TK 5011-5211

PENGENDALIAN
KOROSI

ELEKTROKIMIA KOROSI
TERMODINAMIKA KOROSI
KINETIKA KOROSI
3,4,5
1
 CORROSION ELECTROCHEMISTRY
ELECTROCHEMICAL REACTIONS
Metallic corrosion is almost always an
electrochemical process
Electrochemical reaction is a chemical
reaction (which involves oxidation and
reduction) involving the transfer of electrons

Corrosion reaction consists of one oxidation

and one reduction which are combined on a
single piece of metal
A piece of zinc immersed in HCl solution
corrosion : Zn Zn2+ + 2e- (anodic
oxidation)
Electrons pass through the metal surface to
another site where hydrogen ions are
reduced to hydrogen gas : 2H + + 2e- H2
(cathodic reduction) Cathodic : 2H+ + 2e- H2
corrosion : Zn + 2H+ Zn2+ + H2 O2 + 4H+ + 4e- 2H2O
General form : O2 + 2H2O + 4e- 4OH-
anodic : M(s) Mn+ + ne- Cu2+ + 2e- Cu(s) 2
Fe 3+
+ e Fe
- 2+
FARADAYs LAW
Corrosion reaction involves transfer of electrons
electric current
Example : Ag Ag+ + e-
corrosion of 1 mol Ag produce 1 mol (= 6.022 x
1023) electrons
the charge carried by 1 mol electrons = 1 faraday
(F)
the charge of 1 electron = 1.6 x 10-19 Coulomb (C)
1F = (6.022 x 1023) x (1.6 x 10-19) = 96.485 C/mol
e-
The charge (Q) can be related to the number of
moles change in a reaction (N) and the number of
electrons per molecule of reacting species (n) :
Q = F N n
the charge is also a function of electric current :
where t : the duration of electrochemical process 3
Untuk pengerjaan Tugas dan Ujian, dilarang menggunakan
Tabel ini, konversi satuan HARUS diturunkan sendiri dengan
rumus Faraday !!!
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 Corrosion : the electrons generated at anodic areas react at
cathodic areas restore ELECTRICAL BALANCE of the system
(no net accumulation of charges on a corroding surface)
Ianodic = Icathodic ia x Sa = ic x Sc

implication of surface area ratio on anodic current density

which is proportional to corrosion rate corrosion local cell :
pitting, crevice, galvanic

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 CORROSION THERMODYNAMICS
ENERGY & ELECTROCHEMICAL CELLS
FREE
Electrical work is the product of charge moved (Q) x the cell potential
(E) through which it is moved. If the potential difference is E, and the
charge is that of 1 mole of reaction in which n moles of electrons are
transferred, the electrical work -w done by the cell must be nE
Electrochemical cell operates reversibly no current flows
Under standard conditions, the standard free energy of the cell
reaction G0 is directly related to the standard potential difference
across the cell (E0) :

For a galvanic cell, which operates spontaneously, a positive cell

voltage will be obtained if the difference is taken in the usual way, as
Ecell = Ecathode Eanode
The free energy change in a galvanic cell, or in a spontaneous cell
reaction, is negative and the cell voltage is positive
Other thermodynamic quantities can be derived from electrochemical
measurements. For example, the entropy change (S) in the cell
reaction is given by the temperature dependence of G: ;
and the equilibrium constant can be obtained with
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Standard Electrode Potentials
The potential difference across an electrochemical cell is the
potential difference measured between two electronic
conductors
In the external circuit connected to an electrochemical cell, the
electrons will flow from the least-positive electrode to the most-
positive electrode
Voltmeters can measure the potential differences across
electrochemical cells but cannot measure directly the actual
potential of any single electrode
Standard potential differences are the actual cell potential
differences measured in reversible cells under standard
conditions. Standard conditions are the pure compound or
element; for gases they are 100 kPa pressure, and for solutes
they are the ideal 1 molar (mol/liter) concentration
The standard electrode or standard reference electrode with
which all other electrodes will be compared is called the
standard hydrogen electrode (SHE)
7
The potential difference across a reversible cell made up of any
8
LATIHAN
1. Berdasarkan Tabel Potensial Standar, sebutkan :
a. logam-logam yang dapat terkorosi dalam larutan
asam
b. logam-logam yang terkorosi dalam air
c. logam-logam yang tidak terkorosi dalam larutan
asam, kecuali jika ada O2 terlarut
2. Tuliskan reaksi katodik dan anodik yang terjadi pada
proses korosi :
a. besi di dalam larutan asam
b. magnesium di dalam air
c. tembaga di dalam larutan asam mengandung
oksigen terlarut

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NERNST EQUATION
The (Walther) Nernst equation describes the relation between
the energy and potential of a cell to the concentrations of
participating ions and other species, can be derived from the
equation linking free energy changes to the reaction quotient :
aA + bB + mM + nN +
At equilibrium, G = 0 and Q corresponds to Keq
Substitution : G = - nFE & G0 = - nFE0 into the 1st equation,
and division of both sides by (nF) Nernst equation :
Two Nernst equations corresponding to two half-cell reactions
can be combined into the Nernst equation for a cell reaction

If species that take part in electrode reactions = pure

solid/liquid compounds their activities = 1. In dilute aqueous
solutions water = pure liquid. The activities of gases = their
partial pressures ; the activities of solutes (ions) = their molar
concentrations : ai = i x [i]
where [i] = molar concentration of species i ; i = activity
coefficient of species i
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Reference Electrode
In many practical potential measurements, the standard
hydrogen electrode cannot be used more convenient to use
alternative electrodes whose potentials are precisely known
with respect to the SHE
The electrodes most commonly used for this purpose are the
AgCl/Ag electrode, //AgCl(s),Cl/Ag(c) at E0 = + 0.2224 V vs. SHE,
and the saturated calomel electrode (SCE) at 0.241 V vs. SHE
The effect of changing the reference electrode is to change the
zero of a potential scale while leaving the relative positions of
all of the potentials unchanged

The most commonly used reference electrodes at 60 C

11
Equilibrium Potential at 25C of most commonly used Reference
Electrodes 12
Hitung potensial kesetimbangan (vs SCE) Fe di dalam larutan akuatik
mengandung 10-3 M Fe2+. 13
POTENTIAL pH DIAGRAMS
E pH diagrams = Pourbaix diagrams, represent the
thermodynamic stability of chemical species in given aqueous
environments
Plotted on normal cartesian coordinates with potential (E) as the
ordinate (y-axis) and pH as the abscissa (x-axis)
Uses of E pH diagrams : (1) to predict whether corrosion can
occur or not, (2) to estimate the composition of the corrosion
product, and (3) to predict environmental changes which will
prevent or reduce corrosion attack
E pH Diagram of Water
Equilibrium between hydrogen ion and hydrogen gas can be
written as
2H+ + 2e- = H2 in acidic environments, and, by adding OH- on
both sides
2H2O + 2e- H2 + 2OH- in neutral or alkaline solutions
Both representations signify the same reaction for which the
thermodynamic behavior can be expressed by a Nernst
equation
14
at 25 C and p =1
 Below line (a) in this figure
the decomposition of H2O into
H2 is favored, whereas H2O is
thermodynamically stable
above that line.
As potential becomes more
positive or noble, water can be
decomposed into oxygen, in
the acidic form : O2 + 4H+
+ 4e- 2H2O
and in neutral or basic form :
O2 + 2H2O + 4e- 4OH-
These equations can be used
to develop a Nernst expression
at 25C and pO2 = 1 , represented: by line (b)
above line (b): water can be oxidized to form oxygen
water is only thermodynamically stable between line (a) and line
(b)
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E - pH Diagram of Aluminum
Al provides one of the simplest cases for demonstrating the
construction of E-pH diagrams; only 4 species containing the Al
element will be considered: 2 solid species (Al and Al2O3.H2O)
and 2 ionic species (Al3+ and AlO2-)
Ionic species equilibrium : Al3+ + 2H2O AlO2- + 4H+
independent of potential can be expressed by : where
Assuming that aH2O = 1 and aAl3+ = aAlO2-
At 25C, [Al3+] = [AlO2-], and Goreaction = 120.44 kJ/mol
pH = 4.38 x 10-5 x 120.44 = 5.27
1st equilibrium : Al3+ + 3e- Al Nernst equation :

2nd equilibrium : 2Al + 3H2O Al2O3 + 6H+ + 6e- Nernst

equation :

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 3rd equilibrium : 2Al3+ + 3H2O = Al2O3 + 6H+
Equation : ; ;

4th equilibrium : Al2O3 + H2O = 2AlO2- + 2H+

Equation : ;

TUGAS :
S1 : tentukan rentang pH dimana
Al2O3 stabil
S2 : buat diagram E - pH untuk
sistem Fe H2O yang
melibatkan komponen : Fe,
Fe(OH)2, Fe2+, Fe3+, Fe(OH)3
dan HFeO2-

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 CORROSION KINETICS
OVERPOTENTIAL
When corrosion of a metal consists of 2 processes
corrosion potential Ecorr = compromise between various
equilibrium potentials of anodic & cathodic reactions involved
The difference between the resultant potential (E) and
individual reaction equilibrium potential (Eeq) = polarization,
quantified as overpotential:
Anodic polarization anodic processes are accelerated by
moving potential in the positive (noble) direction ; cathodic
polarization cathodic processes are accelerated by moving
potential in the negative (active) direction
There are 3 distinct types of polarization which are additive :

where act : activation overpotential charge transfer

controlled reaction conc : concentration overpotential
mass transfer controlled reaction
iR : ohmic drop electrolytic resistivity
act : controlling factor during corrosion in strong acids; conc 18
ACTIVATION POLARIZATION
act is due to retarding factors that are an inherent part of the
kinetics of all electrochemical reactions
for reaction such as 2H+ + 2e- H2 : variability of electron
transfer rate from a metal to hydrogen ions the rate of
hydrogen evolution from different metals can vary greatly
The most important variable that cause large differences in the
rate of hydrogen evolution on metallic surfaces : the exchange
current density, io

Exchange current density of hydrogen (io,H) on Pt >> on Hg and

Pb Hg is often added in alkaline batteries, and Pb acid 19
battery can produce power in a highly acidic environment in a
 Exchange current density may change rapidly with changing
conditions at a metallic surface exposed to a given
environment no simple method to estimate the exchange
current density for a specific system
Exchange current density must be determined experimentally
by scanning the potential with a laboratory set up : a
potentiostat/galvanostat, a sample = working electrode (W), an
auxiliary electrode (Aux) and a reference electrode
A general (Ref) of
representation
connected to cell by a Luggin capillary
polarization of electrode
supporting one specific
reaction : Butler-Volmer
equation

where
: charge transfer barrier
(symmetry coefficient) for
anodic/cathodic reaction, usually
0.5
n : the number of participating
electrons
R : universal gas constant
20
T : absolute temperature
 Butler-Volmer equation consists of 2 terms 2 half-cell
reactions; example : polarization of palladium electrode
immersed in a solution containing similar concentration of Fe 3+
and Fe2+ ions reversible reaction : Fe3+ + e- Fe2+

cathodic (< 0) the second term of Butler-Volmer equation

becomes negligible and
where cathodic Tafel slope of - logi plot, bc
anodic (> 0) the first term becomes negligible ; ;

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CONCENTRATION POLARIZATION
= polarization component caused by concentration changes of
a chemical species adjacent to the corroding surface (the
chemical participating in corrosion process is in short supply)
the mass transport of that species to the corroding surface
become rate controlling
A frequent case of concentration polarization : the cathodic
process = reduction of dissolved oxygen (in low/ppm
Mass transport to surface is
concentration) governed by 3 forces: diffusion,
migration and convection ; No
electric field migration is
negligible ; no convection force in
stagnant condition mass
transport is purely diffusion
controlled
The flux of a species O from bulk to
surface (Ficks 1st law) :
JO : the flux of species O (mol s-1
cm-2)
DO : diffusion coefficient of O (cm2 s-
1
)
CO: concentration gradient of 22O
 The concentration distance
profile at the metal surface
approximated by a simple
t=
0 gradient
Well-mixed solutions
t=
concentration is constant in
the bulk (convective region)
t=

t1
im
tL

= the horizontal line where C

= C0
The Nernst diffusion layer =
region where concentration
drops to 0 at the electrode
surface; its thickness ()
depends on the solution : in
stirred
Species O is consumed by cathodic aqueous
reaction at thesolution =
corroding
0.01 0.001
surface depleted CO = 0 cathodic mm,
current in stagnant
is limited,
When i < i solution = 0.05 mm
c L
T = 298.16 K

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OHMIC DROP = OHMIC OVERPOTENTIAL (iR)
Ohmic drop = i x R between anodic & cathodic sites of
corrosion process :
both sites are adjacent to each other iR is negligible, when
the environment = conductive electrolyte
both sites are separated iR = important factor
Water Resistivity: expressed as where R = measured
resistance across the cell, A = cross-sectional area of each
electrode, l = the gap separating the electrodes

Soil Resistivity = f(soil moisture and concentration of soluble

salts) indicator of soils corrosivity : the lower the resistivity,
the higher the corrosivity
Water content & ionic species concentration soil resistivity 24
 Four-Pin Method (Wenner Method): alternating current from Soil
Resistance Meter flow through the soil between pins C1 & C2,
potential is measured between pins P1 & P2
resistivity is computed according to where:
= soil resistivity ( cm); a =distance between probes (cm); R
= soil resistance () read by instrument; = 3.1416
The resistivity values obtained = the average resistivity of soil
to a depth equal to the pin spacing = depth equal to that of
buried system ; typical probe spacing = 0.5 1 m

25
GRAPHICAL PRESENTATION OF KINETIC DATA
(EVANS DIAGRAM)
Useful for explaining parallel corrosion processes; based on
mixed-potential theory any electrochemical reaction can be
divided into oxidation and reduction reactions with total charge
= 0 net measurable current = 0, the corroding metal is
neutral (all electrons produced by metal corrosion are
consumed by one or more cathodic processes)
Processes : purely activation controlled and/or concentration
- each reaction = a straight line on
controls at least one of the corrosion processes
an E log i plot : anodic processes
Activation Controlled Process Tafel slope > 0 ; cathodic
processes Tafel slope < 0
- Carbon steel in deaerated solution
pH 0, at 25C : anodic reaction : Fe
Fe2+ + 2e-
cathodic reaction : 2H+ +
2e- H2
corrosion potential (Ecorr) =
potential of sharp peak when
current = 0 ( 0.221 V vs SHE) =
intercept of anodic and cathodic
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Concentration-controlled Processes
One of the reactions is limited by mass transport of reactant to
the metallic surface being corroded a second cathodic
reaction O2 + 4H+ + 4e- 2H2O
Total cathodic currents (H2 evolution + O2 reduction) anodic
current

CS/stagnant aerated solution at CS/agitated aerated solution at

25C, pH 5 25C, pH 5
O2 reduction also depends on the solution agitation level:
stagnant icorr = 6.3 A/cm2, agitated icorr = 63 A/cm2 ; Ecorr
: - 0.33 to 0,224 V 27
LATIHAN
Besi terkorosi di dalam larutan
asam pH = 0. Hitung potensial dan
rapat arus korosi, jika diketahui
rapat arus pertukaran hidrogen di
permukaan besi = 10-8 A/cm2, dan
rapat arus pertukaran besi = 10-9
A/cm2.
pH = 0 V
dari gambar H = - 1,25
V/dekade
Tafel katodik :
(1)
Korosi EFe = E0Fe = - 0,4 V
dari gambar Fe = 1,25 V/dekade

Tafel anodik :
substitusi
(2) (1) ke (2) :
ikor = A/cm2
(1) :

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 Besi terkorosi di dalam air pH
5 yang mengandung oksigen
terlarut dengan rapat arus
limit 6,3 x 10-5 A/cm2. Hitung
potensial dan rapat arus
korosi besi.
Tafel anodik :

reaksi katodik terkendali oleh

perpindahan massa ikorosi =
ilimit

Ekorosi =

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