Dr.

Fathy Shokry
Fathishoukry@[Link]

Lecture (3) Week 4

 Concentration Cells
is a limited form of a voltic / galvanic cell that has two equivalent half-cells of the same composition differing only
in concentrations

• Notice that 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.

Concentration and Ecell (cont.)
Recall, in general:
DG = DG° + RTln(Q)
• However:
DG = -nFEcell
-nFEcell = -nFE°cell + RTln(Q)

Ecell = E°cell - (RT/nF)ln(Q)

Ecell = E°cell - (0.0591/n)log(Q)

The Nernst Equation
 [ product ]
Q=
Remember
reac tan t 

pH = - log [H+]
similarly, pOH = - log [OH-]
pH = 14 - pOH
Example (1)
 Predict the cell potential for the following reaction when
the pressure of the oxygen gas is 2.50 atm, the hydrogen ion
concentration is 0.10 M, and the bromide ion concentration
is 0.25 M.
 solution
 To calculate the standard cell potential for the reaction,
Eocell:

oxidation: 4 Br-(aq) 2 Br2(l) + 4 e-

Eoox. = - Eored. = - (+ 1.077 V) = - 1.07 V

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

Eored. = + 1.229 V Eocell = + 0.152 V

 n = 4 moles of electrons

 Substitute values into the Nernst equation and solve for the
non-standard cell potential, Ecell.
 Ecell = + 0.152 V - (0.0591/4) log(1.02 x 106)
Ecell = 0.063 V
EXAMPLE (2):
 Calculate the corrosion tendency of Cu in aerated H2SO4 containing o.oo1 M
CuSO4 and pH=1 given that Eo for Cu is 0.34 V while aerated acids solutions is
1.229 V
 Solution:
• reduction: O2 + 4H+ + 4e- → 2H2O
• oxidation: 2Cu → 2Cu +2 + 4 e –
• Overall reaction : O2 + 4H+ + 2 Cu → 2H2O + 2Cu +2
• Eo(cell) = Eo (cathode) - Eo (anode) = 1.229- 0.34 = 0.89 V
• pH = - log [H+] = 1
• [H+] =10 -1
[𝐻 𝑂]2 ∗[𝐶𝑢+2 ]2 [1]2 ∗[0.001]2
• Q = 𝑃𝑂2∗[𝐻 +]4∗[𝐶𝑢]2 = 1∗[10 −1 ]4 ∗[1]2
= 0.01
2

• Ecell = E°cell - (0.0591/n)log(Q)

• Ecell = 0.89 V - (0.0591/4) log(Q) =0.916 V
• ΔG = - nFE = -4*96500*0.916.= -354560 J
Which one would decide the direction of the reaction?
• We must therefore introduce a single function expressing the
combined effect of both DS and DH. Of the total enthalpy of the
system, only a part is converted to useful work, which is called
"Free Energy" (DG).

DHo - DGo = T DSo

This may be rearranged to give

• DGo = DHo - T DSo

• A reaction is not feasible if DGo is positive.

• A reaction is at equilibrium if DGo = 0
Example
Calculate DGo for the following reaction at
500K
Cu(s) + H2 (g)
DHo(500) = -87 kJ/mol DSo(500) = +47
J/K-mol
Solution
DGo = DHo - T DSo
DGo = -87000 - (500 x 47)
DGo = -110.5 kJ/mol
DGo is negative, hence the reaction is feasible.
Free energy potential
• A chemical reaction will occur only if there is an overall decrease in the energy of
the system and its surroundings during a reaction.

• Consider examples (A) and (B)

• Example A
ZnO(s) + C (s) → Zn + CO(g)
DS = +285 J/K-mol DH = +349.9 kJ/mol

• Example B
Fe(s) + 1/2 O2 (g) → FeO(s)
DS = -71 J/K-mol DH = -265.5 kJ/mol

In the above example, both DS and DH work opposite to each other in terms of
direction of energy change.
 Applications of
Oxidation-Reduction
Reactions
Batteries
 Alkaline Batteries
An alkaline battery (IEC code: L) is a type of primary battery that derives its energy
from the reaction between zinc metal and manganese dioxide.
Compared with zinc–carbon batteries of the Leclanché cell or zinc chloride types,
alkaline batteries have a higher energy density and longer shelf life, yet provide the
same voltage.
 Hydrogen Fuel Cells
A hydrogen fuel cell uses the chemical energy of hydrogen to produce electricity.
It is a clean form of energy with electricity, heat and water being the only
products and by-products. Fuel cells offer a variety of applications, from
transportation to emergency back-up power, and can power systems as large as a
power plant or as small as a laptop.
Basics of Corrosion
 BASICS OF CORROSION

Corrosion of Metals

All interactions between a metal (or alloy) with its

environment.

Environment

• Water (fresh or sea water)

• Soil (wetted)
• Atmospheric air (humid)
 BASICS OF CORROSION

Electrochemical Nature of Corrosion

Corrosion of metals (e.g. iron) in water is basically an

irreversible reaction that is electrochemical in nature, i.e.
a chemical reaction accompanied by the passage of an
electric current.
 BASICS OF CORROSION

Why Metals Corrode?

Metals tend to corrode in order to retain their natural form (ore)

Metals are usually extracted and purified from their ores via high-energy
input processes.

For example :

Thermal energy (high furnace for Fe)

Electric energy (electrolytic paths forAl)

 BASICS OF CORROSION

The extracted free metal has a high energy content. i.e. active state
 BASICS OF CORROSION

Active free metals tend to react easily to produce compounds, such as

salts and oxides.

Metals in the compounded forms have less energy content, i.e. stable
state.

Corrosion is governed
by the law of
conservation of energy.
 BASICS OF CORROSION
Thermodynamics of Corrosion

∆G = Gprod – Greact

Since, Gprod < Greact

Therefore,
∆G is –ve

Hence, the corrosion reaction is :

spontaneous
irreversible
 BASICS OF CORROSION

Occurrence of corrosion
Corrosion is initiated at the metal surface defects since they are the
highest energy sites, i.e. the most active sites.

(a) (b) (c)

 BASICS OF CORROSION

A terrace is a “flat” area with the same crystal orientation;

a ledge is a “narrow” step separating the terraces (this provides the “sloping ground” of the surface); and
a kink is an irregular “twist” in the ledge.

Schematic model of a free metal surface

Atom Degree of Freedom
A , Terrace (Plane) 1
B , Step (Ledge) 2
C , Kink 3
Activity Order : C > B >A
Dislocation
 THEORY OF CORROSION

Corrosion Process
Due to the electrochemical nature, the corrosion process involves two reactions:
A. Anodic Reaction (metal dissolution)

B. Cathodic Reactions
 THEORY OF CORROSION

Corrosion Process
A. Anodic Reaction (metal dissolution)
Fe Fe 2+ + 2e-

B. Cathodic Reactions
1. Oxygen reduction reaction
O2 +2H2O + 4e- 4 OH-

Predominates in aerated
Near-Neutral solutions pH > 5
 THEORY OF CORROSION

B. Cathodic Reaction
2. Hydrogen evolution reaction
2H+ + 2e- 2H (adsorbed) H2 (gas)
Predominates in acid solutions pH < 5
 BASICS OF CORROSION

In conclusion:

A piece of metal immersed

in an electrolyte acts as its
own:

Anode
Cathode
Electrical connection
 BASICS OF CORROSION

Factors of Corrosion

1 Water
2 Oxygen
3 Acidity
 BASICS OF CORROSION

Testimony
An environment is considered corrosive if it contains Water
with dissolved Oxygen and / or Acidity ( H+ ions )

Corrosion Rate
The rate at which metal loss occurs due to corrosion is
expressed in terms of:
mpy = mils per year
Or
mmpy milli- meter per year
 There are three main methods that are
used to express the corrosion rate:
a) Thickness reduction of the material per
unit time.
 In the metric system this measure is usually
expressed in mm/year.
b) Weight loss per unit area and unit time.
 Weight loss per unit area and unit time was
commonly used in earlier times, mainly
because weight loss was usually the
directly determined quantity in corrosion
testing. Here the test specimens were
weighed before and after the exposure to
the corrosion medium.
C) Corrosion current density.
• Corrosion current density is a particularly
suitable measure of corrosion rate when treating
corrosion theory and in connection with
electrochemical corrosion testing.
• Common Corrosion Rate Units
• – gmd (grams of metal lost per square meter per
day)
• – mm/y (average millimeters penetration per
year)
• – mpy (avg. milli inches penetration per year, 1
mili = 0.001 in)
A carbon steel test specimen of dimensions
2-in × 3-in × 0.125-in with a 0.25-in hole for
suspending in solution is exposed for 120
hours in an acid solution and loses 150
milligrams. Calculate the corosion rate in gmd,
mpy and mm/y.
Given that the density of carbon is 7.87 g/cm3
 Area = 2* (A1+A2+A3)+A4.

 A3 = (2*3) – 3.14 *(0.25)^2/4

 Corrosion rate = weight loss/ area. Time

Recall
Corrosion of Zinc in acids
 In dilute acids Zinc dissolves with
hydrogen evolution
 Zn Zn+2 + 2e-
 2H+ + 2e- H2
Cathodic Rxns in Acidic & Basic Solns

 In alkaline Deaerated Neutral or Basic Solutions

2H2O + 2e- → H2 + 2OH-
 In alkaline and neutral aerated solutions
O2 + 2H2O + 4e- → 4OH-
(the presence of O2 causes higher corr. rate)
 in deaerated acids soutions
2H+ + 2e- → H2
 In aerated acids solutions
O2 + 4H+ + 4e- → 2H2O
(presence of O2 further increases corrosion , consume more
electrons)
 Anodic Reactions
 Examples
Zn→ Zn2+ + 2e- zinc corrosion
Fe→ Fe2+ + 2e- iron corrosion
Al→ Al3+ + 3e- aluminium corrosion
Fe2+→ Fe3+ + e- ferrous ion oxidation
H2→ 2H+ + 2e- Hydrogen oxidation
H2 + 2OH- → 2H2O + 2e- hydrogen oxidation in water or bases
2H2O → O2 + 4H+ + 4e- oxygen evolution
4OH- → O2 + 2H2O + 4e- oxygen evolution in water or bases
 Oxidation reactions takes place for the Anode
 Produce electrons
Cathodic Reactions
 Examples
O2 + 2H2O + 4e-→ 4OH- oxygen reduction
O2 + 4H+ + 4e- → 2H2O oxygen reduction in acids
2H2O + 2e-→ H2 + 2OH- hydrogen evolution
2H+ + 2e- → H2 hydrogen evolution in acids
Cu2+ + 2e- → Cu copper plating
Fe3+ + e- → Fe2+ ferric ion reduction
 Reduction reactions takes place at the Cathode
 Consume electrons
Example
 Iron is connected to copper and then immersed in a
solution containing both Fe2+ and Cu2+ ions.

(a) Which metal corrodes?

(b) Write equations to describe the reactions which
occur at each electrode, assuming each metal has a
valency of 2.
(c) Calculate the maximum possible potential of the
resulting corrosion cell.
Solutions
 The metal with the most negative reduction potential
will be the anode. From Standard reduction
electrode potentials at 250 , Eo for iron is -0.44 V,
while for copper it is +0.34 V. The iron will thus be
the anode and will corrode. Convention requires
that we write the cell as

Fe| Fe2+ || Cu2+ | Cu

 and the cell potential calculated as The following:
E(cell) = E red(Cu cathode) – Ered (Fe anode)
= (+ 0.34) - (-0.44)
= +0.78 V
The electrode on the left is the anode, and thus the
electrode reactions are:
Fe = Fe2+ + 2e-
Cu2+ + 2e-= Cu
Cell Electrode potential
 The slandered potential for galvanic cell is
calculated according to the following equation:
Example
 Calculate the standard half cell electrode potential
for Fe rode in Hcl
 Solution:

 The cathode is (H+ / H2 ) E0cathode = 0

 The Anode is (Fe /Fe++) E0anode = - 0.440 volt
 E0cell = 0 – (-0.44) = 0.44 volt
 Cell Electrode potential
 The value of E˚cell is related to the thermodynamic
quantities of ΔG˚.
Δ G˚ = – nFE˚cell

 For the corrosion reaction to take place ΔG

should be negative .