Corrosion Engineering

Lecture 12
CHE 311
Thermodynamics of Aqueous Corrosion
 Thermodynamics is a very important science in the field of metallic corrosion. It
describes how equilibrium conditions change as we change the environmental
conditions. With thermodynamics we can determine if the corrosion reaction will
occur or not. Finally thermodynamics relates the free energy to the electrode
potential. A very important remark is that thermodynamics will not tell us about the
rate of the reaction. The corrosion rate concept will be discussed under the subject
of kinetics.
 Nernst Equation
 Nernst equation can be derived from the equation linking free- energy changes to the
reaction quotient (Q):
G  G 0 + RT lnQ (8.1)

 For a general cell reaction in the form:

 aA + bB mC +nD
m
a Cma nD  C  [D]n
Q a b 
a Aa B [A]a [B]b
Thermodynamics of Aqueous Corrosion
m
a Cma nD  C  [D]n
Q a b 
a Aa B [A]a [B]b

Here the (a’s) are the activity of the ionic species or the pressure for gases. The activity
for pure liquids and solids is unity. The value of ai can be calculated from the equation.
At equilibrium, G = 0 and Q corresponds to the equilibrium constant (K):
RT ln K= G 0
ai = γiMi = [ Con.] (8.4)
γi = the activity coefficient
M = the molality of the solution

In case of an electrochemical reaction, substitution of the relations:

G = - nFE and
G 0 = - nFEo

RT 2.303RT
E  Eo  ln Q Ecell  Eocell  log Q
nF nF
Thermodynamics of Aqueous Corrosion
2.303RT
Ecell  Eocell  log Q
nF
 R = 8.3143 J/mol-K
 F = 96487 coulombs / eqiv
 T – Temperature in Kelvin (K)
 The ration 2.303 RT at 25oC gives a value of 0.0591
F
 Application of Nernst Eqn.
 1 - Calculation of half-cell potential () at non-equilibrium conditions
    o  2.303RT log Q or at 25 C    o  0.0591 log Q
nF n

 2 – Calculation of cell potential [Ecell] at non-equilibrium conditions.

 Ecell  Eocell  2.3RT log Q or at 25C Ecell  Eocell  0.0591 log Q
nF n

 3 – Calculation of Ecell or  at any temperature.

 4 – Calculation of concentrations of the products and reactants of the cell.
Thermodynamics of Aqueous Corrosion
 Half Cell Reaction for metal electrode

   o  0.0591 log [M n]

n [M ]
 Half Cell potential for hydrogen electrode
2H   2e  H 2
0.059 [H ] 0.059 P
 o  =   2 log [ H  ]2
o
log 2 2
2 [H ]
 P = 1 atm. and pH = - log [H+]
0.059
o  [ 2 log[ H  ]
2

   o  0.059 pH

Ø = -0.059 pH
Thermodynamics of Aqueous Corrosion
 Principles
G   nFE

 1. When G (E cell has negative value) is positive, this means that the reaction
of the metal is not spontaneous and will not proceed as written.
 2. When G is negative (E cell has positive value), this means that the reaction
of the metal is spontaneous and will proceed as written.

ECell  R  L
Thermodynamics of Aqueous Corrosion
 Important Comments:
 • It is immaterial to where we position each electrode in the cell. The final
conclusion of which electrode will be the anode, and which one will be the
cathode; will be drawn from the direction of the overall reaction and its
value. If G is positive (+) then the overall reaction will not proceed as the
indicated reaction, but if G is negative (-), the overall reaction will proceed
as the indicated reaction.
 • The value of Gor depends on the amount of substances reacting.
This is why we multiply G or by the number of moles reacting.
Thermodynamics of Aqueous Corrosion
 Example 1:
 Predict whether or not Sn will corrode spontaneously in HCl acid solution.
 Corrosion (overall) reaction: Sn + 2HCl SnCl2 + H2 (A)
 Assume Sn in LHS of the corrosion cell and the hydrogen electrode in the RHS.
Using the emf potential values, we can write the half-cell reaction as follows:

 LHS RX: Sn 2 +2e Sn , o = - 0.136 V

 RHS RX: 2H + 2e H 2 , o = 0.0 V

Ecell = 0.0 - (- 0.136) = + 0.136 V

 We notice that Ecell is positive (+0.136 V), therefore the free energy change
( G ) is negative. Therefore reaction (A) is spontaneous as written. It proceeds
from left to right as indicated by the arrow. Therefore, Sn will corrode (or
dissolve) spontaneously in HCL acid.
Thermodynamics of Aqueous Corrosion
 Example 2:
 Consider the half-cell of zinc in 0.1 M ZnCl2 at 40 C, predict the half-cell
potential.
 Solution:
 The half-cell reaction (A): Zn2 + 2e  Zn ,  o = - 0.763 V v.s. SHE

   o  2.303RT log Q
nF

 T = 40 + 273 = 313 K , R = 8.3143 J/mol-K

2.303RT = 0.059138
 F = 96487 coulombs / eqiv , n=2 F
 Q = [1] / [ Zn 2 ] , Notice that [M] = 1

 Zn2  = ( ) (M)  = 0.5 at M = 0.1  Zn2  = ( ) (M) = ( 0.5) (0.1) = 0.05

   

  0.763  0.059138 log (0.05) = - 0.80147 V v.s. SHE

2
 Notice that G is positive, this means that zinc will not corrode in the given solution.
Any zinc ions will plate out on the zinc electrode.
Thermodynamics of Aqueous Corrosion
 Example 3:
 Calculate the tendency for corrosion to occur in the following
metal/electrolyte system:
 a) Silver in cupric acid.
 Solution:
 Assume Cu electrode in LHS of the corrosion cell and Ag electrode in the RHS.
Using the emf potential values, we can write the half-cell reaction as follows:
 RHS RX: 2Ag  + 2e 2Ag , o = 0.8V

 LHS RX: Cu 2 +2e Cu , o = + 0.342 V

Cu + 2Ag  Cu 2  2Ag

ECell  R  L Ecell = 0.8 - (+ 0.342) = + 0.458 V

 E
Cell is found to be positive, which means that the free energy is negative.
Therefore, the spontaneous direction for the cell reaction (A) is left to right;
consequently, silver will not corrode in the given solution. The silver ions will
plate out on the silver electrode.
Thermodynamics of Aqueous Corrosion
 Example 4:
 Predict the spontaneous direction of the reaction
4OH + 2Fe2 O2 + 2Fe + 2H 2O

 Assume O2 electrode in LHS of the corrosion cell and Fe electrode in the RHS.
Using the emf potential values, we can write the half-cell reactions as
follows:
 LHS RX: O2 + 2H2O + 4e 4OH  , o = + 0.401 V

 RHS RX: Fe2  2e Fe , o = - 0.44 V

ECell  R  L Ecell = - 0.44 - (+ 0.401) = - 0.841 V

 E
Cell is found to be negative, which means that free energy is positive.
Therefore, the spontaneous direction for the cell reaction (A) is right to left
as shown by the reaction; consequently, iron will corrode in the aerated
water.
4OH + 2Fe2 O2 + 2Fe + 2H 2O
 =

Thermodynamics of Aqueous Corrosion

 Example 5:
 Determine the thermodynamic tendency for silver to corrode in a de-aerated
acid solution of pH =1, P = 1atm, and aA g  = 106 . The system is at 25ºC
H2

 Solution
 2Ag + 2H+ 2Ag+ + H2
= 106
 Ag│ Ag+ ( aAg  ) ║ H+ (pH= 1) │ and P =1atm H2

 Here the silver electrode is in the left side of the cell and the hydrogen
electrode is in the right side of the cell.

 Potential of LHS (L): Ag  + e Ag , o = + 0.8 V

L = o - 0.0591 log 1  L = 0.8 + 0.0591 log 106 = 0.4454 V

1 Ag 1
Thermodynamics of Aqueous Corrosion
 Example 5:
 Potential of RHS (R): 2H   2e  H 2
 P = 1 atm., and pH = - log [H+]
0.059 [H ] 0.059 P 0.059
 R  o  log 2 2 = 
o
 log  2 = o  [2 log[ H  ]
2 [H ] 2 [H ] 2

   o  0.059 pH

o = 0.0V

R  0.059 pH =  0.059 (1) =  0.059V

ECell  R  L ECell  0.0591 (0.04454) = - 0.5045 V

 ECell is found to be negative, which means thatG is positive. Therefore, the

spontaneous direction for the cell reaction (A) is right to left; consequently,
silver will not corrode in the given solution. The silver ions will plate out on
the silver electrode
Thermodynamics of Aqueous Corrosion
 Example 6:
 Consider the electrochemical cell representation at 25ºC as
 Zn│ Zn2+ (0.5 M ZnSO4) ║ Cu2+ │Cu (0.1 M CuSO4)
 a) Calculate cell potential.
 b) Find the spontaneous direction of the cell reaction.
 c) Indicate the anode, the cathode, and the polarity of the cell.
 Solution:
Thermodynamics of Aqueous Corrosion
 Example 6:
 Solution of Part (a):
 Write the reaction of each cell in the reduction form as:
 RHS Reaction: Cu 2 + 2e  Cu ,  o = + 0.34 V LHS Reaction: Zn2 + 2e  Zn ,  o = - 0.763 V

R = o - 0.0591 log 12 Cu 2  = ( ) (M)

2 Cu   L = o - 0.0591 log 12
2 Zn

 = 0.16 at M = 0.1  = 0.065 at M = 0.5

Cu 2  = ( ) (M) = ( 0.16) (0.1) = 0.016  Zn2  = ( ) (M) = ( 0.065) (0.5) = 0.0325
   

R =  0.34 + 0.0591 log (0.016) = 0.2681 V  =  0.763 + 0.0591 log (0.0325) = - 0.808 V
2 L 2

ECell  R  L

ECell  0.2681  (- 0.808) = + 1.0757 V

Thermodynamics of Aqueous Corrosion
 Example 6:
 Solution of Part (b):

G = - nFECell

 We notice that Ecell is positive (+1.0757 V), therefore the free energy change
(G) is negative. Therefore reaction (A) is spontaneous as written. It proceeds
from left to right as indicated by the arrow.

 Solution of Part (c):

 The negative value of ( G) of reaction (A) indicates that:

 The zinc electrode will corrode and it is the anode with negative polarity.
 The copper electrode will not corrode and it is the cathode with positive
polarity. Notice that copper ions will plate itself on the copper electrode.
Thermodynamics of Corrosion_Pourbaix Diagrams
 Introduction:
 Further application of thermodynamics to corrosion phenomena has been
established by M. Pourbaix. He developed the E-pH diagrams to study the
equilibrium behavior of pure metals in aqueous media at 25 C. The E-pH
diagrams are graphical representation of the domain of stability of metals,
ions, oxides, and other species in solution. Nernst equation was used to
construct these diagrams.
 E-pH diagrams are typically plotted for various equilibrium conditions on
normal Cartesian coordinates with potential E as the ordinate (y-axis) and pH
as the abscissa (X-axis). The potential E and the pH are the two fundamental
variables. Changes in other variables (e.g. oxygen concentration) tend to be
reflected by the changes in the corrosion potential.

In all E-pH diagrams, the potential (E) is relative to the standard hydrogen
electrode (SHE).
Thermodynamics of Corrosion_Pourbaix Diagrams
 In all E-pH diagrams, there are
three important lines, these
lines depends on the type of
reaction.
 The three lines in all E-pH
diagrams were constructed at
four concentrations of the
formed ions. These
concentrations are 10^0, 10^-
2, 10^-4 and 10^-6 gram
ion/kg H2O
Thermodynamics of Corrosion_Pourbaix Diagrams
 1– Horizontal Line (Line 23)
 This represents an
electrochemical reaction
which involves the
production of electrons only.
For example

Fe  Fe 2  2e
Nernst equation
0.059
E  Eo  log Fe  2
2

 This shows that the reaction is

influenced by variations of the
electrode potential
Thermodynamics of Corrosion_Pourbaix Diagrams
 2- Diagonal Line (Line 28)
 This represents an
electrochemical reaction
which involves the production
of electrons and ions. For
example
2Fe 2  3H 2O  Fe2O3  6 H   2e

0.059 [ H  ]6
E  Eo  log
2 [ Fe2 ]2

 Here this reaction is controlled

by both potential and pH.
Notice that
 The potential depends on the
pH and the concentration of
iron ions
Thermodynamics of Corrosion_Pourbaix Diagrams
 3. Vertical Line (Line 20)
 This represents a (pure acid –
base) chemical reaction, which
involves the production of ions
and does not involve electrons (It
does not depend, then on
potential). Therefore, the
reaction is controlled by the pH
(potential independent).

2Fe3  3H 2O  Fe2O3  6 H 

 This is not an electrochemical

reaction; it is a pure acid – base
chemical reaction. Nernst equation
cannot be applied to plot any
vertical line. Instead the solubility
constant (K) will be used to
formulate the relation for the
vertical line as follows:
log  Fe3  = - 0.723 - 3 pH
Thermodynamics of Corrosion_Pourbaix Diagrams
 Important Domains in E-pH Diagrams
 There are three important equilibrium lines (vertical, horizontal, and diagonal)
which create three significant zones or domains. These zones are: corrosion,
immunity, and passivation. The definition of each zone follows:
 1-Corrosion:
 It is the zone where the metal or the solid substance on the surface will be
converted to metal ions. For example: Fe will be oxidized to Fe+2 or Fe2O3 will be
reduced to Fe2+. Water will be reduced to H2 gas or oxidized to O2 gas depending
upon whether the potential value is below line (2) or above line (1) respectively, or
water may stay stable.
 2-Immunity:
 It is the zone where the element metal is in equilibrium with its ions. Here any ions
in the solution or solid substance on the surface will be converted to metal, e.g.
Fe2O3 or Fe2+ will be reduced to Fe. The activity is less that 10^-6 mol ion/lit.
Water will be reduced to H2 gas and any dissolved O2 gas will be reduced to OH-
ions
Thermodynamics of Corrosion_Pourbaix Diagrams
 Important Domains in E-pH Diagrams
 3-Passivation:
 It is the zone where the element metal will be converted to a solid substance on
the surface. The solid substances are in equilibrium with their metal ions at an
activity <10^-6 mol ion/lit. For example, Fe may be converted to Fe2O3, Fe2O4,
Fe(OH) 2, or Fe (OH) 3. These solid substances (oxides) will form an adhering and
non-porous film on the surface to protect it from further dissolution. Water will be
stable at moderate potential value, but at high potential value, it will be oxidized
to O2 gas.
 In all E-pH diagrams, the area of corrosion, immunity, and passivation does vary
from metal to metal. The larger the area of immunity and passivation are the
better the performance of the metal under these conditions. Also some metals
possess more that one corrosion zone and more than one passivation zone.
Thermodynamics of Corrosion_Pourbaix Diagrams
 Important Domains in E-pH Diagrams
Thermodynamics of Corrosion_Pourbaix Diagrams
 Uses of Pourbaix Diagrams
 1. Predict the spontaneous direction of reactions.
 2. Predict the composition of corrosion products.
 3. Predict environmental changes which will reduce or prevent corrosive attack.

 Limitation of Pourbaix Diagrams:

 1. Indicate thermodynamically feasible reactions as corrosion, immunity, and /or passive
regions.
 2. Apply to pure metals only.
 3. Passivation is defined as when corrosion products cover the metal surface and may or
may not find protection.
 4. Give no information on kinetic (rate of reaction , if reaction is slow or rapid)
 5. They do not provide a complete solution to a given problem.
 6. They are qualitative tools only for prediction of a protection system against corrosion.
 7. The pH is not the pH of the Bulk solution.
Thermodynamics of Corrosion_E-pH for Water
 Two important diagonal lines are common in all E/pH diagrams.
 These two lines indicate the domain of stability of water under atmospheric
pressure. The reactions of these two lines are:
 Hydrogen Evolution Line (Line 2)

2 H   2e  H 2
  0.0  0.0592 pH  0.0295 log PH 2

 Oxygen Evolution Line (Line 1)

O2  4 H   4e  2 H 2 O

  1.229  0.0592 pH  0.0148 log PO 2

 The importance of line (a) and (b) is that water is thermodynamically stable between
these two lines. Fig 8.12 in the Appendix shows the stability region for water. This is
also true for all aqueous solutions contain water. Therefore water tends to be
reduced on the cathode with the evolution of H2 gas below line (2) and water tends
to be oxidized on the anode with the evolution of O2 gas above line (1).
E-pH Diagrams for Iron
 Corrosion Zone
 One zone located to the left (oxidizing
and acidic).
 One zone located to the extreme right
(reducing and highly alkaline). It is a
small and narrow zone to
 In both zones, iron react to form soluble
products, and corrosion continues.
 Immunity Zone
 This zone covers reducing conditions
(negative potentials) across the entire
pH range (from acid to alkaline). Under
these reducing conditions, iron is
thermodynamically stable (iron is noble
in the immunity zone). For any
potential –pH combination in the
immunity zone, iron is stable and does
not corrode.
E-pH Diagrams for Iron
 Passivity Zone
 The shaded area represents a zone
of passivity of iron. Under oxidizing
conditions in neutral or alkaline
solutions, iron reacts to form
insoluble (solid) corrosion products
and form a protective film which
blocks further corrosion reaction.
This protection depends on the
degree of perfection of the solid
film.
 Line (a) and (b) are also shown in the E-
pH diagram for iron. Line (a) extends in
the two corrosion zones.
E-pH Diagrams for Iron
 Comments
 1. The E/pH diagrams consider other ions such as Cl  , S2 , NO3

 2. The aggressive ions such as Cl  , S2 , NO3 when exist in water will widen the
corrosion areas.
 3. The passivity areas can be widen by alloying the main metal by more noble
metals such as Cr, Ni, Mo.
 4. The passivity area can be increased by adding inhibitors to water.
 5. In all E/pH diagrams, it is assumed that passivity is formed due to the
formation of insoluble, continuous and adhesive oxide film (Oxide theory).