°  log Q
n
Cu(s) + 2 Fe3+(aq) Cu2+(aq) + 2 Fe2+(aq)
Calculate E°:
Cu(s) Cu2+(aq) + 2 e E° = 0.34 V
Fe3+(aq) + e Fe2+(aq) E° = 0.77 V

E°cell = 0.34 V + 0.77 V = 0.43 V

17 ‫אלקטרוכימיה‬-15
17
 The Nernst Equation
0.0592 V
E = E°  log Q
n
Cu(s) + 2 Fe3+(aq) Cu2+(aq) + 2 Fe2+(aq)
Calculate E:
0.0592 V [Cu2+][Fe2+]2
E = E° – 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

18 ‫אלקטרוכימיה‬-15
18
 Electrochemical Cells (Batteries)

Chemical reaction produces electricity.

Called “voltaic cells”
Happens SPONTANEOUSLY.

19
 Moving Electrons = Electricity

Electrons from oxidized substance

travel towards substance reduced.

Traveling electrons move

through “external circuit”
where they do work.

20
 Parts of a Simple Battery
(Voltaic Cell)

Made of Two “Half Cells” containing:

2 Metal Electrodes
2 Solutions of Ions
External Wire
Salt Bridge

21
 “Charge” flows in a “circuit” that
is connected.

External Wire:
allows e- to flow
between metal electrodes

Salt Bridge:
allows ions to flow
between solutions

22
 What is Ox/Red?

Start with Table J

Electrons travel from more
“Active” metal toward less
active metal.

Metal above = oxidized

Ion on Metal below =
reduced

Ex:
Ox: Zn
23 Red: Cu+2
 Which way do electrons
flow in the external wire?

Electrons flow
“Down Table J”

From metal
above to ion of
metal below e-
from Zn to Cu+2

24
 Which electrode is
negative or positive?

Electrons flow from negative to

positive electrode.

Negative electrode: Zn
Positive electrode: Cu e-

25
 Which electrode is the
anode or cathode?

Anode: metal electrode

where oxidation occurs
Ex: Zn

Cathode: metal electrode

where reduction occurs
Ex: Cu
26
 Remember

AN OX
RED CAT
Anode is where oxidation happens
Cathode is where reduction happens

27
 What are the Half Reactions?
Ox:
Zn0 Zn+2 + 2e-

Red:
Cu+2 + 2e- Cu0 e-

What is the Net Equation?

Net: (add ½ reactions)
Zn0 + Cu+2 Zn+2 + Cu0

Make sure final net equation is

balanced for electrons and atoms!
28
 Which electrode gains/loses weight?
Look at half reactions!!
Which forms solid metal?
Which forms dissolved ions?

Ox:
Zn0 Zn+2 + 2e-
Red:
Cu+2 + 2e- Cu0

29
 Which way do the ions in the salt
bridge “migrate” or move?

Remember:
“The negative ions complete the circuit”

(The ions actually end up moving towards

the solution of opposite charge that forms.)

30
 Dead Battery

Voltage = 0

Means the reaction in the battery has

reached EQUILIBRIUM.

31
 You try it…

Mg/Mg+2//Al+3/Al

•Draw and label Battery

•What is oxidized/reduced?
•What are the half reactions and net(balanced)?
•What is the neg/pos electrode?
•What is the anode/cathode?
•Which way do e- flow in wire?
•Which way do -/+ ions flow in salt bridge?
•Which electrode gains/loses mass?
32
 Lemon Battery Demo
http://youtu.be/AY9qcDCFeVI
Batteries
https://www.youtube.com/watch?v=9OVtk6G2T
nQ
Battery Simulation
https://www.youtube.com/watch?v=8iT9B7aJN
Kc

33
 Finding Voltage of a Battery
(Honors)
Use Voltage Table
Find your half reactions and record voltage

Note:
All ½ reactions shown are reductions.
For oxidation, reverse the sign of the voltage

34
 Nerntz Equation (Honors)

Find voltage of a battery when the conc. of dissolved

ions is not 1 Molar (as on “standard voltage” table)

Ecell = E0 – 0.0592 log [product ion]x

n [reactant ion]y

n = total # of moles electrons being transferred

The concentration of dissolved ions can affect voltage.

Greater concentration of reactant ions (see net)
increases the overall voltage.
35
 Harnessing the Power
of Voltaic Cells

Batteries and Corrosion

36
 Commercial Voltaic Cells
Voltaic Cells are convenient energy sources
Batteries is a self-contained group of voltaic cells arranged in series.
Advantage: Portable
Disadvantage: Very Expensive (.80€ / Kwatt-h)
Need cells in series to provide power

The Processes occurring during the

discharge and recharge of a lead-acid
battery. When the lead-acid battery
is discharging (top) it behaves like a
voltaic cell: the anode is negative
(electrode-1) and the cathode is
positive (electrode-2). When it is
recharging (bottom), it behaves like
an electrolytic cell; the anode is
positive (electrode-2) and the
cathode is negative (electrode-1).

37
 Dry Cell or LeClanche Cell
Dry Cells
Invented in the 1860’s the common dry cell or LeClanche cell, has become a familiar household
item. An active zinc anode in the form of a can house a mixture of MnO 2 and an acidic electrolytic
paste, consisting of NH4Cl, ZnCl2, H2O and starch powdered graphite improves conductivity. The
inactive cathode is a graphite rod.

Anode (oxidation)
Zn(s) g Zn2+(aq) = 2e-
Cathode (reduction). The cathodic half-reaction is complex and even today, is still
being studied. MnO2(s) is reduced to Mn2O3(s) through a series of steps that may
involve the presence of Mn2+ and an acid-base reaction between NH4+ and OH- :

2MnO2 (s) + 2NH4+(aq) + 2e- g Mn2O3(s) + 2NH3(aq) + H2O (l)

The ammonia, some of which may be gaseous, forms a complex ion with Zn2+,
which crystallize in contact Cl- ion:

Zn2+(aq) + 2NH3 (aq) + 2Cl-(aq) g Zn(NH3)2Cl2(s)

Overall Cell reaction:

2MnO2 (s) + 2NH4Cl(aq) + Zn(s) g Zn(NH3)2Cl2(s) + H2O (l) + Mn2O3(s) Ecell = 1.5 V

Uses: common household items, such as portable radios, toys, flashlights,

Advantage; Inexpensive, safe, available in many sizes
Disadvantages: At high current drain, NH3(g) builds up causing drop in voltage,
short shelf life because zinc anode reacts with the acidic NH4+ ions.

38
 Dry Cell or LeClanche Cell
Invented by George Leclanche, a French Chemist.

Acid version: Zinc inner case that acts as the anode and a carbon
rod in contact with a moist paste of solid MnO2 , solid NH4Cl, and
carbon that acts as the cathode. As battery wear down, Conc. of Zn+2
and NH3 (aq) increases thereby decreasing the voltage.
Half reactions: E°Cell = 1.5 V
Anode: Zn(s) g Zn+2(aq) + 2e-
Cathode: 2NH4+(aq) + MnO2(s) + 2e- g Mn2O3(s) + 2NH3(aq) + H2O(l)

Advantage:
Inexpensive, safe, many sizes

Disadvantage:
High current drain, NH3(g) build
up, short shelf life

39
 Alkaline Battery
Alkaline Battery
The alkaline battery is an improved dry cell. The half-reactions are similar, but the
electrolyte is a basic KOH paste, which eliminates the buildup of gases and maintains the
Zn electrode.
Anode (oxidation)
Zn(s) + 2OH- (aq) g ZnO(s) + H2O (l) + 2e-
Cathode (reduction).
2MnO2 (s) + 2H2O (l) + 2e- g Mn(OH)2(s) + 2OH-(aq)

Overall Cell reaction:

2MnO2 (s) + H2O (l) + Zn(s) g ZnO(s) + Mn(OH)2(s) Ecell
= 1.5 V

Uses: Same as for dry cell.

Advantages: No voltage drop and longer shell life than
dry cell because of alkaline electrolyte; sale ,amu sizes.
Disadvantages; More expensive than common dry cell.

40
 Alkaline Battery
Leclanche Battery: Alkaline Version
In alkaline version; solid NH4Cl is replaced with KOH or NaOH. This
makes cell last longer mainly because the zinc anode corrodes less
rapidly under basic conditions versus acidic conditions.
Half reactions: E°Cell = 1.5 V
Anode: Zn(s) + 2OH-(aq) g ZnO(s) + H2O(l) + 2e-
Cathode: MnO2 (s) + H2O(l) + 2e- g MnO3 (s) + 2OH-(aq)
Nernst equation: E = E° - [(0.592/n)log Q], Q is constant !!

Advantage:
No voltage drop, longer shelf life.

Disadvantage:
More expensive

41
 Mercury Button Battery
Mercury and Silver batteries are similar.
Like the alkaline dry cell, both of these batteries use zinc in a basic
medium as the anode. The solid reactants are each compressed with
KOH, and moist paper acts as a salt bridge.
Half reactions: E°Cell = 1.6 V
Anode: Zn(s) + 2OH-(aq) g ZnO(s) + H2O(l) + 2e-
Cathode (Hg): HgO (s) + 2H2O(l) + 2e- g Hg(s) + 2OH-(aq)
Cathode (Ag): Ag2O (s) + H2O(l) + 2e- g 2Ag(s) + 2OH-(aq)

Advantage:
Small, large potential,
silver is nontoxic.

Disadvantage:
Mercury is toxic, silver is
expensive.

42
 Lead Storage Battery
Lead-Acid Battery. A typical 12-V lead-acid battery has six cells
connected in series, each of which delivers about 2 V. Each cell
contains two lead grids packed with the electrode material: the
anode is spongy Pb, and the cathode is powered PbO2. The grids
are immersed in an electrolyte solution of 4.5 M H2SO4. Fiberglass
sheets between the grids prevents shorting by accidental physical
contact. When the cell discharges, it generates electrical energy as a
voltaic cell.
Half reactions: E°Cell = 2.0 V
Anode: Pb(s) + SO42- g PbSO4 (s) +2 e- E° = 0.356
Cathode (Hg): PbO2 (s) + SO42- + 4H+ + 2e- g
PbSO4 (s) + 2 H2O E° = 1.685V
Net: PbO2 (s) + Pb(s) + 2H2SO4 g PbSO4 (s) + 2 H2O E°Cell = 2.0 V

Note hat both half-reaction produce Pb2+ ion, one through

oxidation of Pb, the other through reduction of PbO2. At both
electrodes, the Pb2+ react with SO42- to form PbSO4(s)

43
 Nickel-Cadmium Battery
Battery for the Technological Age
Rechargeable, lightweight “ni-cad” are used for variety of cordless appliances.
Main advantage is that the oxidizing and reducing agent can be regenerated
easily when recharged. These produce constant potential.
Half reactions: E°Cell = 1.4 V
Anode: Cd(s) + 2OH-(aq) g Cd(OH)2 (s) + 2e-
Cathode: 2Ni(OH) (s) + 2H2O(l) + 2e- g Ni(OH)2 (s) + 2 OH-(aq)

44
 Fuel Cells

45
 Fuel Cells; Batteries
Fuel Cell also an electrochemical device for converting
chemical energy into electricity.
In contrast to storage battery, fuel cell does not need to involve a
reversible reaction since the reactant are supplied to the cell as needed
from an external source. This technology has been used in the Gemini,
Apollo and Space Shuttle program.
Half reactions: E°Cell = 0.9 V
Anode: 2H2 (g) + 4OH-(aq) g 4H2O(l) + 4e-
Cathode: O2 (g) + 2H2O(l) + 4e- g 4OH-(aq)
Advantage:
Clean, portable and product is water.
Efficient (75%) contrast to 20-25% car,
35-40% from coal electrical plant

Disadvantage:
Cannot store electrical energy, needs
continuous flow of reactant, Electrodes
are short lived and expensive.
46
 CORROSION

47
 Corrosion
Not all spontaneous redox reaction are beneficial.
Natural redox process that oxidizes metal to their oxides and
sulfides runs billions of dollars annually. Rust for example is
not the direct product from reaction between iron and oxygen
but arises through a complex electrochemical process.

Rust: Fe2O3 • X H2O

Anode: Fe(s) g Fe+2 + 2e- E° = 0.44 V
Cathode: O2 (g) + 4H+ + 4e- g 2H2O (l) E° = 1.23 V
Net: Fe+2 will further oxidized to Fe2O3 • X H2O

48
 Conditions for Corrosion
Conditions for Iron Oxidation:
Iron will oxidize in acidic medium
SO2 g H2SO4 g H+ + HSO4+
Anions improve conductivity for oxidation.
Cl- from seawater or NaCl (snow melting) enhances rusting

Conditions for Prevention:

Iron will not rust in dry air; moisture must be present
Iron will not rust in air-free water; oxygen must be present
Iron rusts most rapidly in ionic solution and low pH (high H+)
The loss of iron and deposit of rust occur at different placm on object
Iron rust faster in contact with a less active metal (Cu)
Iron rust slower in contact with a more active metal (Zn)

49
 Iron Corrosion; Chemistry
Most common and economically destructive
form of corrosion is the rusting of iron. Rust
is not a direct product of the reaction
between iron and oxygen but arises through
complex electrochemical process. The
features of a voltaic cell can help explain this
process.

Iron will not rust in dry air; moisture must be present.

Iron will not rust in air-free water; oxygen must be present
Iron rusts most rapidly in ionic solutions and at low pH (High H+)

The loss of iron and the

depositing of rust often occur at
different places on the same
object.
Iron rust faster in contact with a
less active metal (such as Cu)
and more slowly in contact with
a more active metal (such as Zn).

50
 Electro-chemical Considerations :
For metallic materials, the corrosion process is normally
electrochemical, that is a chemical reaction in which there is
transfer of electrons from one chemical species to another. Metal
atoms characteristically lose or give up electrons in what is called
an oxidation reaction. The site at which oxidation takes place is
called the anode; oxidation is sometimes called an anodic reaction.
The electrons generated from each metal atom that is
oxidized must be transferred to and become a part of
another chemical species in what is termed a reduction
reaction. The location at which reduction occurs is
called the cathode.
Corrosion Cell : For Corrosion to take place ,the information of a
corrosion cell is essential. A corrosion cell essentially comprised
of the following four components.
1 ) Anode . 2 ) Cathode . 3 ) Electrolyte . &
4 ) Metallic path.

51
 Anode ( -ve of cell ): One of the two dissimilar metal electrodes in an
electrolytic cell. Electrons are released at anode , which is the more reactive
metal .Electrons move through the wire in to the cathode.

Cathode ( +ve of cell ) :The other Electrode in the electrolytic cell

.Reduction takes place at cathode and electrons are consumed .
Electrolyte ( e.g. salt solution ) : It is the electrically conductive solution
for corrosion to occur. Positive electricity passes from anode to cathode
through the electrolyte as cations .
Metallic path : The two electrodes are connected externally by a metallic
conductor. Current flow from (+) to (-) which really electrons flowing from
( - e ) to ( +e ).

Current flow : Conventional current flows from anode ( - ) to cathode ( + )

as Zn++ ions through the solution. The circuit is completed by passage
of electrons from the anode to the cathode through the wire ( outer
current ).
Electron Flow : The circuit is completed by negative ions (-)
Which migrate from cathode (+) , through the electrolyte , towards the
anode (-).
52
 Example :
In the dry Battery
Zinc casing acts as anode.
Carbon electrode acts as
cathode.
Moist ammonium chloride
acts as
Electrolyte .
e.g. Zn ions dissolve from
a zinc
anode and thus carry
positive
current away from it ,
through the Aqueous
electrolyte.
53
 Anodic And Cathodic Reactions

Anodic reactions characteristics :

The process of oxidation in most metals and

alloys represents corrosion. If oxidation is
stopped , corrosion is stopped.
54
 Cathodic reactions characteristics :
The Process of reductions which occur at
the cathode represents protection .Electrons
released by the anodic reactions are
consumed at the cathode surface. Unlike an
anodic reaction , there is a decrease in
valence state. ( most common Cathodic
reactions mentioned above ).
Types of Corrosion Cells :

55
 (1) Galvanic cells :
The galvanic cell may
have an anode or
cathode of dissimilar
metals in an
electrolyte or the
same metal in
dissimilar conditions
in common
electrolyte.
(2) Concentration Cells :
This is similar to galvanic cells except the anode and
cathode are of same metals in a heterogeneous electrolyte.
A pipe in soil, Concentration cells may be set up by:
(a) Variation in the amount of oxygen in soils.
(b)Differences in moisture content of soils.
(c) Differences in compositions of the soil.

56
 Concentration cells are commonly observed in underground
corroding structures, such as buried pipes or tanks.

There are three general types of concentration cell corrosion:

1)Metal Ion Concentration Cells
In the presence of water, a high concentration of metal ions will
exist under faying surfaces and a low concentration of metal ions
will exist adjacent to the crevice created by the faying surfaces. An
electrical potential will exist between the two points. The area of the
metal in contact with the low concentration of metal ions will be
cathodic and will be protected, and the area of metal in contact with
the high metal ion concentration will be anodic and corroded.

57
 2)Oxygen Concentration Cells
A water solution in contact with the metal surface will normally
contain dissolved oxygen. An oxygen cell can develop at any point
where the oxygen in the air is not allowed to diffuse uniformly into the
solution, thereby creating a difference in oxygen concentration
between two points.Corrosion will occur at the area of low-oxygen
concentration (anode).

3)Active-Passive Cells
Metals that depend on a tightly adhering passive film (usually an
oxide) for corrosion protection; e.g., austenitic corrosion-resistant
steel, can be corroded by active-passive cells. The corrosive action
usually starts as an oxygen concentration cell; e.g., salt deposits on
the metal surface in the presence of water containing oxygen can
create the oxygen cell.

The inequality of dissolved chemicals causes a

potential difference which establishes anode in the
more concentrated region and cathode in the less
concentrated region.
58
 (3) Electrolytic Cells :
This type of cell is formed when an
external current is introduced into the
system. It may consist of all the basic
components of galvanic cells and
concentration cells plus an external source
of electrical energy. Notice that anode has
a (+) polarity and cathode has (-) polarity in
an electrolytic cell, where external current
is applied. This is the type of cell set up for
electrically protecting the structures by
Cathodic protection. The polarity of an
electrolytic cell is opposite to that in a galvanic
(corrosion) cell.

59
 (4) Differential Temperature Cells :
This type of cell is formed when two electrode of same
metals present in different temperatures , causing in
different potential ,high temp. electrode will be the
cathode and the lower temp. will be the anode . ( e.g. heat
exchangers & condensers ).
The Electro Motive Series ( EMF )
When a metal is immersed in an electrolyte, a dynamic equilibrium is
established across the interface with a potential difference between
the metal and electrolyte. If a metal is immersed in a solution of its
own ions , such as Zn in ZnSO4 solution ,or copper in CuSO4 the
potential obtained is called the reversible potential ( Erev ) .
If the metals are in their standard stats , such that activities of the
metallic ions are equal to unity or gases are at 1 bar pressure , the
potentials obtained are called ' Standard Electrode Potentials ' . A
standard potential refers to the potential of pure metal measured with
reference to a hydrogen reference electrode ( H2 / H+ ) which is
arbitrarily defined as Zero .It is not possible to establish a reversible
potential for alloys containing two or more reactive components , so
only pure metals are listed in table below .
60
61
62
 Galvanic series : In actual corrosion problems , galvanic
coupling between metals in equilibrium with their ions rarely
occurs. In general , the positions of metals and alloys in the
galvanic series agree closely with their constituent elements
in the emf series .

This
represents
the relative
reactivities of
a number of
metals and
commercial
alloys in
seawater.

63
64
 Example 1 : A galvanic cell consist of ( Zn ) electrode in( ZnSO4 )
solution with ( 1 mole ) concentration . The other is of ( Ni ) electrode
in ( NiSO4 ) solution with ( 1 mole ) concentration . The two electrodes
are separated with porous partition to prevent mixing of the two
solutions . The two electrodes are contacted with conductive wire .

Find.
a ) On which electrode the
oxidation reaction will be .
Zn electrode Ni electrode
b ) Which electrode will be the
anode .
c ) Which electrode will
NiSO4
corroded .
d ) what is the EMF for this
galvanic cell , circuit close.

Ni2+

65
 Solution :
The half cells reactions are :

(a) Oxidation reaction will take place on Zn electrode .Because the

potential deference in Zn half cell more negative (- 0.763 V) compare
with (-0.250 V) for Ni half Cell .
(b) From previous answer, Zn electrode is the anode , because the
oxidation reaction take place on anode electrode.
(c) In galvanic cell , the anode electrode is the corroded electrode , for
that Zn electrode will corroded.
(d) Cell potential is the sum of the two half cells potential.

66
 The result of the Cell reaction . Ni potential changed with respect
to standard potential cell .This is due to its potential in the EMF
series . Also if we connect Pt electrode with Cu electrode we get :
Pt+2+2e Pt Eo=+1.200V
Cu+2+2e Cu Eo=+0.337V
By subtraction the lower potential from the higher we get
Pt+2+2e Pt Eo=+1.200V
Cu Cu+2+2e Eo=-0.337V
Eo= +0.863V

If the galvanic Cell contain two electrodes , One of them with ( - ve )

potential and the other with ( + ve ), such as Zinc with Copper .
Zn+2+2e Zn Eo=-0.763V
Cu+2+2e Cu Eo=+0.337V
In this case ,if we subtract Cu potential from Zn potential the result is :
Cu+2+2e Cu Eo=+0.337V
Zn Zn+2+2e Eo=+0.763V
Eocell=+1.10V
We change reduction sign to get the
cell potential difference .

67
 Example 2 : Write the reactions of the anodic half cell ( oxidation )
and Cathodic half cell ( reduction ) . For the following
electrodes and electrolytes , by using standards potential
values :
(a) Zinc and copper electrodes are immersed in dilute ( CuSO4 ).
(b) Copper electrode is immersed in water saturated with oxygen.
(c) Iron electrode is immersed in water saturated with oxygen.
(d) Magnesium electrode is immersed in water saturated with oxygen.

Solution :

(a) Zn Zn+2 + 2e Eo = - 0.763V

Oxidation ( Anodic reaction )

= Reduction ( Cathodic reaction )

Changing the sign of Cathodic reaction , we observed that Zinc reaction
possess more negative , so it is the anode and oxidation reaction
occurred on it.
68
 b) May be there is a low rate corrosion or may be there is no
corrosion , because the potential difference between Cu oxidation
(0.337 V) and that formed in water from hydroxide ion (0.401 V) is
very small .

c)
Oxidation ( Anodic reaction )

Reduction ( Cathodic reaction )

Iron potential's difference is more negative, so it is the anode and
oxidation reaction occurred on it.

d)
( Anodic reaction )

( Cathodic reaction )

Mg is more negative in potential, so it is the anode and oxidation

reaction occurred on it.

69
 Galvanic Cell with Electrolytes that are not one molar :-
Most of electrolyte solutions of the real galvanic cells are not to be
(1 mole ) .But they are always dilute solutions , which they are less than
(1 mole ) .If the ions concentrates in the electrolyte surround to the anode
electrode is less than 1 mole , the reaction motive force to dissolve or
corrode the anode will be higher .Because there is less concentrate of
ions that causes the reverse reaction .There for it will be more negative of
electro-chemical series on the anodic half cell.

Truly the metal ion concentration effects (Cion) on the standards potential
of the electrochemical series (Eo(at (25o)Temperature are given by Nernst
equation for the half anodic cell reaction .Where there is one kind of ions
are produced . Nernst equation can be written as follow :
RT  a products 
E  Eo  ln  
nF  a reactives 
8.3 J/K o .mole X 25  273K o
E  E  2.3
o
log Cion
n X 96,500 coulomb

70
 Where are :
E = New electrochemical potential for the half cell .
Eo = standard electrochemical potential for the half cell .
n = No. of electrons transferred ( the valence ).
Cion = molar concentrations of the ions .
R = gas constant = 8.3 J/Ko/mole.
T = Temperature = 25 + 273 = 298 Ko.
F = Faraday constant = 96,500 coulomb .
For the Cathodic reaction , the final potential sign must be inverses .

Example 3:
A galvanic cell in ( 25 Co ) temp. it is formed from Zinc electrode in (
0.10 mole ZnSO4 ) solution , the other electrode is of Nickel in ( 0.05 mole
NiSO4 ) solution .The two electrodes are separated with porous wall and
connected with external wire. What is the value of the cell potential, when
the circle is connected

71
 Solution :
First we suppose that the solutions are in ( 1 mole ) concentrate. So
the potentials of Zn & Ni be in standard value of EMF serious . Zn electrode
will be the anode because its potential( - 0.763 v ) is more negative in the
electrochemical cell of Zn – Ni Than of Ni ( - 0.250 v ).
Then using Nernst equation to correct the potentials of the cell .

In the modern theory principles we shall take the free energy to solve
Nernst equation .

72
73
E1o

Electrochemical cell potential for two standard half-cells that

are electrically coupled
Consider the generalized reactions involving the oxidation of metal M1
and the reduction of metal M2 as
M1  M1n   n e - - E1o ………(
M n2   n e -  M 2  E o2 1)
Where the Eos are the standard potentials as taken from the standard
emf series. Since metal M is oxidized, the sign of E1o
……...(
is opposite to that as it appears in Table of standard emf the2)
two above
equations yields. n n
M1  M 2  M1  M 2 ……….(3)

And the cell potential E o is

E o  E o2  E1o ………..(4)

For this reaction to occur spontaneously, E Must be positive ;if it is negative,

o

The spontaneous cell direction is just the reverse of equation(3) . When

standard half-cell are coupled together, the metal that lies lower in emf
table will experience oxidation (i.e., corrosion), whereas the higher one will
be reduced.

74
 Influence of Concentration and Temperature on Cell Potential

Nernst equation electrochemical cell potential for two half-

cells that are electrically coupled and for which solution ion
concentrations are other than 1M.


E  E  E 
RT M
  n
................(5)
 
o o 1
2 ln 1 n
nF M 2

Simplified form of Eq. (5) for T = 25oC ( room temperature).


E  E  E 
0.0592 M
  n

 
o o 1
2 log 1 n
n M 2

75
 Corrosion Prevention

76