Thermodynamics Final
Thermodynamics Final
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
CORROSION MECHANISM
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
lL mM qQ rR
Nernst Equation:
Zn
Zn
2e Zn RT Zn 0 Zn ln 2 2 F Zn
Hydrogen Electrode
It is assumed arbitrarily that the standard potential for the following reaction is equal to zero at all temperatures So
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
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.
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