Department of Mechanical Engineering

Chittagong University of Engineering and Technology

Thermodynamics: The mist of science clarifying the relationship of energy is called

Thermodynamics. Or, The science of energy in which the storage, the transformation and the
transfer of energy are studied. Or, Thermodynamics is the science of energy dealing various forms
of energy

System: The region in space containing a quantity of matter whose behavior is

Boundary
being investigated. Or, A thermodynamic system is a definite quantity of matter
contained within some closed surface.
System

Surrounding: All matter and space external to a system is collectively called its
surroundings. Or, Everything external to the system which is affected by Surroundings

changes occurring to the system.

Universe
Boundary: The line that separates the system from the surroundings.
Universe: The system and the surroundings together are called a universe

ME 6351 Thermodynamics of Corrosion Page # 1

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Transition State Theory

Consider a reaction occurring spontaneously having A and Transition State

B are the reactants and C and D are the products of the

∆G~ (Energy Barrier)
reactants.  

Reactants

Free Energy, G
A+B AB C+D A+B
∆G

To produce the products, the reactants must come together

Products
C+D
and physically join together forming an intermediate
species, AB. Reaction Coordinate

Figure 1: Energy profile for a reaction [4]

The intermediate species (AB) is called transition state and its re-organization leads directly to
products (C+D).
 In reality, Intermediate species are formed for very short time when the reactant possess
sufficient energy.

ME 6351 Thermodynamics of Corrosion Page # 2

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

 
Thermodynamics aspect of Corrosion reaction:
1. All interactions between elements and compounds are governed by the free energy changes
available for them.
2. Stability is clearly connected with tendencies for change in system. A well-known tendency in
nature is to move towards more stable state, that is, a state of minimum internal energy (Most
metals have inherent tendency to corrode)

Some Useful Definitions

The Internal Energy (U): The portion of energy stored in the chemical bonds of substances.

The Entropy (S): The randomness of a system is expressed in quantity is called entropy which is
written as. Entropy is small in ordered systems like crystals and large in disordered systems like
solutions, melts, vapors.
Free Energy (G): The portion of substances internal energy which is available to perform work.
Mathematically, G H -TS = U + PV - TS

ME 6351 Thermodynamics of Corrosion Page # 3

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

General rules for processes to occur

Spontaneous process must be negative or

Equilibrium
Equilibrium process
process must be equal to 0 or

No commencing of the process must be Positive or

No commencing of the process

 
Why do Gold, Platinum and other precious metals do not corrode?
Mg + H2O + O2 Mg (OH)2

Au + H2O + O2 Au (OH)3

Cu + H2O + O2 Cu (OH)2

ME 6351 Thermodynamics of Corrosion Page # 4

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Mercel Pourbaix developed  method of summarizing thermodynamic data in a diagram which

relates electrode potential (E) and pH

a) The hydrogen line - Below which H2 is evolved

b) The oxygen line - Above which O2 is evolved

c) Between these two lines (a-b) - water is stable.

Figure1: Pourbaix diagram for water at 25 ° C [7]

ME 6351 Thermodynamics of Corrosion Page # 5

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

 Line a represents the cathodic evaluation of H2 gas and

expressed by E = 0 – 0.059 pH:
1) In Acid solution: 2H+ + 2e- H2

2) In basic solution: 2H2O + 2e- H2 + 2OH-

 Line b represents the anodic evolution of oxygen and

expressed by E = 1.228 – 0.059 pH :
1) 2H2O O2 + 4H+ + 4e-

Line “a” is important because it informs the conditions

necessary for formation of H2 gas, indicating the possibility of
hydrogen embritllement.
Figure 2: Pourbaix diagram for water at 25 °C [9]

ME 6351 Thermodynamics of Corrosion Page # 6

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Applications of Pourbaix diagram

1) Evaluate resistance to uniform corrosion of metals in aqueous solution
2) Evaluate passivation conditions for different pH and potential conditions
3) Evaluate the use of corrosion inhibitors, for example CrO4
4) Identify the set of internal conditions within a localized corrosion cell; Pourbaix Diagrams

Limitations of Pourbaix Diagrams

 Equilibrium conditions are assumed
 No information is given regarding corrosion rates
 The diagrams apply to pure metals only (for single phase alloys, the diagrams can be
estimated by superposition, but otherwise must be determined experimentally)
 Any solid corrosion products are considered to be passive regardless of their properties
 Localized corrosion by chloride ions is not considered
 No detail information about the nonstoichiometric metal films formation

ME 6351 Thermodynamics of Corrosion Page # 7

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

Limitations of Thermodynamics consideration

1. It is impossible to get rate of reactions

2. Galvanic series showing practical resemblances with electrochemical series of

metals, but there are discrepancies in several metals

3. Hard to expect that the same equilibrium potential for components taking part

in dissolution reaction.

ME 6351 Thermodynamics of Corrosion Page # 8

 Department of Mechanical Engineering
Chittagong University of Engineering and Technology

ME 6351 Thermodynamics of Corrosion Page # 9