Evans Diagrams

Where we left off

Tafel Equation

Butler-Volmer Equation

where: I = electrode current, m!s Io= e"change current densit#, m!$m% E = electrode !otential, V Eeq= equili&rium !otential, V = electrode active surface area, m% T = a&solute tem!erature, ' n = num&er of electrons involved in the electrode reaction ( = (arada# constant ) = universal gas constant * = so-called s#mmetr# factor or charge transfer coefficient dimensionless The equation is named after chemists +ohn lfred Valentine

Butler-Volmer Equation - .igh (ield /trength

(1 ) nF a ia ` = i0 exp RT at high anodic overpotential nF c ic ` = i0 exp RT at high cathodic overpotential
ia and ic are the exhange current densities for the anodic and cathodic reactions

These equations can be rearranged to give the Tafel equation which was obtained experimentally

Butler Volmer Equation - Tafel Equation

c = c = a =
RT RT ln i0 ln ic c nF c nF 0.059 0.059 log i0 log ic at !5 0 cn cn cathodic reaction anodic reaction

0.059 0.059 log i0 log ia at !5 0 (1 c ) n (1 c ) n

The equation is the well known Tafel equation

= a + b log i
a= b= 0.059 0.059 ln io or a = ln io n (1 ) n 0.059 0.059 or (1 ) n n

0urrent Voltage 0urves for Electrode )eactions

Without concentration and therefore mass trans!ort effects to com!licate the electrol#sis it is !ossi&le to esta&lish the effects of voltage on the current flowing1 In this situation the quantit# E - Ee reflects the activation energ# required to force current i to flow1 2lotted &elow are three curves for differing values of io with = 0.51

0urrent Voltage 0urves for /ingle Electrode )eactions

"oltage

#lectrochemical reactions of different i0 or degrees of reversibility

The i# curves from the previous slide have been rotated$

urrent

/ingle 0hemical )eaction

%nly at appreciable over& potentials does the reverse reaction become negligible

't #e the forward and reverse currents are equal

#lectrochemical reaction which has a large exchange current density( i0( This means that a small applied voltage results in an appreciable increase in current$

#lectrode reactions which have a high exchange current density are not easily polarised$ #xamples are the hydrogen evolution reaction on )t and 'g l * e 3 g 4 0lThe +*,+!-)t. and 'g,'g l make good reference electrodes because they are not easily polarised

#lectrochemical reaction in which the i0 value is very low$ This means that it takes an appreciable over& potential to produce a significant current$

This electrode is easily polarisable since a small current would result in a significant change in voltage

11

t low over!otential the Butler Volmer equation is linear 5/tern 6ear# equation7

nF i = io RT

1!

/o far we have loo8ed mainl# at single electrochemical reactions

KINETICS OF AQUEOUS CORROSION

nodic and cathodic reactions are cou!led at a corroding metal surface

/chematics of two distinct corrosion !rocesses1 5a7 The corrosion !rocess , 4 ; ,n4 4 ) showing the se!aration of anodic and cathodic sites1 5&7 The corrosion !rocess involving two 9: cathodic reactions1

1utler "olmer graphs for two electrochemical reactions

/agner Traud 0ethod

The cathodic and anodic reactions are drawn together on the same graph to show how the currents are equal at the corrosion potential

 <ote in the !revious diagram that:

ia = ic = icorr

at the corrosion !otential

Ecorr

Ecorr is a mi"ed !otential which lies &etween 5Ee7c and 5Ee7a1 In this case it is closer to 5Ee7a &ecause the i= and
the 8inetics of the anodic reaction is faster1 The metal dissolution is driven &# the anodic activation over!otential

>a = Ecorr - 5Ee7a >c = Ecorr - 5Ee7c

The cathodic reaction is driven &# the cathodic activation over!otential The thermod#namic driving force

?E = 5Ee7c - 5Ee7a
is usuall# large enough to !ut Ecorr in the Tafel region for &oth reactions, i1e1 the reverse reaction is negligi&le1

?E

Evans Diagrams
2t is convenient to represent the linear plots of i and E as log i/E plots with the negative cathodic current plotted positively( i$e$ both the anodic and cathodic current appear in the positive quadrant$ The linear region gives us the Tafel slopes The i0 for the individual reactions can be obtained by extrapolating back to -Ee.a and -Ee.c if these values are known$

Evans Diagrams
The intersection of the two curves at Ecorr gives us icorr ;f course #ou do not see the !ortion of the E$logic and E$logia at !otentials more !ositive and more negative of Ecorr res!ectivel#1 .owever, it is im!ortant to realise that the# e"ist1 I &elieve it is worthwhile to loo8 at #our Tafel t#!e measurements as a linear re!resentation of current and voltage1 The logarithmic !lots involve a mathematical mani!ulation of data and errors can &e introduced1 <evertheless Evans Diagrams are a convenient

Evans Diagrams
2n this case the cathodic reaction with the higher oxidation potential is controlling the reaction

Evans Diagrams
2n this example because of the faster kinetics$ the cathodic reaction taking place at the lower oxidation -*ve. )otential is influencing the corrosion rate more(

Evans Diagrams
The situation in the !revious e"am!le often occurs for a metal corroding in acid, com!ared with the metal corroding in dissolved o"#gen1 Des!ite the thermod#namic driving force, Ee, &eing greater for o"#gen than .%$.4, the acid corrosion is faster1 In some cases the o"#gen and acid have a s#nergistic effect1 (or e"am!le in the case of <i corrosion1 The reaction is quite slow in sul!huric acid 5=1@ ,7 and it is also slow in water saturated with air at !. A1 In the latter case a !assive !rotective o"ide film is formed1 .owever, in the !resence of sul!huric acid and air1 The corrosion rate is relativel# ra!id1 The acid dissolves the !rotective o"ide film allowing o"#gen to corrode

Evans Diagrams
The relative corrosion rates of metals de!ends on the i0 and mass transfer1 With acid corrosion: %.4 4 e B .%

i= can var# from 9=-C - 9=-9%

cm-%

The Tafel slo!e 9%= mV$decade (or o"#gen corrosion ;% 4 .% ; 4 :e B :;. I= is difficult to difficult to determine &ecause it is ver# low, &ut it is of the order of D9=-9= The Tafel slo!e E9%= mV$decade cm-%

E"change 0urrent Densities in 9 ,olal .%/;:

Electrode ,aterial 2latinum )hodium <ic8el 6old Tungsten <io&ium Titantium 0admium ,anganese Iead ,ercur# log9=5 $cm% C1= C19 C1F @1% @1: @1G F1H H1% 9=1H 9=1G 9% 9%1C 2alladium

* Values for /ome )eactions

Metal 2t 2t .g .g <i g System (eC4 4 e 3 (e%4 0e:4 4 e 3 0eC4 Ti:4 4 e 3 TiC4 %.4 4 %e 3 .% %.4 4 %e 3 .% g4 4 e 3 g =1@H =1A@ =1:% =1@= =1@H =1@@

Evans Diagrams
The slowest reaction controls the rate of corrosion$ 3ormally this is the cathodic reaction$ 2n this example4 ' small changes in kinetics of cathode have a large effect on corrosion rate$ ' small changes in kinetics of anode have small effect on corrosion

,ass Transfer 0ontrol

If the cathodic reagent at the corrosion site 5e1g1, dissolved ;% in the ;% reduction7 is in short su!!l#, mass transfer of the reagent can &ecome rate limiting1 The cathodic charge-transfer reaction at the metal$solution interface is fast enough to reduce the concentration of the reagent at interface 5cathodic sites7 to a value less than that in the &ul8 solution1 This sets u! a concentration gradient and the nFD Cdiffusion b Cs reaction &ecomes controlled1 i =

(i )

c 5im

nFD( Cb ) = = ( icorr ) max

,ass Transfer 0ontrol

When the corrosion rate is limited &# mass transfer it can &e increased &#: B# altering the &ul8 concentration B# stirring and reducing the thic8ness of the <ernst diffusion la#er nFD( Cb C s ) ic = nFD( Cb ) ( ic ) 5im = = ( icorr ) max /here 4 ic = the cathodic current n = the number of electrons F = the 6araday constant Cb = the bulk concentrat ion C s = the surface concentrat ion = the 3ernst diffusion layer

,ass Transfer 0ontrol

'ctivation ontrolled 7iffusion or 0ass Transfer ontrolled

,ass Transfer 0ontrol

2ncrease in corrosion potential( #corr( and the corrosion current( icorr( due to an increase in mass transfer caused by stirring$

,i"ed Transfer 0ontrol

The cathodic Tafel plot often shows deviation from ideal Tafel behavior )olari8ation curve for the cathodic process showing4 1$'ctivation polari8ation !$9oint activation& concentration polari8ation :$0ass transport& limited corrosion control

Evans Diagrams
'nodic ontrol athodic ontrol

0ixed ontrol

6alvanic 0orrosion - Influence of i=

The peak height of the adsorption,desorption processes is directly proportional to scan( i$e$( the charge i# or area under the curve$ This contrasts with a diffusion process where the peak height is proportional to the square root of the scan rate$

0#clic Voltammetr# at a 2t Electrode in /ul!huric cid /olution

6ormation of adsorbed + -)t&+.

%xygen 'dsorption )t&%

%xygen #volution %! J

;eduction of adsorbed + -)t&+. +ydrogen #volution +! J ;eduction of adsorbed oxide film -)t&%.