ELECTROCHEMICAL KINETICS

i.e. how fast will corrosion occur? A knowledge of kinetics will help develop corrosion resistant structures through rate control mechanisms ______________________________ FARADAYS LAW Current = I = Ampere = 1 Coulomb of charge (6.2x1018 electrons)/second

Ita m= Faradays Law: n where m mass reacted

n = no. of equivalents exchanged = Faraday constant (96500C) a = atomic weight t = time equivalents? - no. of electrons moving according to electrochemical reaction e.g. Zn + 2H+ Zn++ + H2 n=2

CORROSION RATE (r) at a surface of area A

r= m ia = tA n
where i = current density = I/A

hence corrosion rate i not I Thus if the same current is concentrated on a smaller area the corrosion rate increases Also, r 1/A

If the density (D) of the material is known, corrosion rates can be conveniently expressed in terms of actual depths e.g.

r = 0.00327

ai mm/year nD

for iron: For a current density of 1A/cm2,

r = 0.00327

(55.8)(1) = 11.88m/year ( 2)(7.68)

These results often tabulated often tabulated: Here equivalent weight has accounted for alloy constituents of different valancies and is merely a weight ratio combination of n/a values for each constituent.

EXCHANGE CURRENT DENSITY

At equilibrium in a reaction such as 2H+ + 2e- H2 electron traffic must be the same in both directions (forward and reverse) i.e. 2H+ + 2e- H2 so at equilibrium:

r f = rr =

io a n

where io = exchange current density

Relates to the current flowing in an equilibrium situation (until the material is used up) Like E, io cannot be calculated from first principles and must be experimentally determined Unlike E, io is very influenced by the surface on which the reaction occurs Platinum: io is very high - Pt used as a catalyst _______________________________

Polarization
Polarization = potential change from equilibrium condition caused by change in surface reaction rate

Cathodic polarization c:
Electrons are supplied to the surface - build-up in the metal due to slow reaction rate - causes surface potential E to become negative to equilibrium potential c = negative

Anodic polarization a:
Electrons are removed from the metal - deficiency results in positive charge build-up - due to slow liberation of electrons by surface reaction a = negative There are two types of polarization: Activation polarization and concentration polarization ___________________________

Activation Polarization
When some step in the half-cell reaction controls the rate of electron flow we have activation control and deviation from equilibrium - hence activation polarization of the corrosion process Steps? consider hydrogen evolution at a metal surface ions converted to atoms atoms converted to gas molecules converted to gas

H+ + e- H H + H H2 H2 + H2 bubble

Rate of reaction controlled by slowest step Activation polarization = overpotential = a

a = a log c = c log
where

ia io ic io

= Tafel constant, ia = anodic current density and ic = cathodic current density

whenever = zero (i.e. no polarization), i = io

also - log i Experimentally easy to verify Firstly polarization diagram for the aqueous environment

Lines have a gradient of and meet at the overpotential value Here = 0 (see the standard emf table) Also lines meet at io the exchange current density Below this reversible half-cell potential reduction occurs whilst above it oxidation occurs 2H+ + 2e- H2 H2 2H+ + 2e-

Remember Faradays Law? i = measure of corrosion rate increase ia or ic and you increase the corrosion rate

Concentration Polarization
Here the reaction rate limited by diffusion in solution

If the rate is low and/or concentration of H+ is high - there is an adequate supply of ions at the surface If not a depletion zone results From Nernst equation depleting H+ results in decreasing electrode potential decrease = conc = and
i 2.3RT log1 c i n L in the cathodic case
B

iL =

Dz nCB

where CB = bulk H+ concentration = thickness of concentration gradient Dz = diffusivity of reacting species, z

B

Thus, to increase iL increase T (which decreases Dz) or increase CB or increase the agitation of the solution (decreases ) Concentration polarization usually limited to cathodic reduction sites anodic regions number of metal atoms usually unlimited depletion doesnt exist

Here plots of conc (cathodic concentration polarization) v. reaction rate (i) and solution conditions More broadly total cathodic polarization = activation + concentration values = T ,c = c log

i ic 2.3RT log1 c + i io n L

and the corresponding anodic polarization is still

a = a log

ia io

_______________________

Corrosion potential in engineering systems

4 parameters effectively describe the corrosion in an engineering system: c a io and iL Knowledge (or educated guesses) allow for corrosion to be predicted hence engineered Key principle = law of conservation i.e. all cathodic reactions = all anodic reactions

Anodic reactions: M Mn+ + neor as a redox reaction: Mn+ M(n+1)+ + eCathodic reactions: Evolution of H2: 2H+ + 2e- H2 (acid) 2H2O + 2e- H2 + 2OH- (neutral/alkali) Reduction of dissolved O2: O2 + 4H+ +4e- 2H2O (acid) O2 + 2H2O + 4e- 4OH- (neutral/alkali)

Redox reduction: Mn+ + e- M(n-1)+

Example:
Zn in acid solution: We know that Zn will oxidize to Zn++ and H+ will reduce to H2 In an actual system e.g. sea water what will the potential of the system be? (hence how fast will corrosion occur) Each half-cell has its own polarization characteristics hence its own io value Both reactions exist on the same surface (the metal anode) and cannot exist separately or independently the polarization caused by each reaction must be the same i.e. Ecorr Ecorr = corrosion

potential or mixed potential

Diagrammatically very revealing:

note: Icorr and Ecorr

At Ecorr,

a log

ia i = c log c io io

Importantly: corrosion rate icorr = ia = rate of anodic dissolution in a system equilibrium

Importance of io and half-cell kinetics

shows same as before but with iron superimposed on top

For iron half-cell electrode potential whereas for Zn it is -0.76V

Fe Fe2+ + 2e- is -0.44V

Zn should corrode faster in the aqueous environment where H+ H2 has a potential of zero erm no For Zn potential is higher but for Fe icorr is higher icorr relates to corrosion rate so Fe corrodes faster than Zn, but at a lower equilibrium potential must differentiate between half-cell thermodynamic data and half-cell kinetic data READING TOPICS Effect of added oxidizer to a corrosion system Experimental polarization curves Galvanostatic circuits Design and use of polarization cells