CORROSION THERMODYNAMICS

MATERIAL CHEMICATRY

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OUTLINE

 Introduction
 Nernst Equation
 Reference Electrode
 Potential-pH Diagram

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 INTRODUCTION

 We can use thermodynamics, e.g. Pourbaix or E-pH diagrams, to evaluate the theoretical activity of a
given metal or alloy in a corrosion situation provided the chemical make-up of the environment is
known.
 But for practical situations, it is important to realize that the environment is a variable that can
change with time and conditions.
 It is also important to realize that the environment that actually affects a metal corresponds to the
micro-environmental conditions this metal really 'sees', i.e. the local environment at the surface of the
metal.
 It is indeed the reactivity of this local environment that will determine the real corrosion damage.
 Thus, an experiment that would investigate only the nominal environmental condition without
consideration for local effects such as flow, pH cells, deposits, and galvanic effects is useless for
lifetime prediction.
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 CORROSION THERMODYNAMICS

 Corrosion is thermodynamically driven to lower the overall energy of the system

 Involves electron/charge transfer
 Controls the spontaneous direction for corrosion
 Thermodynamics provides an understanding of the energy changes involved in corrosion
 Thermodynamics show how conditions may be adjusted to prevent corrosion, i.e., ΔG>0
 Thermodynamics can indicate corrosion is possible, i.e., ΔG<0, but thermodynamics
cannot predict the rate

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WHAT IS THERMODYNAMICS?

Energy can neither be created or destroyed

(Entropy of any isolated system always increase)
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 GIBBS FREE ENERGY
 In the late 19th century Josiah Willard Gibbs formulated a theory to
predict whether a chemical reaction is spontaneous based on the
free energy
 ΔG = ΔG0 + RT ln Q
❖ ΔG = change in Gibbs free energy
❖ T = absolute temperature
❖ R = gas constant,
❖ Q = reaction quotient
 Gibbs' key contribution was to formalize the understanding of the
effect of reactant concentration on spontaneity
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8
THERMODYNAMIC FUNCTION OF STATE

Δ E, Δ H, ΔS, ΔG, ΔA and Δµ

ΔG = ΔH – T ΔS
Free energy Enthalpy Entropy
The total energy which The heat content The unavailable energy of
can be utilized for work. a substance due to the
internal motion of the 9
molecules.
 FREE ENERGY OF A CORROSION REACTION
• In an electrochemical cell at equilibrium, no current flows and the energy change
occurring in a reaction is expressed in equation:
W = ΔG = -nFE
• Under standard conditions, ΔG0 is directly related to the standard potential of the
cell, E0:
ΔG° = −nFE°
• For a galvanic cell, such as the Daniell cell,
Ecell= Ecathode –Eanode
• The equilibrium constant (Keq) for the same electrochemical reaction

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STANDARD ELECTRODE POTENTIALS

 The potential difference across an electrochemical cell is the potential difference measured
between two electronic conductors connected to the electrodes.
 A voltmeter may be used to measure the potential differences across electrochemical cells
but cannot measure directly the actual potential of any single electrode.
 We use reference electrode to measure the potential of another electrode.
 Standard hydrogen electrode (SHE) can be used as reference
 Standard potential of a reaction in reference to its reduction (E0red) as shown again in a
Table

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STANDARD-STATE REDUCTION HALF-CELL POTENTIALS

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EXAMPLE → TUGAS

1. Rank the following elements in order of their thermodynamic ease of being oxidized in
solution: Hg, Al, Fe, Au, Cr, Zn, Ag, Mg

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 NERNST EQUATION
 The Nernst equation was named after the German
chemist Walther Nernst who established very useful relations
between the energy or potential of a cell to the concentrations of
participating ions.

 For a generalized reaction equation:

 At equilibrium, ΔG = 0 and Qreaction = Keq

 In the case of an electrochemical reaction by substitution
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 NERNST EQUATION

 Combining constants at 25°C (298.15 K) gives the simpler form of the Nernst equation for
an electrode reaction at this temperature:

 For two half-cell reactions Nernst equation can be modified as:

 For simplicity we usually take

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EXAMPLE → TUGAS

1. Using standard potentials and molarity for ion concentrations calculate the open circuit
potential of the following electrochemical reactions (balance the equations with water
related chemical species when necessary, i.e. H+, OH- and H2O):
a) H2O2 + Ni → H2O + Ni2+
b) H2O + Mg2+ → H2O2 + Mg
c) Ni + PbO2 → Pb2+ + Ni2+
d) Al3+ + OH- → Al + O2

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GIBBS FREE ENERGY CALCULATION

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  The standard hydrogen half-cell is not common to use under many conditions.
REFERENCE
 The other half-cells most frequently used in corrosion studies, are listed in the following Table.
HALF-CELLS

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CONVERSION BETWEEN
REFERENCE
ELECTRODES

 When reporting electrochemical

potential measurements, it is always
important to indicate which
reference half-cell was used to
carry out the work.

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EXAMPLE

 -0.7 V using copper sulfate electrode is -0.382 V vs SHE.

 What does a measured potential value of 0.8 V vs. SHE would be if the potential
had been measured with a saturated silver chloride electrode? ... with a saturated
copper sulfate electrode?

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SILVER/SILVER CHLORIDE
REFERENCE ELECTRODE

 The silver/silver chloride

reference electrode is a widely
used reference electrode
because it is simple,
inexpensive, very stable and
non-toxic.

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COPPER/COPPER SULFATE
REFERENCE ELECTRODE
(CCSRE)

 Copper/copper sulfate half-

cells are typically favored
for potential measurements
of systems buried in soils.

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MEASURING THE CORROSION
POTENTIAL
THE POTENTIAL OF A CORRODING METAL, OFTEN TERMED ECORR

Be aware of the sign

ECORR metal M is -0.405 V.
In the reverse case
ECORR metal M is +0.405 V.

The minus sign indicates that

the metal is negative with
respect to the reference
electrode.
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 MEASURING PH

 Electrodes: A pH electrode consists of two half-cells; an indicating electrode and a reference

electrode. Most applications today use a combination electrode with both half cells in one body.
Over 90% of pH measurement problems are related to the improper use, storage or selection of
electrodes.

 Meters: A pH meter is in reality a high precision and high impedance voltmeter capable of reading
small millivolt changes from the pH electrode system. The meter is seldom the source of problems
for pH measurements. Modern pH meters have temperature compensation (either automatic or
manual) to correct for variations in slope caused by changes in temperature.

 Buffers: These solutions of known pH value allow the user to adjust the system to read accurate
measurements. 24
 POTENTIAL-PH DIAGRAM

 Also called E-pH diagram or Pourbaix Diagram

 Delayed 1945 Ph. D. thesis of Marcel Pourbaix (Belgium)
 Used of thermodynamic theory (Nernst equation) to
create potential – pH diagrams
 Analogous to the composition – temperature diagrams
(phase diagrams) for alloy systems
 Both diagrams are “maps”

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POTENTIAL-PH DIAGRAM

 The stability of a metal when exposed to a

given environment depends on a multitude
of factors that may vary greatly with the
pH and oxidizing or reducing power of that
environment.
 E-pH diagrams are typically plotted for
various equilibria on normal Cartesian
coordinates with potential (E) as the
ordinate (Y axis) and pH as the abscissa (X
axis).
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POTENTIAL-PH DIAGRAM

 The major uses of such diagrams, which can be constructed for all metals,
are:
 Predicting whether or not corrosion can occur
 Estimating the composition of the corrosion products formed
 Predicting environmental changes which will prevent or reduce
corrosion attack

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 POURBAIX DIAGRAM DOMAINS

The horizontal, vertical and sloping

lines in the diagram form the following
three types of regions or domains.
I. Immunity domain.
II. Passive domain.
III. Corrosion domain.

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 POURBAIX DIAGRAM DOMAINS

 Diagrams have three domains:

• Immunity – region of thermodynamic stability of the pure metal. Corrosion
is thermodynamically impossible.
• Corrosion - region of thermodynamic stability of the metal ion and
dissolution of metal will occur
• Passivity - region of thermodynamic stability of the metal oxide. Corrosion
is mitigated by the formation of a “passive” protective oxide.

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E-PH STABILITY
DIAGRAM OF WATER AT
25°C.

The chemical behavior of is

divided into three regions.
 In the upper region, water can
be oxidized to produce oxygen
 In the lower region it can be
reduced to form hydrogen gas.
 Water is therefore only
thermodynamically stable
between lines (a) and (b).

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LIMITATION OF E-PH DIAGRAMS:

1. These diagrams give no information on the corrosion rate, since they are
based on thermodynamic and not on kinetic data.
2. The effect of impurities in solution is difficult to consider.
3. The effect of alloy element has not been considered
4. Generally the diagrams are drawn for room temperature conditions.

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 ALUMINUM E-PH DIAGRAM
 The E-pH diagram of aluminum is one of the simplest E-pH diagrams.
 There are four species containing the aluminum element will be considered:
❖ two solid species (Al and Al2O3.H2O)
❖ two ionic species (Al3+ and AlO2-)

 The first equilibrium to consider examines the possible presence of either Al3+ or AlO2- expressed in equation.
𝑜
∆𝐺𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = 120.44 𝑘𝐽/𝑚𝑜𝑙

 Assuming that the activity of H2O is unity and that the activities of the two ionic species are equal

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ALUMINUM E-PH
DIAGRAM

 This diagram
show the
soluble species
of aluminum in
water at 25oC

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ALUMINUM E-PH
DIAGRAM

 The next phase is

to consider all
possible reactions
between the four
chemical species i.e.
Al, Al2O3.H2O, Al3+,
and AlO2-.
 These reactions are
summarized in the
following Table.

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ALUMINUM E-PH
DIAGRAM

 By computer
program we can
consider all
reaction involved in
terms of their
thermodynamic
stability for all
conditions of pH
and potential

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ALUMINUM E-PH
DIAGRAM

 In corrosion
practice,
concentration of
soluble species
never reach 1 M.

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POURBAIX
DIAGRAM
FOR IRON
SYSTEM

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POURBAIX DIAGRAM FOR IRON SYSTEM

Four types of reactions:

1. Independent of H+ ions (pH) and E (electrons):
Fe2+ + 2OH- ⇌ Fe(OH)2
2. pH dependent and E independent: Vertical Line
Fe2+ + 2H2O ⇌ Fe(OH)2 + 2H+
3. E dependent and pH independent: Horizontal Line
Fe2+ ⇌ Fe3+ + e-
4. E and pH dependent Sloping Line

2Fe2+ + 3H2O ⇌ Fe2O3 + 6H+ + 2e-

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POURBAIX DIAGRAM FOR FE-H2O AT 25 °C

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POURBAIX DIAGRAM FOR FE-H2O AT 25 °C
LINE 1

𝑜 0.059 𝑎𝐹𝑒2+
𝐸𝐹𝑒 2+ /𝐹𝑒 3+ = 𝐸𝐹𝑒 2+ /𝐹𝑒 3+ − log
𝑛 𝑎𝐹𝑒3+
𝑜
𝑛 = 1, 𝑎𝐹𝑒 3+ = 10−6 , 𝑎𝐹𝑒 2+ = 10−6 , 𝐸𝐹𝑒 2+ /𝐹𝑒 3+ = 0.77
0.059 10−6
𝐸𝐹𝑒 2+ /𝐹𝑒 3+ = 0.77 − 1 log 10−6 = 0.77
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POURBAIX DIAGRAM FOR FE-H2O AT 25 °C
LINE 2

𝑜 0.059 𝑎𝐹𝑒
𝐸𝐹𝑒/𝐹𝑒 2+ = 𝐸𝐹𝑒/𝐹𝑒 2+ − log
𝑛 𝑎𝐹𝑒2+
𝑜
𝑛 = 2, 𝑎𝐹𝑒 2+ = 10−6 , 𝑎𝐹𝑒 = 1, 𝐸𝐹𝑒/𝐹𝑒 2+ = −0.44
0.059 1
𝐸𝐹𝑒/𝐹𝑒 2+ = −0.44 − 2 log 10−6 = −0.62

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POURBAIX DIAGRAM FOR FE-H2O AT 25 °C
LINE 4

2
𝑜 0.059 𝑎𝐹𝑒2+ 𝑎𝐻2𝑂 3
𝐸𝐹𝑒 2+ /𝐹𝑒2𝑂3 = 𝐸𝐹𝑒 2+ /𝐹𝑒 𝑂 − log 6
2 3 𝑛 𝑎𝐹𝑒2 𝑂3 𝑎𝐻+
𝑜
𝑛 = 2, 𝑎𝐹𝑒 2+ = 10−6 , 𝑎𝐹𝑒2𝑂3 = 𝑎𝐻2𝑂 = 1, 𝐸𝐹𝑒 2+ /𝐹𝑒 𝑂
2 3
= 0.73
2
0.059 10−6 1 3
𝐸𝐹𝑒 2+ /𝐹𝑒2𝑂3 = 0.73 − 2 log 6 = 1.084 − 0.177 𝑝𝐻
1 𝑎𝐻+
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POURBAIX DIAGRAM FOR FE-H2O AT 25 °C
LINE A - HYDROGEN

0.059 𝑃𝐻2
𝐸𝐻2/𝐻+ = 𝐸𝐻𝑜2/𝐻 + − log
𝑛 𝑎𝐻+
𝑛 = 1,𝑃𝐻2 = 1 , 𝐸𝐻𝑜2/𝐻 + = 0
0.059 1
𝐸𝐻2/𝐻+ = 0 − log = −0.059 pH
1 𝑎𝐻+

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POURBAIX DIAGRAM FOR FE-H2O AT 25 °C
LINE B - OXYGEN

𝑜 0.059 𝑎𝑂𝐻− 4
𝐸𝑂𝐻− /𝑂2 =𝐸𝑂𝐻 − /𝑂 − 𝑛 log 𝑃 2
2 𝑂2 𝑎𝐻2𝑂
𝑜
𝑛 = 4, 𝑃𝑂2 = 𝑎𝐻2𝑂 = 1,𝐸𝑂𝐻 − /𝑂 = 0.401
2
0.059 𝑎𝑂𝐻− 4
𝐸𝑂𝐻− /𝑂2 = 0.401 − 4 log 1 1 2 = 1.084 − 0.177 𝑝𝐻
𝑝𝐻 + 𝑝𝑂𝐻 = 14 → log 𝑎𝑂𝐻− = 𝑝𝐻 − 14
𝐸𝑂𝐻− /𝑂2 = 1.23 − 0.059 𝑝𝐻 49
REFERENCE

 Chapter 4, Roberge, Corrosion Engineering Principles and

Practice

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