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KOROSI

PENDAHULUAN
TERMODINAMIKA KOROSI
KINETIKA KOROSI
KOROSI GALVANIK
PERLINDUNGAN KOROSI
PENDAHULUAN

Corrosion dari bahasa Latin


corrodere
Corrodere menggerogoti

Korosi adalah degradasi metal/logam melalui reaksi elektrokimia dengan


lingkungannya.

It was calculated that in the UK, 1 ton of steel is converted completely to


rust every 90 s

Fokus pada korosi logam pada lingkungan berair/lembab.


Umumnya, ketika oksidasi logam terjadi maka hal yang memungkinkan
terbentuk:
ion/kompleks logam terlarut
Oksida tidak terlarut, hidroksida dan garam lainnya

Faktor yang mempengaruhi korosi:


Adanya O2
Kehadiran agen pengomplex
pH
Reaksi kebanyakan logam dengan O2 sangat aktiv secara termodinamik
Beberapa reaksi membentuk protecting oxide layer (lapisan pasif)
e.g.
Al sangat reaktif dengan O2
lapisan oksida yang terbentuk sangat tipis
dan bersifat sangat melindungi

Ti non-corrodable oleh pembentukan lapisan


oksida
(sangat tahan terhadap sea water and Cl2) Titanium hip prosthesis

Stainless steel: baja tahan karat yang terbuat dari alloying dengan Cr
membentuk lapisan Cr2O3
Lapisan tipis yang sulit terlihat logam tetap berkilau.
Lapisan yang tdk dpt dipenetrasi oleh air dan udara,
logam bawah terlindungi
lapisan yang sangat cepat dibentuk pada proses pelapisan
akan nampak seperti goresan.
Chrysler Building - type 302 stainless steel (chromium-nickel alloy)
Beberapa memiliki kinetika reaksi yang lambat

Logam seperti Zn, Mg, Cd proses


korosinya berjalan lambat
walaupun G < 0

Galvanised metal sheeting

Grafit menghasilkan energi besar saat teroksidasi, tapi


prosesnya berlangsung sangat lambat hal ini
menyebabkannya immune terhadap korosi termokimia
dibawah kondisi normal.
Kenapa logam mulia tidak terkorosi???? e.g. Au, Pt

Au + 3/2H2O + 3/4O2 Au(OH)3

Au nuggets Pt nuggets
TERMODINAMIKA KOROSI
Is the corrosion of copper in an acidic solution spontaneous? Always?

Consider:
Copper metal is in contact with a 1 M acid solution containing 10-6 M Cu2+.

Calculate the equilibrium potential for this solution:


E(Cu2+/Cu) = +0.34 V (vs SHE)

Cu2+(aq) + 2e- Cu(s) E = +0.34 V

RT 0.05916
E Eo ln Q E Eo log Q
nF n
In an aerated 1 M acid solution:

O2 + 4H+ + 4e- 2H2O E = 1.23 V


Cu2+ + 2e- Cu E = 0.16 V

Overall:
2Cu + O2 + 4H+ 2Cu2+ + 2H2O

In a deaerated 1 M acid solution:


2H+ + 2e- H2 E = 0 V
Cu2+ + 2e- Cu E = 0.16 V

Overall:
Cu + 2H+ Cu2+ + H2

Is the corrosion of copper in an acidic solution spontaneous? Always?


Pourbaix diagram: for copper in a non-complexing aqueous soln at 25C

Pourbaix diagrams give info about thermodynamics only


Kinetic factors may predominate in many situations
What info can be found on a Pourbaix diagram?

Potentials for redox couples as a function of pH


e.g. M/Mn+ and Mn+/M(n+1)+
Most stable metal compounds as a function of pH
predict corrosion products
Zones where metal would corrode or not corrode or become passive

Passivation dissolution occurs


only to a point such that a maximum
of 10-6 M is in solution

In these diagrams we get 4 types of lines:


1) horizontal
2) vertical
3) sloping
4) dashed
Vertical lines:
Equilibria involving hydrolysis, but
NOT e- transfer

e.g. Cu2+ + H2O CuO(s) + 2H+


At pH 7: Cu2+ concentration is reduced
below 10-6 M passivation.
Above pH 7, Cu2+ will not be the major
corrosion product.

Horizontal lines: Sloping lines:


Equilibria involving e- transfer, but Equilibria involving both hydrolysis
NOT H+/OH- and e- transfer

e.g. Cu2+ + 2e- Cu(s) e.g. 2Cu(s) + 2H2O Cu2O(s) + 2H+ + 2e-
Between pH -2 to 6 Cu dissolves for pH 6-14: corrosion product may be Cu2O,
potentials ~0.16 V. but this may oxidise further.
pH > 7: Cu2+ will not be the major
corrosion product if other oxidising
agents are present.
H
slope 0.05916 V per pH unit at 25 o C
n

B
O2 + 2H2O + 4e- 2OH- E = 0.4 V

O2 + 4H+ + 4e- 2H2O E = 1.23 V


A H2O is stable in the region
between the lines
2H+ + 2e- H2 E = 0 V
2H2O + 2e- H2 + 2OH- E = -0.83 V
Dashed lines:
Equilibria involving the redox couples A = H+/H2 and B = H2O/O2 as a
function of pH
Slope = 0.059 V per pH unit.

If the dashed line is above the solid line, the corrosion reaction obtained by
adding the two equilibria will be spontaneous.
If the dashed line is below the solid line, the corrosion process is
thermodynamically unfavourable and the metal is immune to corrosion.
KINETICS OF CORROSION
Corrosion potential:
- the potential of the metal surface in contact with electrolyte where
corrosion occurs.
- no net current flows at the corrosion potential.

Oxidation =
corrosion of metal

ia
ic

Reduction of substance
in contact with the metal

Corrosion current:
- the exchange current at the corrosion potential.
How is the rate of corrosion determined?

Measure steady state current for metal oxidation and H2 evolution as a


function of potential.
Plot graph of logi vs E a Tafel plot
Extrapolate lines till they overlap
i.e. logia = log-ic = logicorrosion

Change in io or
the Tafel slope
change in
corrosion rate
GALVANIC CORROSION
Galvanic corrosion: The electrochemical process in which one metal
corrodes preferentially when it is in contact with a different type of metal
and both metals are in an electrolyte.

Cu2+(aq) + 2e- Cu(s) E = +0.34 V


Fe2+(aq) + 2e- Fe(s) E = -0.44 V
Zn2+(aq) + 2e- Zn(s) E = -0.76 V

When different types of metal come into contact in the presence of an


electrolyte a galvanic couple is set up as different metals have different
electrode potentials.
The electrolyte provides a means for ion migration from the anode to the
cathode.
The anodic metal corrodes faster than it would otherwise.
Corrosion of the cathodic metal is retarded even to the point of stopping.
The presence of electrolyte and a conducting path between the metals
may cause corrosion where otherwise neither metal alone would have
corroded.

Factors that influence galvanic corrosion:


Relative size of anode and cathode
Degree of electrical contact
Aeration of electrolyte
Electrical resistance of electrolyte
Type or concentration of electrolyte
Temperature
Humidity
Potential difference between the two metals
Oxide formation
Covering by bio-organisms
CORROSION PROTECTION
1) CATHODIC PROTECTION
The potential of the metal is shifted more negative lower oxidation rate.

i) Electrolysis ii) Sacrificial anode


Surround metal to be protected by inert Another metal with a more negative m
anodes and pass a current (icath) potential is place in good electrical
between the metal and anodes. contact with the metal to be protected.

log
log
log log

Rate of metal dissolution reduced from Sacrificial metal will enforce its
icorrosion to iprotected. corrosion potential on the metal surface
i) Electrolysis ii) Sacrificial anode

log
log
log log

Problem:
H2 evolution also increases.

Some metals absorb this hydrogen at grain boundaries or into the metal
lattice can change metal structure and hence chemical and physical
properties of metal
Leads to hydrogen embrittlement
Example of sacrificial anodes used in cathodic protection:

Al anodes mounted on
a steel jacket structure

Eo /V
Zn -0.76
Common sacrificial anodes: Zn, Mg, Al
Mg -2.36
Al -1.66
Sacrificial anodes will corrode at a higher rate than protected metal
anodes need to be replaced periodically
2) ANODIC PROTECTION
The potential of the metal is shifted more positive to a region where it is
passivated.
The thin layer of corrosion product on metal surface can act as a barrier to
further oxidation of the metal.

Achieve passivation by:


i) Electrochemical means
Surround metal by cathodes and apply a potential (e.g. anodisation of Al)

ii) Chemical means


Add an oxidising agent to the solution (e.g. dichromate) OR
add an alloying element to the metal which act as small local cathodes which can
lead to film formation (e.g. Cr to stainless steel)
3) MEDIUM MODIFICATION Useful for closed systems
i) Remove aggressive species from medium to reduce corrosion
e.g. O2, acid, number of ions in the electrolyte

ii) Add inhibitors


to catalyse passive film formation
to act as redox reagents
shifts metal potential to regions where metal is anodically or cathodically
protected
to adsorb on to metal surface to decreases rate of anodic and/or cathodic
reaction
adsorption must occur close to the corrosion potential

4) SURFACE COATINGS
Reduce rate of corrosion by removing metal from the environment.
Examples of surface coatings:
Plating with others metals which corrode more slowly
Forming oxide films
Coating with organic polymers (e.g. paint)

Localised damage to coating could lead to


rapid corrosion in that region Self-study!