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PENGENDALIAN
KOROSI
ELEKTROKIMIA KOROSI
TERMODINAMIKA KOROSI
KINETIKA KOROSI
3,4,5
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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
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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) :
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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
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3rd equilibrium : 2Al3+ + 3H2O = Al2O3 + 6H+
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
: charge transfer barrier
(symmetry coefficient) for
anodic/cathodic reaction, usually
0.5
n : the number of participating
electrons
R : universal gas constant
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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+
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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
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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
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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
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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 :
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