CH.2 CH. 2.

THERMODYNAMICS OF CORROSION

Image Source: Corrosion Doctors, www.corrosion-doctors.org

Why y Do Metal Corrode?

Any spontaneous reaction in the universe is associated with a lowering in the free energy of the system, i.e., a negative free energy change. All metals except some noble metals have free energies greater than those of their compounds. Therefore, they tend to become their compounds through the process of corrosion. As an example, take the following examples:

1 Mg + H O + O Mg(OH) , G = 596 kJ/mol 2 2 2 2 1 Cu + H O + O Cu(OH) , G = 119 kJ/mol 2 2 2 2 3 3 Au + H O + O Au(OH) , G = +66 kJ/mol 3 2 2 4 2

It is obvious from G that Mg and Cu will corrode. Au has a positive G and does not corrode. T d Tendency to t corrosion: i Mg M > Cu C >> Au A

Electrochemical Nature of Corrosion

All metallic corrosion are electrochemical reactions, i.e., metal is converted to its ions and compounds with a transfer of electrons. The overall reaction may be split into oxidation (anodic) and reduction (cathodic) partial reactions. reactions Electrochemical reactions take place in electrochemical cell.

Electrochemical Cell
Metallic Path

e-

+ ions
-

ions

Electrolytic Path

Conventional Current Flow

Electrochemical Cells
Two types:
1.

Electrolytic Cells - these are cells in which an external electrical source forces a non-spontaneous reaction to occur. (One common process is called electrolysis.) (not to be covered in this course)

2.

Galvanic Cells also called voltaic cells. In these cells, , spontaneous chemical reactions generate electrical energy and supply it to an external circuit. (e.g., corrosion, battery and fuel cell, etc.)
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e 2e lost per Zn atom oxidized Zn Zn2+ 2e gained per Cu2+ ion reduced Cu2+
Cu e

Voltmeter e e Anode Salt bridge Cathode + Zn () Na SO 2 (+) Cu

4

Zn2+ Oxidation half-reaction Zn(s) Zn2+(aq) + 2e

Cu2+

Reduction half-reaction Cu(s) Cu2+(aq) + 2e Overall (cell) reaction Zn2+(aq) + Cu(s) Zn(s) + Cu2+(aq)
Image Source: M.S. Silberberg, Chemistry: The Molecular Nature of Matter and Change, 2nd ed.

Cell Notation
Zn (s) | Zn2+ (aq, (aq 1.0M) 1 0M) || Cu2+ (aq, (aq 1.0M) 1 0M) | Cu (s)

C ll Notation Cell N i

Write components in sequence Separate phases with a single vertical line | A salt bridge or membrane is represented by a double vertical line || Included a specification of the species concentration

In a galvanic cell, voltage/potential difference between the electrodes drops to 0 as the reaction proceed (to be covered in Chapter 3).

Corrosion Process
Consider what happens when a metal electrode M is dipped into a solution containing the metal ions Mn+. The concentration of Mn+ in the metal is much larger than in the solution, l ti which hi h creates t a chemical h i l driving d i i force f that th t tends t d to t equalize li the th concentration. t ti A charge separation occurs as a result of the metals tendency to oxidize. M Mn+ (s) + ne- (M) : Dynamic equilibrium.

+ + + Zn

e-

+ +
M t l Metal Forces of ionization

+ + + + + + +
water

++++

+ + + + + + +

Cu

+ + + +

+ +

WATER

Image source: Prof. H.S. Kwons Lecture Note (corrosion.kaist.re.kr)

Solvation Shells (Hydration Sheaths) of a Cation

Schematic of the primary and secondary solvent molecules for a cation in water.

Primary shell with completely oriented water moves as and where the ion moves. Secondary shell with partly partly-oriented oriented water is a region of disturbance.. disturbance

Structure of Electrified Interfaces

The metal electrode - solution interface is also hydrated because of the charge effects.

Schematic of a charged interface and the location of cations at the electrode surface.

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Structure of Electrified Interfaces

Because of adsorbed H2O on surface and primary hydration shell, ions can only approach to within a fixed distance from the electrode: the OUTER HELMHOLTZ PLANE (OHP). The resulting double layer of charge is often treated theoretically as a capacitor..

M M

+ + + + +

Scattered ions

'Stuck' ions

S x
St Stern model d l for f EDL Simplified double layer at a metal-solution interface.

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Structure of Electrified Interfaces

The electric double layer (EDL; ) at the surface acts as a barrier to electron transfer. A potential drop develops at the metal-solution interface (At equilibrium, this potential drop is representative of the reversible (electrode) potential ) potential.) This causes the surface to polarize, i.e., the potential has to change in order for the electrons to overcome the barrier. This is called ACTIVATION POLARIZATION (CH.3).

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Corrosion Thermodynamics y
The free energy for any species, G: G = G0 + RT ln a Consider the generic chemical reaction: aA + bB = cC + dD The free energy change, G, which is a measure of driving force for the reaction to proceed, is given by the difference of the free energy of the products and reactants.

G = Gproducts Greac tan ts = (cG C +dGd ) (aG A + bGB )

0 0 0 = (cG 0 C + cRT ln a C + dGD + dRT ln aD ) (aG A + aRT ln a A + bGB + bRT ln aB ) d ac C aD = G + RT ln a b a A aB 0

In generalized form:

(aproducts ) j G = G + RT ln k (a reac tan ts )

0

IF G<0, to proceed spontaneously in the direction written. IF G=0, at equilibrium. 13

Gibbs Function and Work

Start with the First Law of Thermodynamics and some standard thermodynamic relations. We find

dU = dq + dw

dq = T dS dw = P dV + dwelectrical

dU = T dS P dV + dwelectrical

dGT = dHT T dS = dUT , P + P dV T dS

dH P = dU P + P dV

= T dS P dV + dwelectrical + P dV T dS
dGT , P = dwelectrical
Thus the Gibbs function is at the heart of electrochemistry, for it identifies the amount of work we can extract electrically from a system.
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Free Energy gy and Electrode Potential

Here we can easily see how this Gibbs function relates to a potential.

w electrical = V Q since = nF E

Q =nF

By convention, convention we identify work which is being done by the system on the surroundings has a negative sign. And negative free energy change is identified as defining a spontaneous process.

GT , P = welectrical = n F E

Note how a measurement of a cell potential directly calculates the Gibbs free energy change for the process.
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Free Energy gy and Electrode Potential

Associated with each electrochemical (galvanic) cell is a potential difference between the electrodes called the equilibrium cell potential, Ecell (also ( l called ll d reversible ibl or electrochemical l h i l potential i l or electromotive l i force emf) Ecell = Ecathode Eanode = (ea+ec)

The electrodes are considered not connected to each other so no reaction takes place on them yet, i.e., each electrode is at equilibrium with its environment. E measures the spontaneity of the cells redox reaction G = -nFEcell

Higher cell potentials (more negative G) indicate a great driving force f th for the reaction ti as written itt (i (in forward f d direction, di ti i.e., i from f left l ft to t right). i ht)
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HalfHalf -cell p potential

Synonyms

(Single) electrode potential Redox (reduction/oxidation) potential

Cathode Cathode Cat ode Potential ote t al Difference e e ce Electrolyte Ecell A d Potential Anode P t ti l Diff Difference Anode

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Standard state 298K, at unity activity

Selection of hydrogen evolution reaction as having a standard halfcell potential of 0.000V. 0 000V

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HalfHalf -cell Potential

We do not have a means of measuring the potential difference between the electrode and the solution.

?
Cathode

?
Ecell Anode Electrolyte
S l Solution: Adopt an arbitrary reference electrode.

?
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HalfHalf -cell ( (electrode) ) Potential

Measurement of voltage with electrical circuit

Connection for an electrochemical measurement

Source: P.J. Moran, E. Gileadi. J. Chem. Educ. 66 (1989) 912.

Inclusion of second interface allows combined voltage of the two interfaces to be measured with a voltmeter 20

Standard Hydrogen y g Electrode

The convention is to select a particular electrode and assign its standard d d reduction d i potential i l the h value l of f 0.0000V. 0 0000V This Thi electrode l d is i the Standard Hydrogen Electrode (SHE).

2H+(aq) + 2e H2(g)
H2 Pt

0 eH = 0.000 V + /H
2

The standard aspect to this cell is that the activity of H2(g) and that of H+(aq) are both 1. This means that the pressure of H2 is 1 atm and d the h concentration i of f H+ is i 1M, 1M given i that h these are our standard reference states.

H+
21

HalfHalf -Cell Potential Measurement

e0 = 0.762 VSHE Zn2 + / Zn

Zn and Pt are at equilibrium with their environments at standard conditions. The measured potential is the equilibrium potential at standard conditions vs SHE. vs. SHE

22

23

Standard Electrode Potential

For convenience, all half-cell reactions are written in the table in reduction form.

Zn=Zn2++2e- and Zn2++2e-=Zn are identical and represent zinc in

equilibrium with its ions with a potential of -0.762V vs. SHE.

The more positive Th iti th the e0 value l for f a half-cell h lf ll reaction ti th the greater t the tendency for the reaction to proceed as written (in reductioncathodic form) at standard conditions. The more negative the e0 value, the more likely is the reverse of the reaction as written (in oxidation-anodic form) at standard conditions. However, usually concentrations of reactants differ from one another and also change during a reaction, in that case E0cell (or e0half-cell) and the actual Ecell (ehalf-cell) are related by the Nernst Equation.
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Nernst Equation q
Consider the following reaction involving electron transfer aA + bB b + cC + dD d +
d ac C aD G = G + RT ln a a ab = nFE A B 0
d d ac RT 2.303RT 2.303RT RT ac 0 0 0 C aD C aD ln E ln K E log = E log K E=E = = a b a a ab nF nF nF nF a a A B A B 0

And for the following g half-cell reaction in reduction form aA + bB + + ne- cC + dD +

c d d ac RT aC aD 2.303RT 0 C aD e=e ln = e log a b a a ab nF nF a a A B A B 0

O1 + O2 + + ne- R1 + R2 +

e = e0 +

RT [O] ln [ ] nF R
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Activity y

Activity of a dissolved species A (aA or (A) in textbook) is equal to its concentration in moles per 1000 grams of water (molality) multiplied by the activity coefficient, f. Activity coefficients are extensively tabulated in numerous chemical and a d electrochemical e ect oc e ca handbooks. a dboo s Activity of a gas is approximated at ordinary pressures by its partial pressure in atmospheres (atm) (atm). The activities of pure solids and water are set equal to unity in aqueous solutions. At 25C, C 2.303RT/F 2 303RT/F 0.0592 0 0592 Vequivalent

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Activity y Coefficient

Source: Corrosion and Corrosion Control, H.H. Uhlig and R.W. Revie, John Wiley and Sons, 1985. 27

Prediction of Spontaneity p y
1.

2.

3. 4.

5.

First, write the half-cell reaction with the more positive (less negative) e0 for the reduction reduction-cathodic cathodic along with its half half-cell cell electrode potential. Write the other half-cell reaction as an oxidation-anodic and include its ts half-cell a ce e electrode ect ode pote potential ta Balance the electron transfer Obtain the cell reaction by adding the reduction and oxidation halfcell reactions Determine the overall cell potential, Ecell from Ecell = ec - ea

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Example 1
(Notation: e for the halfhalf - cell rxn, rxn E for the overall cell rxn.) rxn )

For the reaction 2H+ + 2e- = H2 at 25oC and 1 atm.

e = e0

(H ) 0.0592 (H ) 2.303RT log +2 2 log +2 2 = e 0 nF 2 (H ) (H )

PH2 0.0592 log + 2 e=0 2 (H ) 0.0592 e= log PH2 log(H+ )2 2

] ]
pH = log(H+ )

e= e=

0.0592 log PH2 2 log(H+ ) 2 0.0592 log PH2 + 2pH 2

e = 0.0592pH

when PH2 = 1 atm

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Example p 2
Lets consider the emf (E) of the following Cu-Zn cell at 250C.

Zn

Cu

Zn2+

Cu2+

30

Example p 2
Reduction reaction for Cu: Cu2+ + 2e- Cu and e0 = 0.337 V

e = 0.337 +

0.0592 log(Cu2 + ) 2
e0 = -0.763 V

Reduction reaction for Zn: Zn2+ + 2e- Zn and

e = 0.763 +

0.0592 log(Zn2+ ) 2

Lets assume that copper corrodes (i.e., Cu is anode, Zn is cathode). Overall reaction = [reduction rxn at cathode] [oxidation rxn at anode] Cu + Zn2+ Cu2+ + Zn emf (E) of the cell is then;

E = e cathode e anode = e Zn e Cu = 1.100 +

0.0592 (Zn2+ ) log 2 (Cu2 + )

Lets assume that the activities of Cu & Zn to be the same, then the emf, E = -1.100V (vs. SHE).

Negative E (i.e., positive G) means that the reaction is not spontaneous as written, but goes instead in the opposite direction direction.
In other words, the Zn electrode corrodes (anode), and Cu2+ plated out on the Cu electrode (cathode). 31

Example p 3

( Prb Prb. . 2 - 3 a) )

Assuming standard states for all reactants and products, determine the spontaneous direction of the following reactions by calculating the cell potential: Cu + 2HCl = CuCl2 + H2

Anodic Cu2+ + 2e- = Cu Cathodic 2H+ + 2e- = H2 E = ec ea = 0.342 V > 0

ea = ea0 = -0.342 V vs. SHE ec = ea0 = 0.000 V vs. SHE

The reaction is spontaneous as written ().

NOTE A spontaneous reaction does not necessarily mean a fast reaction !!!

32

A Note for The Sign g Notation

Note that the sign notation used in the text is different and confusing The text uses E = ec+ ea which is actually identical to the notation presented above since the text takes ea as the negative value of the anode half-cell electrode potential.

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Secondary y Reference Electrodes

If a reference electrode other than SHE is used to measure the equilibrium potential of a rxn, the potential of the reference electrode relative to SHE should be added to the measured potential if one wants to determine the equilibrium potential of the reaction relative to SHE. The reference electrodes are also used to measure the corrosion potential of a corrosion cell (E p ( corr) (to ( be covered later). )

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Potential Values for Common Secondary Reference Electrodes

(Standard Hydrogen Electrode included for reference)

Image source: A A.J. J Bard Bard, L L.R. R Faulkner Faulkner, Electrochemical Methods Methods, 2nd ed., ed John Wiley & Sons, Sons Inc., Inc 2001. 2001

Name Mercury-Mercurous Sulfate Copper-Copper Sulfate Saturated Calomel Silver Silver Chloride (saturated) Silver-Silver Standard Hydrogen

Half-Cell Reaction HgSO4 + 2e- = Hg + SO42CuSO4 + 2e- = Cu + SO42Hg2Cl2 + 2e- = 2Hg + 2ClAgCl + e- = Ag + Cl2H+ + 2e- = H2

Potential, V vs. SHE +0.615 +0.318 +0.241 +0 222 +0.222 +0.000

35

Reference Electrode Conversion Scale

Image source: R.G. Kelly et al., Electrochemical Techniques in Corrosion Science and Engineering, Marcel Dekker Inc., 2002.

36

Example p Problems
A corrosion potential of -0.229 V versus SCE was measured for a corroding metal. What is the potential versus (a) SHE, (b) Ag/AgCl (saturated), (c) Cu/saturated CuSO4?

(a) Ecorr vs. ref 1 = Ecorr vs. ref 2 + eref 2 vs. ref 1 Ecorr = Ecorr vs SCE + eSCE vs. SHE eSCE = 0.241 V vs. SHE Ecorr = -0.229 + 0.241 = 0.012 V vs. SHE (b) & (c) Home Exercise

37

Homework Problems

Problems 3, 5, 6, 12 of Chapter 2 in textbook.

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