UN1001: REACTOR CHEMISTRY AND CORROSION Section 13: Kinetics of Aqueous Corrosion By

D.H. Lister & W.G. Cook
Department of Chemical Engineering University of New Brunswick
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UN1001: Section 13: Kinetics of Aqueous Corrosion

KINETICS OF AQUEOUS CORROSION
Anodic and cathodic reactions are coupled at a corroding metal surface

Schematics of two distinct corrosion processes. (a) The corrosion process M + O Mn+ + R showing the separation of anodic and cathodic sites. (b) The corrosion process involving two cathodic reactions.

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UN1001: Section 13: Kinetics of Aqueous Corrosion

The ³corrosion current´ .. icorr .. related to amount of metal corroded by Faraday¶s law«

icorr t !

nFw M

n = no. electrons involved in metal dissolution ( valency); F = Faraday constant (96,500 coulomb/mol); w = mass corroded metal; M = molecular weight of metal. Note: there may be more than one cathodic reaction (i.e., more than one ³ic´) and more than one anodic reaction (i.e., more than one ³ia´..e.g. for alloy); icorr = ™ ia = -™ic
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UN1001: Section 13: Kinetics of Aqueous Corrosion

Also: because areas of anodic regions, Aa, are generally different from areas of cathodic regions, Ac, CURRENT DENSITIES are generally not equal « thus « while ia = -ic Aa  Ac So Ia = ia/Aa  ic/Aa = Ic «

(remember examples of rapid perforation arising from large cathode Vs small anode combinations).

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UN1001: Section 13: Kinetics of Aqueous Corrosion

Corrosion consists of charge transfer reactions « e.g. « anodic Mlattice M+surface + e Mn+surface + (n-1)e cathodic O2 surface + 2H+ + 2e H2O2 surface H2O2 surface + 2H+ +2e 2H2Osurface and mass transport « e.g. « anodic Mn+surface Mn+solution cathodic O2 solution O2 surface H2Osurface H2Obulk solution
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The anodic reactions and the cathodic reactions in a system can be studied INDIVIDUALLY by electrochemical methods « e.g.. the changes in potential of an electrode caused by changes in the current flowing through it (or vice versa) can be measured « i..UN1001: UN1001: Section 13: Kinetics of Aqueous Corrosion 13: Activation control is when the corrosion is controlled by charge transfer reactions « EITHER the anodic charge transfer OR the cathodic charge can control. we can measure the POLARIZATION. 6 .e.

i. but ia = -ic = io (i. = 0. E = Ee.. E.UN1001: Section 13: Kinetics of Aqueous Corrosion Consider metal dissolution and metal deposition « M Mn+ + ne If we drive the reaction (with our electrochemical apparatus) in the anodic direction. io) 7 . required to give a net dissolution of metal and the equilibrium potential. the forward and backward reactions are equal and the rate corresponds to the exchange current. At equilibrium.e. we can measure the overpotential (the difference between the applied potential. i = 0. Ee) and the net current.

T = absolute temperature. cathodic) reaction. 8 . = ³symmetry coefficient´ ( 0. is the Butler-Volmer equation « ® ¨ nF ¸ nF ¸¾ ¨ L ¹  exp©  [1  F ] L ¹¿ i ! io ¯exp© F RT ºÀ ª ° ª RT º where « R = gas constant.UN1001: Section 13: Kinetics of Aqueous Corrosion The expression relating the OVERPOTENTIAL. F = Faraday (96. n = no. charges transferred ( valency). i. the second term in { } describes the backward (metal deposition. to the net current. . anodic) reaction.5). io = exchange current density (a constant for the system). The first term in { } in B-V describes the forward (metal dissolution.500 coul/mol).

UN1001: Section 13: Kinetics of Aqueous Corrosion A plot of the B-V equation for the metal dissolution/deposition reaction gives the polarization curve: Current-potential relationship for a metal dissolution (M Mn+) / deposition (Mn+ M) process 9 .

for metal dissolution: or ¨ nF ¸ ia ! io exp© F La ¹ ª RT º i (high overpotential or high-field L a ! ba log io approximation) ba ! 2. the curve is symmetrical about (i = 0. Thus.303RT F nF where « Tafel coefficient.5.UN1001: Section 13: Kinetics of Aqueous Corrosion If the symmetry coefficient = 0. the reaction is essentially all in one direction « one of the terms in the B-V-E is negligible and can be dropped.303 RT bc !  (1  F )nF 10 . Note: At large enough overpotentials. The Tafel coefficient for metal deposition: 2. Ee) and the B-V equation has a sinh form.

UN1001: Section 13: Kinetics of Aqueous Corrosion Note Also: In the narrow region of small overpotentials. the relation becomes linear « In the linear region « i ! io nF L RT (low overpotential or low-field approximation) 11 .

12 . the curve is shallow and a large current is obtained for a small overpotential « the reaction is not easily polarized (approaching non-polarizable). io.UN1001: Section 13: Kinetics of Aqueous Corrosion If a reaction has a large exchange current.

io. 13 .UN1001: Section 13: Kinetics of Aqueous Corrosion If a reaction has a small exchange current. the curve is steep and a large overpotential is needed for a small current « the reaction is readily polarized.

flows « similarly. ia. then the reaction must move away from equilibrium so that a net cathodic current.UN1001: Section 13: Kinetics of Aqueous Corrosion Consider now a reaction that is cathodic to the metal dissolution « viz « O + ne R If this is coupled to metal dissolution in the corrosion process. -ic. flows. the metal dissolution « M We know « ia = -ic (=icorr). 14 . Mn+ + ne must move away from equilibrium so that a net anodic current.

UN1001: Section 13: Kinetics of Aqueous Corrosion We plot the cathodic reaction on the same diagram as the anodic reaction « Butler-Volmer expression« Current-potential relationships for a metal dissolution/deposition and an accompanying redox reaction showing how the two reactions couple together at the corrosion potential. Ecorr 15 .

e.(Ee)a Usually. 16 ..Ecorr And the cathodic reaction is driven by the cathodic activation overpotential: Note: the thermodynamic driving force for corrosion.(Ee)c = (Ee)c . the reverse reactions are negligible) ± unless oxide films interfere. ¨Etherm is large enough to put Ecorr in the Tafel regions for both reactions (i.UN1001: Section 13: Kinetics of Aqueous Corrosion Note: ia = -ic (=icorr) at one spot on the diagram « the corrosion potential Ecorr Ecorr is the mixed potential « (Ee)a < Ecorr < (Ee)c Metal dissolution is driven by the anodic activation overpotential: A a A c = Ecorr . ¨Etherm « ¨Etherm = (Ee)c .

UN1001: Section 13: Kinetics of Aqueous Corrosion The coupled portions of the curves for the anodic and cathodic reactions (i. logarithm of the current. This is the Evans Diagram Evans diagram for the corrosion process M + O Mn+ + R 17 . ic ±ve) are usually plotted as potential vs. ia +ve.e. with the ±ve sign of the cathodic curve neglected « Both curves appear in the +ve quadrant..

the bigger the difference in equilibrium potentials (i. the greater the corrosion)« 18 . The exchange currents. icorr. with Tafel slopes indicated earlier. (io)a and (io)c.e. don¶t forget that the origin ( i = 0) cannot be shown on a logarithmic plot. The intersection of the two curves in the Evans diagram occurs at the corrosion current.UN1001: Section 13: Kinetics of Aqueous Corrosion The straight line portions of the curves are the Tafel region... can be obtained by extrapolating the Tafel lines back to the equilibrium potentials (Ee)a and (Ee)c « N. the bigger the value of icorr (i.B. N. the bigger the value of ¨Etherm).B.e.

so « ( aA)´ < ( aA)´´ Note: 19 .(Ee)a] < for reaction´´ «.(Ee)a] so « i´corr < i´´corr Also: anodic activation overpotential for reaction´ [E´corr . (Ee)c´´ and (Ee)c´ ¨E´therm [= (E´e)c .(Ee)a] < ¨E´therm [= (E´e)c .UN1001: Section 13: Kinetics of Aqueous Corrosion Two possible cathodic reactions Evans diagram for a metal dissolution coupled separately to two cathodic reactions with distinctly different equilibrium potentials.

e. so that i´´corr < i´corr « i. in which the impact of relative kinetics is greater than the thermodynamic driving force. Evans diagram for a metal dissolution coupled separately to two cathodic reactions. ¨Etherm Even though (Ee)c´´ > (Ee)c´ .UN1001: Section 13: Kinetics of Aqueous Corrosion Two possible cathodic reactions . activation overpotential ( aA)´´ < ( aA)´. the corrosion couple with the smaller thermodynamic driving force (E´therm ) produces the larger corrosion current « kinetics are 20 controlling.. .different kinetic factors.

Pourbaix Diagram for Ni). acid corrosion is faster. Arises from kinetic factors « and .UN1001: Section 13: Kinetics of Aqueous Corrosion This situation often occurs for a metal corroding in acid. compared with corroding in dissolved oxygen « though the thermodynamic driving force is greater in oxygen (remember.

I o H .

bc H  / H2 / H2 = ~ 10-3 ± 10-2 A/m2 120 mV/decade  (« depending on metal surface) while « 2 / H2 and 2 / H 2O     .

I o .

bc O ~ > 10-10 A/m2 120 mV/decade (« depending on metal surface). 21 .

) Differences in steepness of curves mean that activation overpotentials are different « and polarizations are different (steep curve strongly polarized). reaction with smaller exchange current.. io. b.e. (Remember. and/or larger Tafel coefficient. large b also means curve close to axis ± with steep slope. 22 . small io means that curve close to vertical axis.UN1001: Section 13: Kinetics of Aqueous Corrosion Corrosion Rate Controlled by Anodic or Cathodic Reactions Overall corrosion rate controlled by slower reaction « i.

icorr. Evans diagram showing the impact on the corrosion current. A2) or a slow cathodic process (C1. and potential.UN1001: Section 13: Kinetics of Aqueous Corrosion Cathode reaction in diagram strongly polarized « controls corrosion « small changes in kinetics of cathode have large effect on corrosion rate. small changes in kinetics of anode have small effect on corrosion rate. C2) 23 . of varying the kinetics of a fast metal dissolution (A1. Ecorr.

UN1001: Section 13: Kinetics of Aqueous Corrosion Mass Transfer Control (not to be confused with erosion-corrosion in which film formation is involved) If the cathodic reagent at the corrosion site (e.g. the cathodic charge-transfer reaction is fast enough to reduce the concentration of the reagent at the surface corrosion site to a value less than that in the bulk solution. Then. dissolved O2 in the O2 reduction) is in short supply.. mass transfer of the reagent can become rate limiting. 24 .

UN1001: Section 13: Kinetics of Aqueous Corrosion Activation control Mass transfer control 25 .

UN1001: Section 13: Kinetics of Aqueous Corrosion From the simple Nernst Diffusion Layer model « flux of cathodic reagent to surface. given by « s b  D CO  CO J ! H . J.

at steady state. s b ic  D CO  CO ! H nF . so that.

CO 0« . s *In the limit.

ic lim b nFDCO ! ! .

). CO . (by flow. it can only be changed by altering the bulk b concentration. and/or the diffusion layer thickness.icorr max H When corrosion rate is at this limit. 26 . etc.

joint activation-concentration polarization (point 2). c infinite. Point 2: Control: activation + concentration . overpotential total = A + C Point 3: Large shift from equilibrium ± reaction rate maximum. no limitation on reagent supply ± activation control. 27 ..UN1001: Section 13: Kinetics of Aqueous Corrosion Such concentration polarization is shown on the Evans diagram (partial) Polarization curve for the cathodic process showing activation polarization (point 1).. and transportlimited corrosion control (point 3) Point 1: Small shift from equilibrium potential .

Lines 2 and 3 show the effect of increasing the transport rate of reagent 28 . improved stirring would decrease Ecorr. Ecorr.UN1001: Section 13: Kinetics of Aqueous Corrosion Effect of increasing mass transport rate (e. If anodic reaction were masstransfer controlled (difficulty of metal ions diffusing away). Increase in corrosion potential.. by stirring the solution surrounding a corroding surface).g. DISCUSS Evans diagram for a corrosion process initially controlled by the transport of cathodic reagent to the corroding surface (line 1). caused by decrease in cathodic overpotential as concentration polarization decreased.

they involve the study of polarization characteristics. current curves « i. 29 .g. evaluating the performance of a metal specimen in a test solution) often involve the construction of potential vs..e.UN1001: Section 13: Kinetics of Aqueous Corrosion Electrochemical Methods for studying corrosion (e..

UN1001: Section 13: Kinetics of Aqueous Corrosion Polarization Measurements The simple potentiostat for applying a fixed potential (relative to a reference electrode) and measuring the current (flowing from the working electrode to the counter or auxiliary electrode) « A typical arrangement of the classical potentiostat *ensure specimen potential (w. 30 . counter) constant « even though solution resistance might alter.t.r.

icorr. to yield the corrosion current. Tafel Method Measure potential and current at some distance on either side of Ecorr ± extrapolate E .UN1001: Section 13: Kinetics of Aqueous Corrosion Remember: we can only measure the net current across the specimen electrode ± at the corrosion potential there is no net current (only local anode ± cathode currents which constitute the corrosion current).log i curves (in same quadrant) back to Ecorr « Plot of the total current (iT = io + ic) versus potential showing the extrapolation of the Tafel regions to the corrosion potential. We cannot measure corrosion rate directly « though we need icorr. Ecorr. 31 .

If we know « (for the anodic or cathodic reaction) « ‡ the exchange current (io)a.UN1001: Section 13: Kinetics of Aqueous Corrosion N.B. say. ‡ the equilibrium potential (Ee)a. ba. Ecorr) we can calculate the corrosion rate « icorr ! io exp¯ . then from one measurement (of the corrosion potential. ‡ the Tafel coefficient.

Ecorr  .

Ee a ¾ 2.303 ba ¿ À We don¶t usually know these. 32 . though.

Sc 33 . mV).UN1001: Section 13: Kinetics of Aqueous Corrosion Linear Polarization Method Valid for corrosion under activation control.e..B. ¨i for summed curve = ia + |¨ic| (¨ia=x) Slope of summed curve (measure E vs i for system) is difference between slopes of curves for the coupled reactions: Sa . ¨E § 10 N. Involves applying a small perturbation to the potential around Ecorr (i.

303icorr d di ! Sc ! redox bc 2.303 ba  bc ( Polarization Resistance .. The Tafel coefficient ba and (i bc must be known.303icorr slope S a ! ( x slope S c ! (E (i  x @ (E ! S a  S c (i Sa Sc or icorr ba bc 1 (i ! ™ 2. is measured. ( . 34 . For ¨E around Ecorr..UN1001: Section 13: Kinetics of Aqueous Corrosion The curves are ~linear within ~20mV ± Sa and Sc are constant. Sa and Sc are related to icorr (the required quantity): assuming the high-field approximation for the individual reactions « d di Now: ! Sa ! anodic ba 2.

35 .UN1001: Section 13: Kinetics of Aqueous Corrosion Remember: during linear polarization measurements we plot E vs i (not log i) around the corrosion potential: (E = polarization resistance (i Negative sense (E < Ecorr. i < 0) is preserved.

they passivate: Pourbaix diagram for the iron/water/dissolved oxygen system showing the effect of potential in moving the system from a corrosive (active) region (point 1) to a passive region (point 2) We can examine the kinetics via an Evans diagram « 36 .e.UN1001: Section 13: Kinetics of Aqueous Corrosion Passivation Under certain conditions of potential and pH.. some metals form protective films « i.

.g. reaction rate required to initiate film growth by precipitation of Mn+) The region attained by the metal in a given environment depends upon the cathodic reaction « i. Cr2O3 CrO42-) ³Flade´ (Ee)M/MO is the equilibrium potential for oxide/hydroxide formation Tafel region (icrit is min. .e.UN1001: Section 13: Kinetics of Aqueous Corrosion The polarization curve for the anodic reaction of a passivating metal drawn for potentials more noble than the equilibrium potential (Ee)a « Oxidative dissolution of oxide (e. where the cathodic curve cuts the above anodic 37 curve..

corrodes actively. . iinitial 38 (intersecting Tafel line) > icrit) « passivates. Cathodic Reaction 2: (Ee)C2 < Epass. however. curve intersects Tafel line for anodic reaction below icrit « passive film cannot form.UN1001: Section 13: Kinetics of Aqueous Corrosion Impact of various cathodic reactions on the corrosion current and potential for a metal capable of undergoing an active-passive transition Cathodic Reaction 1: (Ee)C1 < Epass. so (Ecorr)1 must also < Epass « corrodes actively. Cathodic Reaction 3: both passivating conditions are met ((Ee)C3 < Epass.

UN1001: Section 13: Kinetics of Aqueous Corrosion Other Corrosion Examples on Evans Diagrams (from Fontana) Velocity Effects Effect of velocity on the electrochemical behavior of an active-passive metal corroding under diffusion control. 39 .

UN1001: Section 13: Kinetics of Aqueous Corrosion only approximately zero: residual corrosion is very small. Effect of velocity on the corrosion rate of an active-passive metal corroding under 40 diffusion control .

H2 evolution occurs on platinum « 41 . when coupled « zinc corrosion increases. But.UN1001: Section 13: Kinetics of Aqueous Corrosion Galvanic Effects Isolated zinc corrodes in acid « Zn Zn2+ + 2e 2H+ +2e H2 Platinum is inert in acid.

UN1001: Section 13: Kinetics of Aqueous Corrosion Effect of galvanically coupling zinc to platinum (equal areas). NOTE: the thermodynamic driving force remains the same .

H2 evolution on Zn decreases.E ( therm ! ( Ee ) H  / H  ( E e ) Zn / Zn 2  but the kinetics change ± exchange currents on 2 Zn and Pt are different: potential increases. total 42 reaction increases .

UN1001: Section 13: Kinetics of Aqueous Corrosion Effect of H+/H2 Exchange Current The more efficient the hydrogen evolution process (i. 43 . the larger the effect of galvanic coupling « Comparison of zinc-platinum and zinc-gold couples (equal areas)..e. Pt is a very efficient cathode. the higher the exchange current).

. (Remember. corrosion [mixed] potential determined by point where total oxidation rate equals total reduction 44 rate « rates of individual processes determined by mixed potential).UN1001: Section 13: Kinetics of Aqueous Corrosion Effect of Cathode Surface Area Effect of cathode-anode area ratio on galvanic corrosion of zinc-platinum couples. Increasing cathode area increases corrosion.

45 N. actual rates depend on Tafel slopes. exchange currents. etc. more noble metal corrodes slower. more active metal becomes anode.UN1001: Section 13: Kinetics of Aqueous Corrosion Galvanic couple between two corroding metals. « without detailed information we only predict trends.B. . more noble becomes cathode. ‡ ‡ more active metal corrodes faster when coupled.

UN1001: Section 13: Kinetics of Aqueous Corrosion Effect on Passivating Metals Spontaneous passivation of titanium by galvanically coupling to platinum. 46 . Only works if passivating potential (i. Flade potential) less than E H2 / H  NOTE: Raise the possibility of anodic protection.e..

Passivating potential too noble for couple to passivate metal. If very large Pt 47 cathode coupled.UN1001: Section 13: Kinetics of Aqueous Corrosion Galvanic couple between an active-passive metal and platinum in air-free acid solution. . corrosion can be increased to P.

UN1001: Section 13: Kinetics of Aqueous Corrosion Anodic and cathodic half-cell reactions present simultaneously on a corroding zinc 48 surface. .

. icorr. and a corrosion rate (current density). Ecorr.UN1001: Section 13: Kinetics of Aqueous Corrosion Polarization of anodic and cathodic half-cell reactions for zinc in acid solution to give 49 a mixed potential.

B. N. Currents must balance for the coupled reactions. Current densities are equivalent to currents when surface areas are accounted for. 50 .UN1001: Section 13: Kinetics of Aqueous Corrosion Comparison of electrochemical parameters for iron and zinc in acid solution. demonstrating the importance of io on determination of corrosion rates.

present. 51 . Fe3+/Fe2+.UN1001: Section 13: Kinetics of Aqueous Corrosion Determination of the mixed potential Ecorr for a corroding metal M exposed to acid solution with a second oxidizer.

2 52 .UN1001: Section 13: Kinetics of Aqueous Corrosion Rates of reduction ( iFe 3 p Fe 2  and iH  p H ) and oxidation (icorr) from above.

UN1001: Section 13: Kinetics of Aqueous Corrosion No effect on corrosion when oxidizer of low io is added to an acid. 53 .

aeration.UN1001: Section 13: Kinetics of Aqueous Corrosion Effect of deaeration. . and stirring on corrosion of active-passive stainless steel 54 in neutral saltwater.

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