Basic Concepts :

Lecture 1b

rini riastuti corrosion - 2006

Topics :

Theory of aqueous corrosion

Electrochemical aspect

Electrochemical Nature of aqueous corrosion

Metallic corrosion process involve transfer of electronic charge in aqueous solutions Thus, it is necessary to discuss the electrochemical nature of corrosion before discussing of the various form of corrosion.

Corrosion of Zinc in Acid

Electrochemical reactions :
Example of corrosion between zinc and hydrochloric acid, represented by : Zn + 2 HCl ZnCl2 + H2 (1)

Zinc reacts with the acid solution forming soluble zinc chloride and liberating hydrogen bubbles on the surface.

Acids and Bases

An

acid is a substance that produces excess hydrogen ions (H+) when dissolved in water

examples are HCl, H2SO4

base is a substance that produces excess hydroxyl ions (OH-) when dissolved in water

examples are NaOH, KOH

Corrosion of Zinc in Acid

Zinc

dissolves with hydrogen evolution Zn + 2HCl ZnCl2 + H2

known as a base or active metal

Zinc

One atom zinc metal plusof two molecules hydrogen reacts toof form one molecule of molecule zinc chloride plus one of hydrogen gas chloride (hydrochloric goes to acid)

Corrosion of Platinum in Acid

Platinum

does not react with acids Platinum is known as a noble metal

Connection of Platinum to Zinc

electrons

Zinc and platinum not connected, noplatinum reaction Zinc and on platinum connected, current flows and hydrogen is evolved on platinum Pt

Zn

HCl
2H+ + 2e- H2 Zn 2HCl ZnCl Zn+ Zn2+ + 2e 2 + H2 hydrogen ions + electrons hydrogen gas metal + acid ions salt + + electrons hydrogen metal metal

Connection of Platinum to Zinc

Zn + 2HCl ZnCl2 + H2 But we can separate metal dissolution and hydrogen evolution Zn Zn2+ + 2e-

2H+ + 2e- H2 These are known as electrochemical One oneatom zinc ion of zinc in solution metal two electrons in the metal reactions

Reactions that involve both chemical change and the transfer of charge

External Current Applied to Platinum in Acid

Hydrogen evolved on negative electrode 2H+ + 2e- H2 Oxygen evolved on positive electrode + 2H2O O2 + 4H+ + 4e-

Acid - chemical species Pt Pt that produces hydrogen ions in water

HCl

Overall reaction
2H2O 2H2 + O2

Alkali

The product of [H+] times [OH-] is 10-14, so in pure water both [H+] and [OH-] are 10-7. This leads to the + concept of pH, which is Note that H and OH are in defined as -log[H+] Alkali - chemical species that equilibrium in water: -) Hence pH = 0 is strong acid, is neutral, and produces hydroxyl ions7(OH + + OH14 isin strong alkali H O H water 2

External Current Applied to Platinum in Alkali

Hydrogen evolved on negative electrode 2H2O + 2e- H2 + 2OHPt Oxygen evolved on positive electrode + 4OH- O2 + 2H2O + 4ePt

NaOH Overall reaction 2H2O 2H2 + O2

External Current Applied to Platinum

Hydrogen

or

evolution at one electrode A piece of m 2H+ + 2e- H2 (acids) in the soluti 2H2O + 2e- H2 + 2OH-(alkalis)

Oxygen evolution at the other electrode 2H2O O2 + 4H+ + 4e- (acids) or 4OH- O2 + 2H2O + 4e- (alkalis)

Electrodes
Electrodes

are pieces of metal on which an electrochemical reaction is occurring An anode is an electrode on which an anodic or oxidation reaction is occurring A cathode is an electrode on which a cathodic or reduction reaction is occurring

Anodic Reactions
Examples

Zn Zn2+ + 2ezinc corrosion Fe Fe2+ + 2eiron corrosion Al Al3+ + 3ealuminium corrosion Fe2+ Fe3+ + eferrous ion oxidation H2 2H+ + 2ehydrogen oxidation 2H2O O2 + 4H+ + 4e- oxygen evolution Oxidation reactions Produce electrons

Cathodic Reactions
Examples

O2 + 2H2O + 4e-4OH2H2O + 2e- H2 + 2OHCu2+ + 2e- Cu Fe3+ + e- Fe2+

Reduction

oxygen reduction hydrogen evolution copper plating ferric ion reduction

reactions Consume electrons

Metal Ion Hydrolysis

Note

that metal ions may react with water (a hydrolysis reaction) e.g. Al3+ + 3H2O Al(OH)3 + 3H+ or 2Al3+ + 3H2O Al2O3 + 6H+
Note

that in an electrochemical reaction, we have the same number of each atom on each side of the equation, and the same overall charge

Faradays Law
Charge

is related to mass of material reacted in and electrochemical reaction: 2H+ + 2e- H2

Two hydrogen ions To produce one molecule of hydrogen gas

React with two electrons

Faradays Constant
One

mole of hydrogen ions (1 g) contains Avogadros number (6 1023) ions Hence electrons will react with each mole of hydrogen ions Charge on the electron is 1.6 10-19 C Hence one mole of ions requires 96500 C This is known as Faradays constant

Faradays Law
nFm Q M where Q charge (C) F Faraday' s constant (96500 C/mole) n number of electrons transferr ed m mass of metal oxidised (g) M atomic weight of metal (g/mole)

Effect of Potential
Electrochemical

reactions involve transfer of

charge Hence, we expect that the voltage of the metal with respect to the solution will affect electrochemical reactions Voltage of metal with respect to solution is known as the electrochemical potential

Corrosion of zinc in acid

When

zinc is placed in acid the metal will start to dissolve and hydrogen will start to be liberated according to the potential of the metal Consider the anodic zinc dissolution reaction Zn Zn2+ + 2e-

Energy: the Rule of Law

The law: energy can neither be created nor destroyed. The Rule: all spontaneous changes occur with a release of free energy from the system to the surroundings at constant temperature and pressure. Points to note:

corrosion is a spontaneous process. free energy is released in the process. metals returned to its stable state.

Free energy: the portion of internal energy available for powering engines or causes corrosion reaction.

The driving force for corrosion reaction: chemical energy - energy stored in chemical bonds of substances -internal energy.

Transition state theory concerns

A+ B= AB= C + D The transition sate must be of higher free energy than the sum of the free energies of the separate species.