Basic Corrosion

• Electrochemical
• Chemical
• Degradation
– Metals
– Non-metal
• Return to lowest energy state
 Anode is Where the Action Is
• This is the part of the metal that undergoes active
metal loss.
• This is where the positively charged metal atoms
leave the metal surface and go into the solution as
ions.
• They leave behind negatively charges in the form
of electrons that can flow throughout the metal or
into a external electrical conductor.
• The Anode has a negative electrical charge.
 Anodic Reaction

+2 −
Fe → Fe + 2e
 Cathodic Reaction
• The place on a metal surface where the
electrons, generated at the Anode, are
Consumed.
• To have electrochemical corrosion, one
must have a “sink” for the electrons.
• Often the only place where the rate of
corrosion can be controlled.
 Cathodic Reactions
Acidic Solutions

+ −
2 H + 2e → 2 H → H 2
0

+ −
O2 + 4 H + 4e → 2 H 2O
 Cathodic Reaction
Alkaline Solutions

+ −
O 2 + 4 H + 4e → 2 H 2 O
Other Cathodic Reactions

+3 − +2
Fe +e → Fe
+2 −
Cu + 2e → Cu
 Electrodes

• Electrodes are pieces of metal on which an

electrochemical reaction is occurring
• An anode is an electrode on which an anodic
or oxidation reaction is occurring
• A cathode is an electrode on which a cathodic
or reduction reaction is occurring
How Do You Control Corrosion?
• Control the release and consumption of
electrons.
• Slowing down the rate of consumption at
the Anode is called Anodic Polarization.
• Slowing down the rate of consumption at
the Cathode is called Cathodic Polarization.
 Modern Electrochemistry
• Free Energy of chemical reactions
• The more negative, the more the reaction
want to go to completion
• Does not talk about rate
• Δ G = − nFE
n = no of electrons
F = Faraday Constant
E = Electrochemical Potential
 Standard Chemical Potentials
• μ These are available in tables
• H2O (l) - 56690 cal
• Fe(OH)2 (s) -115,570 cal
• Fe++ -20,300
• H+ 0
• H2 0
• Fe 0
 ΔG
• The Free energy of a reaction is the sum of
the standard chemical potentials
ΔG = μ H 2 0 − μ H 2 −2
1
μ O2

• For this reaction

1
H 2 + 2 O 2 → H 2O
 General Solution for μ
• Tables list μo - the standard at 25°C

μ = μ o
+ RT ln[ M γ ]
• M = the activity or partial pressure
• Condition of equilibrium is:
∑ ν γ M γ = 0 = ∑ ν γ μγ
γ γ
 Solving and Converting
• Equilibrium Laws for Chemical Reactions
∑γ ν γ log[ M γ ] = log K
∑ ν γ μ γο
log K = −
1363

• We call M γ = activity or molar concentrat ion

 Using Energy of Formation
• Combining the energy of formation with the
Nernst equation and the Equilibrium K of
the reactions,
• The equilibrium can be written in the form
of an equation expressing
• pH as a function of Electrochemical
Potential
 Where Does pH Come From?
• We write the equations to have H+ ions

− +
aA+ cH2O + ne = bB+ mH
+ m
[B] • [H ]
b
log = log K
[ A] a
Where Does pH Come From?

+
pH = − log[ H ]

b
[B]
log a
= log K + m pH
[ A]
 Where Does E come From?
• Nernst Equation

RT [B] b
E = E o + 2 .3 log
E
a
nF [A]
• Eo can be calculated

E o
=
∑ vμ o

23 , 060 n
 Free Enthalpies in Tables
• Look up the μ in tables of Free enthalpy of
formation
• Cu++ = +15,530 cal
• Cu = 0 (a condensed body)
• H2O = -56,690 cal
• Etc.
 For Electrochemical Reactions
• 25ºC
• A= oxidized species
• B = reduced species
• m = number of H+ ions
a
0 0.0591 0.059 [ A]
E = E0 − m pH + log b
n n [ B]
 For Chemical Reactions
a
[ A]
log b
= log K + m pH
[B]

log K = −
∑ vμ o

1363
 Why Are We Doing This?
• To construct a Pourbaix Diagram
• To get a visual picture of the corrosion
resistance of the various metals
• Pourbaix Diagrams can be made with other
species such as acetic acid
 To Construct the Diagram
• Plot all of the lines for the equations
• Erase those parts of the lines that make no
sense
– THIS IS A HARD PART
• Define the regions of passivity by innate
intelligence
– THIS IS YOUR CHOICE
 Water Stability
• Two lines (a) and (b)
• (a) is the reaction + −
H 2 = 2 H + 2e
• (b) is the reaction + −
2 H 2 O = O2 + 4 H + 4 e
• Between (a) and (b) water is stable
The
The Pourbaix
Pourbaix (E-pH)
(E-pH) Diagram
Diagram
2.0
1.6 O2 is stable
1.2
0.8
Potential

0.4 H2O is stable

0.0
-0.4
-0.8
-1.2 H2 is stable
-1.6
0 7 14
 Water Stability
• Above the (b) line the partial pressure of
oxygen is above 1 atmosphere and oxygen
is liberated and the solution becomes acidic
– Because O2 is liberated, more H+
predominates
• Below the (a) line the partial pressure of H2
is above 1 atmosphere and H2 is liberated
and the solution becomes more alkaline
-
– Because H2 is liberated, more OH
predominates
 Why is Water Stability
Important?
• First approximation our solutions will fall within
the ranges of water stability
• Most corrosive solutions are dilute water mixtures
• For most solutions, the range of water stability is
larger
– Dissolved species increase the stability in a similar
manner to the freezing point being depressed.
The
The Pourbaix
Pourbaix (E-pH)
(E-pH) Diagram
Diagram
2.0
1.6 O2 is stable
1.2
0.8
Potential

0.4 H2O is stable

0.0
-0.4
-0.8
-1.2 H2 is stable
-1.6
0 7 14
Iron with Water Overpotential
Pourbaix Diagram for Zinc
2.0
1.6
1.2
0.8 Zn(OH)2
Potential

0.4 stable
solid
0.0 Zn2+ stable
-0.4
in solution
-0.8
-1.2
Zn metal stable
-1.6
0 7 14
Pourbaix Diagram for Zinc
2.0
1.6
1.2

Corrosion
Passivity
0.8 Zn(OH)2
Potential

0.4 Corrosion stable

ZnO22-
solid
0.0 Zn2+ stable stable in
-0.4 solution
in solution
-0.8
-1.2 Immunity
Zn metal stable
-1.6
0 7 14
Pourbaix Diagram for Gold
2.0
1.6 C Passivity
1.2 C
0.8
Potential

0.4
Gold metal stable
0.0
Immunity
-0.4
-0.8
-1.2
-1.6
0 7 14
Pourbaix diagram for Aluminium
1.2
1.2
0.8
0.8
0.4
0.4
0.0
0.0
Potential
Potential

-0.4
-0.4
Al 3+
-0.8
-0.8 Al2O3
-1.2
-1.2 AlO2-
-1.6
-1.6
-2.0
-2.0 Al
-2.4
-2.40
0 77 14
14
Pourbaix diagram for Copper
2.0

CuO22- stable in soln.

1.6
Cu oxides
1.2
stable
0.8 Cu2+ stable
Potential

0.4 in solution
0.0
-0.4
-0.8 Cu metal stable
-1.2
-1.6
0 7 14
 Other Systems
• Pourbaix Diagram for systems other than
water
• Acetic Acid
• Oxalic acid
• All others in which enough thermo-
chemical information is available
5M Acetic Acid at 80ºC
5 M Acetic Acid at 150ºC
5M Acetic Acid at 200ºC
 Pourbaix Diagrams
• Can confirm that corrosion will not occur
• If it does imply passivity, may not occur
• Does nothing to talk about rate of corrosion
• Great for:
– Prediction of direction of reactions
– Composition of corrosion products
– Predicting if changes will be beneficial or
harmful
 Process Change Example
• Look at the corrosion of titanium in oxalic
acid
• Add some sodium chloride and see if this
increase in impurities will change the
corrosiveness
1M Oxalic Acid at 100C
1M Oxalic Acid 1M NaCl 100C
Polarization of a Single Metal
 Polarization Curves

• Iron in hydrochloric acid

Electrode Potential

log |current density|

Corrosion of zinc in acid
Electrochemical Potential

Zn → Zn2+ + 2e-
Rate
Rateof
ofReaction
Reaction

EEcorr
corr

2H+ + 2e- → H2

iicorr Rate
Current
of Reaction
density
corr
 Other Cathodic Reactions
• Oxygen reduction is the common reaction
in a water mixture with 8 ppm dissolved
oxygen
Couple- Mixed Cell
Hydrochloric Acid on Zn-Fe Couple
 Plots of E vs log i
• Mixed Corrosion Potential
• These are called polarization diagrams or
Tafel Plots
• At Ecorr there is a corresponding icorr
• If you know the current flowing in the
reactions, you can predict the corrosion rate
• 1 mol electrons has a total charge of 96,500
C (coulombs) or 1amp-second.
 Corrosion Rate
+2 −
Fe → Fe + 2e
• 96500 C (coulombs) = 1 A s
• 1 mol Fe = 56 g = 0.056 kg Fe releases 2
mol electrons = 2 · 96500 C electric charge
• A current of 1 A corresponds to a corrosion
rate of 0.056/(2 · 96500) kg/s iron
• In “Normal Units” a current density of
1 micro amp/cm2 = 1 mpy (one electron Rx)
 Activation Polarization
• The polarization necessary for the reaction
to go at the given rate
• Obeys Tafel’s Law
β = slope of the straight line
 E-log i and Evans Diagrams

• Plot E against log |i|, then activation

polarization gives a straight line
Electrode Potential

log |current|
 Activation Polarization
• Slow Step in the reaction sequence
• Not normally associated with the anodic
reaction
• Almost always the cathodic reaction
• For example the hydrogen reduction
reaction can have 4 steps – one is
controlling
Activation Polarization
 Concentration Polarization
• Additional polarization caused by a drop in
concentration of a reactant at the electrode
surface
• As the concentration falls, more
polarization is need to make the current
flow
• Finally, no more current can flow because
no more reactant can reach the metal and a
LIMITING Current Density is reached
 Concentration Polarization

• Oxygen reduction is often affected by

concentration polarization
Electrode Potential

log |current density|

 Passivation
• When a passive film is developed, this
causes a major reduction the the rate at
which current is flowing
• The current density goes low
• The film impedes the flow of electrons
because of:
– High electrical resistance
– Barrier to diffusion
 Passivation

Electrode Potential

log |current density|

 Pitting and Pitting Potential
• The localized pitting of passive alloys is
from having a chemical system that is too
oxidizing for the service.
• The concept of Protection Potentials
• Perfect Passivation
• Imperfect Passivation
 Perfect Passivation
• It is the potential below which even existing
pits will not grow.
• Occurs when the metal & solution are such
that the metal is passivated without any
chance of pitting
• In a Potentiodynamic scan, the “loop” on
the return scan is small
 Passivation

Electrode Potential

log |current density|

 Workshop/Class Project
• Draw Scans for Type I, II, and III systems

• From a Pourbaix Diagram, estimate the

shape of a scan

• Show that only slightly negative shift in

potential may be necessary to stop pitting