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Bob
Cottis
This presentation is copyright Bob Cottis 1997. All rights reserved. It may not be copied as a whole or in part in any form without prior written permission of the author.
Recommended Books
Corrosion
What is Corrosion?
Reaction
Examples of Corrosion
Rusting
of steel
of magnesium in air
acid is a substance that produces excess hydrogen ions (H+) when dissolved in water
examples are HCl, H2SO4
base is a substance that produces excess hydroxyl ions (OH-) when dissolved in water
examples are NaOH, KOH
dissolves with hydrogen evolution Zn + 2HCl ZnCl2 + H2 known as a base or active metal
Zinc
One atom zinc metal plusof two molecules hydrogen reacts toof form one molecule of molecule zinc chloride plus one of hydrogen gas chloride (hydrochloric goes to acid)
Connection of Platinum to Zinc Zinc and platinum Zinc and platinum not
electrons
Zn
Pt
HCl
Zn 2HCl ZnCl 2H+ + 2e- H2 Zn + Zn2+ + 2e 2 + H2 metal + acid salt+ +electrons hydrogen hydrogen ions + electrons hydrogen gas metal metal ions
one zinc ion in solution Reactions that involve both chemical change and the transfer of charge
Overall reaction
2H2O 2H2 + O2
or
evolution at one electrode 2H+ + 2e- H2 (acids) 2H2O + 2e- H2 + 2OH- (alkalis)
Oxygen evolution at the other electrode 2H2O O2 + 4H+ + 4e(acids) or 4OH- O2 + 2H2O + 4e(alkalis)
Faradays Law
Charge
Faradays Constant
One
mole of hydrogen ions (1 g) contains Avogadros number (6 1023) ions Hence electrons will react with each mole of hydrogen ions Charge on the electron is 1.6 10-19 C Hence one mole of ions requires 96500 C This is known as Faradays constant
Faradays Law
nFm Q M where Q charge (C) F Faraday' s constant (96500 C/mole) n number of electrons transferr ed m mass of metal oxidised (g) M atomic weight of metal (g/mole)
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
Anodic Reactions
Examples
Zn Zn2+ + 2eFe Fe2+ + 2eAl Al3+ + 3eFe2+ Fe3+ + eH2 2H+ + 2e2H2O O2 + 4H+ + 4e Oxidation reactions Produce electrons
zinc corrosion iron corrosion aluminium corrosion ferrous ion oxidation hydrogen oxidation oxygen evolution
Cathodic Reactions
Examples
O2 + 2H2O + 4e- 4OH2H2O + 2e- H2 + 2OHCu2+ + 2e- Cu Fe3+ + e- Fe2+ Reduction reactions Consume electrons
that metal ions may react with water (a hydrolysis reaction) e.g. Al3+ + 3H2O Al(OH)3 + 3H+ or 2Al3+ + 3H2O Al2O3 + 6H+
Note
that in an electrochemical reaction, we have the same number of each atom on each side of the equation, and the same overall charge
Effect of Potential
Electrochemical
charge Hence, we expect that the voltage of the metal with respect to the solution will affect electrochemical reactions Voltage of metal with respect to solution is known as the electrochemical potential
zinc is placed in acid the metal will start to dissolve and hydrogen will start to be liberated according to the potential of the metal Consider the anodic zinc dissolution reaction Zn Zn2+ + 2e-
Ecorr
kinetics
potential theory:
The corrosion potential will be that potential at which the sum of all anodic (positive) and cathodic (negative) currents on the electrode is zero
Polarization
Types of Polarization
Activation
Polarization
The polarization necessary for the electrochemical reaction to go at the given rate Given by Tafels Law:
i E Eo b log io
E against E log |i|, then activation and i for the o o polarization gives a straight cathodic reaction line
Electrode Potential
Anodic reaction, Tafel slope Mixed equilibrium icorr for the Tafel slope E is corr and Cathodic reaction, expressed as occurs when sum of reaction positive corrosion slope is mV Tafel per decade all currents is zero negative Eo and io for the of current anodic reaction mV log (-i2) - log (-i1) log |current|
Concentration Polarization
Additional
polarization caused by drop in concentration of a reactant at the electrode surface As concentration falls, more polarization is needed to make the current flow Eventually, no more current can flow because no more reactant can reach the metal, and a limiting current is reached
Concentration Polarization
Oxygen
Resistance Polarization
If
there is a resistance between the anode and the cathode in a cell, then the current flowing through that resistance will cause a potential drop given by Ohms Law: V = IR This is important for paint films and for high resistance solutions
Resistance Polarization
Electrode Potential
Resistance Polarization causes potential of anode and cathode to differ due to potential drop across solution, hence corrosion current is reduced
Passivation
When
a passive film is formed, this causes a marked drop in current density due to the resistance of the film and its effect as a barrier to diffusion This effect is seen on the anodic curve
Passivation
Electrode Potential The rate of corrosion will be When aRapid stable passive film rate of cathodic critically affected by the has formed, the current has reaction leads to passivation, cathodic curve Lower rate of cathodic a steady, low value the and low rate of corrosion But it slow may lead to and low Current fallsalso as passive reaction leads to the activity, passive current density Very cathodic reaction rate ofof corrosion? film starts to form the Active corrosion gives normal high rate corrosion leads to low rate of corrosion active-passive transition activation polarization
Polarization Curves
Iron
in hydrochloric acid
Electrode Potential
Polarization Curves
Iron
in sulphuric acid
Electrode Potential
Anodic iron dissolution (with active-passive transition) Oxygen evolution on passive film (or transpassive corrosion Cathodic hydrogen evolution as metal is oxidised to a higher oxidation state)
Polarization Curves
Iron
hydrogen evolution reaction 2H+ + 2e- H2 The concentration of hydrogen ions will influence the rate of the reaction As the hydrogen ion concentration is increased (i.e. the solution made more acid), so the rate of the reaction increases Similarly the potential will influence the reaction - the more negative the potential the faster the reaction
Faster
pH
platinum no metal dissolution will occur, but to balance the charge a reaction which creates electrons must occur If the solution contains dissolved hydrogen, the reverse of the hydrogen evolution reaction can occur: H2 2H+ + 2e-
2H+ + 2e-
This
reaction will go faster in alkaline solution (since H+ will be removed by H+ + OH- H2O)
reaction will go faster at more positive potentials (because electrons will be removed from metal)
This
Thermodynamic Equilibrium
2H+ + 2e- H2 The potential at which it occurs for a given solution composition is known as the equilibrium potential. The concentrations of reactants controls the rates of the forward and reverse reactions and hence the equilibrium potential
Potential
2H2O = O2 + 4H+ + 4eEquilibrium potential as pH increases Ofalls is stable 2 2H+ + 2e- = H2 Equilibrium potential falls as H2O is stable pH increases
Potential
Corrosion
Potential
14
Will iron Will iron corrode corrode in in alkaline neutral waters? solution?
Potential
Al3+
Al2O3
AlO2-
Al
0 7 14
us what can happen, not necessarily what will happen No information on rate of reaction Can only be plotted for pure metals and simple solutions, not for alloys