Oil & Gas Refining Engineering Corrosion Eng.

Lecture (4): Thermodynamics and Its

4th Class In Petroleum Refinery Application on Corrosion
Asst. Lect.: Zainab D. Mohammed

Thermodynamics and Its Application on Corrosion

Thermodynamics can provide a basis for the understanding of the
energy changes associated with the corrosion reaction. It can, in general,
predict when corrosion is possible. Thermodynamics cannot predict
corrosion rates. The rate at which the reaction proceeds is governed by
kinetics.

Free Energy Change

The tendency for any chemical reaction to go, including the reaction of
a metal with its environment, is measured by Gibbs free energy change
(ΔG).
If the change in free energy accompanying the transition of a system
from one state to another is negative, this indicates a loss in free energy
and also the spontaneous reaction direction of the system.
If the change in free energy is positive, this indicates that the
transition represents an increase in energy, and this requires that
additional energy be added to the system.
These principle are illustrated in the figure ‫مثال على ذلك‬
‫ باعث‬exo ‫تفاعل‬:
by a mechanical analogy. The transition ‫للحرارة ميحتاج طاقة‬
‫إضافية حتى يتم‬
from position (1) to position (2) is the ‫التفاعل بينما‬
‫ بالعكس‬endo ‫ال‬
spontaneous direction for this particular
system (represents a decrease in free
energy)

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Oil & Gas Refining Engineering Corrosion Eng. Lecture (4): Thermodynamics and Its
4th Class In Petroleum Refinery Application on Corrosion
Asst. Lect.: Zainab D. Mohammed

The more negative the value of ΔG, the greater is the tendency for the
‫كلما كان الرقم اكبر‬
reaction to go. For example: ‫ب السالب يكون‬
‫التفاعل اسرع‬
0
1- Mg + H2O (L) +1/2O2 (g) Mg (OH) 2(s) ΔG = -142600 cal

0
2- Cu +H2O(L) +1/2O2(g) Cu(OH)2(s) ΔG = -28000 cal

The reaction tendency of (2) is less than that of (1)

0
3- Au + 3/2H2O(L) + 3/2O2(g) Au(OH)3(s) ΔG = +15700 cal

The free energy is positive, indicating that the reaction has no

tendency to go at all, and gold correspondingly, does not corrode in
aqueous media to form Au(OH)3.

Cell Potential
Electrochemical cells generate electrical energy due to electrochemical
reactions. The electrical energy available is:
Electrical energy=volts×current×time
=volts×coulombs
=EQ
where:
Q=nF
n is the number of electrons involved in the chemical reaction
F is Faraday’s constant = 96 500 Cmol-1
E is electromotive force (emf) of the cell (volts).
Any work performed can only be done through a decrease in free energy
of the cell reaction, hence,
ΔG = −n F E

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Oil & Gas Refining Engineering Corrosion Eng. Lecture (4): Thermodynamics and Its
4th Class In Petroleum Refinery Application on Corrosion
Asst. Lect.: Zainab D. Mohammed

where:
ΔG = free energy change.
E = potential of the reaction.
n = number of electrons involved in the reaction.
F = Faraday’s constant.
If all substances are in their standard states the expression becomes:
ΔG ֩ = − n F E ֩

Nernst Equation

Consider the system in which metallic iron is immersed in a solution of

copper sulfate. In course of time metallic copper begins to appear. This
process is known as a cementation reaction.

Then, we may write the reactions occurring as:

The equilibrium constant K and the free energy change in the overall
cementation reaction may be written as:

Since the corrosion of iron in copper sulfate solution involves an oxidation

and reduction reactions with exchange of electrons, the reaction must
involve an electrochemical potential difference, related to the equilibrium
constant. This relationship may be written as (Under standard state
conditions):

ΔG ֩ = − n F E ֩
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Oil & Gas Refining Engineering Corrosion Eng. Lecture (4): Thermodynamics and Its
4th Class In Petroleum Refinery Application on Corrosion
Asst. Lect.: Zainab D. Mohammed

Neglecting solids we may write, for the reaction of iron in copper sulfate
solution:

Division by -nF leads to:

In general terms:
𝑅𝑇 [𝑃𝑟𝑜𝑑𝑢𝑐𝑡]
𝐸 = 𝐸° − 𝑙𝑛
𝑛𝐹 [𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡]
Converting to log and T = 298, and inserting numerical F; R values:
0.059 [𝑃𝑟𝑜𝑑𝑢𝑐𝑡]
𝐸 = 𝐸° − 𝑙𝑜𝑔
2 [𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡]
This equation is known as the Nernst equation, and is extensively used in
o
electrochemical measurements. Under equilibrium conditions E = E and
o o
the experimentally obtained values of E are tabulated in the literature. E
values can be used to determine whether a reaction will occur or not.

Example (1)
For the cell [Cu/Cu2+(1.0M)]//[Zn2+(1.0M)/Zn], and the cell reaction
Cu + Zn2+→ Cu2+ + Zn:
If ΔG◦298K = −147.5 kJ mol−1 for Zn2+
and ΔG◦298K = 63.35 kJ mol−1 for Cu2+
does the reaction take place simultaneously?
Solution:
ΔG◦Reaction = ∑ niΔG(i)− ∑ njΔG(j)
where
i = products

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Oil & Gas Refining Engineering Corrosion Eng. Lecture (4): Thermodynamics and Its
4th Class In Petroleum Refinery Application on Corrosion
Asst. Lect.: Zainab D. Mohammed

j = reactants

∴ΔG◦Reaction =2 [63.35 + 0 − (−147.5 + 0)]

ΔG◦Reaction = 425.1 kJ mol-1
Since,
ΔG◦Reaction = − n F E֩
425.1 kJ mol-1 = 2 × 96500 C mol-1× E◦
E◦ = −0.002 V
Reaction does not take place simultaneously.

Example (2)

Represent the cell in which the following reaction takes place. Calculate
its E(cell) if E(cell)֩ = 3.17 V.
Mg(s) + 2Ag+ (0.0001M) → Mg2+ (0.130M) + 2Ag(s)
Solution:

Mg(s) → Mg2+ + 2e-

2Ag+ + 2 e- → 2Ag(s) n=2
0.059 [Product]
E = E° − log
n [Reactant]

0.059 [Mg2+ ]
E𝑐𝑒𝑙𝑙 = E ° 𝑐𝑒𝑙𝑙 − log
2 [Ag+ ]2

0.059 0.13
E𝑐𝑒𝑙𝑙 = 3.17 − log
2 (0.0001)2

E𝑐𝑒𝑙𝑙 = 2.96 𝑉

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Oil & Gas Refining Engineering Corrosion Eng. Lecture (4): Thermodynamics and Its
4th Class In Petroleum Refinery Application on Corrosion
Asst. Lect.: Zainab D. Mohammed

Example (3)

For Daniel cell, Calculate the standard Gibbs energy for the reaction:

Solution:

Zn(s) → Zn2+ + 2e- E ֩Zn/Zn2+ = -0.763 V

Cu2+ + 2 e- → Cu(s) E ֩Cu/Cu2+ = 0.337 V n= 2
° ° °
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝐶𝑢/𝐶𝑢 2+ − 𝐸𝑍𝑛/𝑍𝑛2+

°
𝐸𝑐𝑒𝑙𝑙 = 0.337 − (−0.763)
°
𝐸𝑐𝑒𝑙𝑙 = 1.1 𝑉
ΔG֩cell = − n F E֩cell
= − 2 * (96500 C/mol) * (1.1 V)
= 212300 J/mol = 212.3 KJ/mol

Example (4)
Calculate the potential of hydrogen electrode in contact with a solution of
pH =10.
Solution:
For Hydrogen electrode the reaction is:
2H+ + 2e- H2 n= 2
Concentration of [H+] of the solution with pH =10 is:
[H+] = 10–pH, Therefore [H+] = 10−10 M
0.059 [Product]
E = E° − log
n [Reactant]
0.059 PH
E = E° − log +2 2
n [H ]
°
PH2 for hydrogen electrode = 1 atm and Ecell =0
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Oil & Gas Refining Engineering Corrosion Eng. Lecture (4): Thermodynamics and Its
4th Class In Petroleum Refinery Application on Corrosion
Asst. Lect.: Zainab D. Mohammed

0.059 1
E=0− log
2 (10−10 )2
E = −0.59 V

Example (5)
Determine the thermodynamic tendency for silver to corrode in a deaerated
-6
acid solution of pH = 1.0 Assume ɑAg+ = 10 and PH2= 1atm.
+ +
Ag(s) + H Ag + 1/2 H2

Solution:
+
Ag Ag + e- E ֩Ag/Ag+ = 0.799 V
H+ + e- 1/2H2 E ֩H2/H+ = 0 V n= 1
°
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝐻° 2 /𝐻 + − 𝐸𝐴𝑔/𝐴𝑔
°
+

°
𝐸𝑐𝑒𝑙𝑙 = 0 − 0.799
°
𝐸𝑐𝑒𝑙𝑙 = −0.799 𝑉

0.059 [Product]
E = E° − log
n [Reactant]

°
0.059 [𝐴𝑔+ ]. (𝑃𝐻2 )1/2
E𝑐𝑒𝑙𝑙 = E 𝑐𝑒𝑙𝑙 − log
n [H + ]
[H+] = 10–pH

[H+] = 10–1 = 0.1 M

0.059 10−6 ∗ 1
E𝑐𝑒𝑙𝑙 = −0.799 − log
1 0.1
E𝑐𝑒𝑙𝑙 = −0.504 𝑉

ΔGcell = −n F Ecell
ΔGcell = −1 * 96500 C/mol * −0.504 𝑉
ΔGcell = +48636 J/mol ΔG = + silver will not corrode