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CORROSION THERMODYNAMICS

PRESENTED BY: GAUTAM AHUJA M.TECH-POLYMER TECHNOLOGY 2K11/PTE/02 DTU

INTRODUCTION
Corrosion the disintegration of an engineered material into its constituent atoms due to chemical reactions with its surroundings. Corrosion also refers to other materials than metals, such as ceramics and polymers, although in this context the term degradation is more common. In the most common use of the word, this means electrochemical oxidation of metals in reaction with an oxidant such as oxygen.

UTILITY OF THERMODYNAMICS
Thermodynamic considerations allow the determination of whether a reaction can occur spontaneously If metal dissolution is unfavorable thermodynamically in a given set of circumstances the job of the corrosion engineer is done
Example: Copper in pure deoxygenated water

Four components are essential to set up an electrochemical corrosion cell:


1. ANODE The corroding electrode 2. CATHODE- The passive, non-corroding electrode 3. THE CONDUCTING MEDIUM The electrolyte or the corroding fluid 4. COMPLETION OF THE ELECTRICAL CIRCUIT- Through the material

CORROSION MECHANISM

FREE ENERGY OF A REACTION


The tendency for any chemical reaction, including corrosion, is measured by the G. Mg + H2O +1/2O2 Mg(OH)2 Cu + H2O +1/2O2 Cu(OH)2 Au + 3/2H2O +3/4O2 Au(OH)3 G = -142,600 cal G = -28,600 cal G = +15,700 cal

Tendency to corrosion : Mg > Cu Au

RELATION OF G AND EMF

G EnF

G is in Joules E is emf in volts n is the number of electrons involved in the reaction F is the Faraday (96500 C/equivalent)

The larger the value of E for any cell more is the tendency for the overall cell reaction to proceed Ecell = Ecathode - Eanode

The Nernst Equation


General Reaction for a Galvanic Cell

lL mM qQ rR
Nernst Equation:

RT aQ .aR ... EE ln l m nF aL .aM ...


0

Half Cell Potential


When a metal M is immersed in an aqueous electrolyte, it acquires a certain potential. If the activity of the metal ions M++ in the aqueous environment is unity, then the acquired potential is known as standard potential 0 Potential of each electrode can be calculated using Nernst equation

Example: Zinc Electrode

Zn

Zn

2e Zn RT Zn 0 Zn ln 2 2 F Zn

STANDARD ELECTRODE POTENTIALS


The potential difference across an electrochemical cell is the potential difference measured between two electronic conductors connected to the electrodes. A voltmeter may be used to measure the potential differences across electrochemical cells but cannot measure directly the actual potential of any single electrode.

Standard Hydrogen Electrode (SHE)


The potential of the electrode equals zero if the hydrogen ion activity and the pressure of hydrogen gas in atmospheres are both unity. This is the standard hydrogen potential The half - cell potential for any electrode is equal to the emf of a cell with the standard hydrogen electrode as the other electrode. The half - cell potential for any electrode expressed on this basis is said to be on the normal hydrogen scale or on the standard hydrogen scale , sometimes expressed as H or ( S.H.E. )

Hydrogen Electrode
It is assumed arbitrarily that the standard potential for the following reaction is equal to zero at all temperatures So

Reference Half Cells


It is not always convenient to have a hydrogen electrode in the laboratory Other reference half-cells (reference electrodes) have been introduced.
Calomel reference electrode Ag-AgCl half cell The Saturated Copper-Copper Sulfate half cell

EMF Series
All metals have been arranged in a series according to their standard potential (0) values. The more positive value corresponds to noble metals and the more negative value corresponds to more reactive metals (when arranged according to reduction potential) Of the EMF series if two metals make up a cell, the more active metal acts as the anode and the more noble metal of the two will act as cathode

EMF Series

Problems with EMF Series


In real situation, the activities of the metal ions in equilibrium with the respective metals usually do not equal unity The position of a metal in the EMF series with respect to another metal may change because of complex formation as is the case with tin (Sn) and steel (Fe) Alloys are not included in the EMF series In oxidizing environment, some metals undergo passivation and are known as active-passive metals. Transition metals usually show passive behaviour in aerated aqueous environment. This dual position of some metals is not reflected in the EMF series.

Galvanic Series
Galvanic series is an arrangement of both metals and alloys according to their actual measured potentials in a particular environment. There would be one Galvanic series for each environment Metals and alloys showing active-passive behaviour are listed in both active and passive states.

Pourbaix Diagram
Marcel Pourbaix developed potential-pH diagrams to show the thermodynamic state of most metals in dilute aqueous solutions With pH as abscissa and potential as ordinate, these diagrams have curves representing chemical and electrochemical equilibria between metal and aqueous environment These diagrams ultimately show the conditions for immunity, corrosion or passivation.

Benefits of Pourbaix Diagram


Pourbaix diagrams offer a large volume of thermodynamic information in a very efficient and compact format. The information in the diagrams can be beneficially used to control corrosion of pure metals in the aqueous environment By altering the pH and potential to the regions of immunity and passivation, corrosion can be controlled. For example, on increasing the pH of environment in moving to slightly alkaline regions, the corrosion of iron can be controlled Changing the potential of iron to more negative values eliminate corrosion, this technique is called cathodic protection. Raising the potentials to more positive values reduces the corrosion by formation of stable films of oxides on the surface of transition metals

Limitations of Pourbaix Diagrams


These diagrams are purely based on thermodynamic data and do not provide any information on the reaction rates Consideration is given only to equilibrium conditions in specified environment and factors, such as temperature and velocity are not considered which may seriously affect the corrosion rate

THANK YOU !

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