SEMINAR ON SIGNIFICANCE OF H2-H2O-O2 LINES IN POURBAIX DIAGARM

PREPARED BY: VISHNU V NAIR ROLL NO.929

DEPARTMENT OF METALLURGICAL AND MATERIAL ENGINEERING FACULTY OF TCHNOLOGY & ENGINEERING M.S UNIVERSITY VADODARA

SIGNIFICANCE OF H2-H2O-O2 LINES IN POURBAIX DIAGRAM As most of us recall from our struggles with balancing redox equations in beginning chemistry courses, many electrontransfer reactions involve hydrogen ions and hydroxide ions. The standard potentials for these reactions therefore refer to the pH, either 0 or 14, at which the appropriate ion has unit activity. Because multiple numbers of H+ or OH ions are often involved, the potentials given by the Nernst equation can vary greatly with the pH. It is frequently useful to look at the situation in another way by considering what combinations of potential and pH allow the stable existence of a particular species. This information is most usefully expressed by means of a E-vs.-pH diagram, also known as a Pourbaix diagram.

Pourbaix diagram (Electrode potential --PH diagram) is a graphical presentation of the thermodynamic equilibrium states of a metal-electrolyte system. Pourbaix diagrams are plotted in the axes Electrode potential of the metal vs. PH of the electrolyte. Oxidizing conditions are described by the top part of the diagram (high positive electrode potential). Reducing conditions are described by the bottom part of the diagram (high negative electrode potential).

Stability of water
As was noted in connection with the shaded region in the figure below, water is subject to decomposition by strong oxidizing agents such as Cl2 and by reducing agents stronger than H2. The reduction reaction can be written either as 2H+ + 2e H2(g) or, in neutral or alkaline solutions as H2O + 2 e H2(g) + 2 OH These two reactions are equivalent and follow the same Nernst equation

which, at 25C and unit H2 partial pressure reduces to E = E - (.059/2) 2 pH = 0.059 pH Similarly, the oxidation of water H2O O2(g) + 4 H+ + 2 e is governed by the Nernst equation

which similarly becomes E = 1.23 0.059 pH, so the E-vs-pH plots for both processes have identical slopes and yield the stability diagram for water shown below.

Stability (Pourbaix) diagram for water

T The two E values shown at the left refer to "standard" conditions of unit H+ activity (pH=0) and gas pressures of 1 atm. At combinations of pH and E that lie outside the shaded area, the partial pressures of O2 or H2 exceed 1 atm, signifying the decomposition of water. The unity partial pressures are of course arbitrary criteria; in a system open to the atmosphere, water can decompose even at much lower H2 partial pressures, and at oxygen pressures below 0.2 atm. Fortunately, these processes are in most cases quite slow. The above diagram has special relevance to electrochemical

corrosion of metals. Thus metals above hydrogen in the activity series will tend to undergo oxidation (corrosion) by reducing H+ ions or water.

Thus there are 3 regions: 1) Upper region:-H2O electrolyzed anodically to O2 2) Lower region :- H2O electrolyzed cathodically to O2 3) Middle region:- H2O stable and wont decompose THIS EXAMPLE--- BASIC /OXIDATION/REDUCTION REACTIONS FOR AQUEOUS SYSTEMS CAN BE SUPERIMPOSED ON A METAL TO GIVE A CORROSION SYSTEM!!! & WILL SHOW UNDER WHAT CONDITIONS, A METAL WILL CORRODE POURBAIX DIAGRAM OF IRON

Stability diagrams are able to condense a great amount of information into a compact representation, and are widely employed in geochemistry and corrosion engineering. The Pourbaix diagram for iron is one of the more commonly seen examples.
Pourbaix diagram for iron

Three oxidation states of iron (0, +2 and +3) are represented on this diagram. The stability regions for the oxidized iron states are shown only within the stability region of H2O. Equilibria between species separated by vertical lines are dependent on pH only. The +3 oxidation state is the only stable one in environments in which the oxidation level is controlled by atmospheric O2. This is the reason the Earths crust contains iron oxides, which developed only after the appearance of green plants which are the source of O2. Iron is attacked by H+ to form H2 and Fe(II); the latter then reacts with O2 to form the various colored Fe(III) oxides that constitute rust. Numerous other species such as oxides and hydrous oxides are not shown. A really complete diagram for iron would need to have at least two additional dimensions showing the partial pressures of O2 and CO2.

 POURBAIX DIAGRAM OF COPPER

Cu metal is unstable in Free State. It is stable in form of oxides in water, as shown in fig. Three kinds of lines separate copper species in this diagram First is vertical: CuO + 2 H+ = Cu2+ + H2O; CuO + H2O = CuO22 + 2 H+ Reactions involve exchange of H+, but no electrons (no oxidation/reduction); independent of E Second type of line is horizontal: Cu2+ + 2 e = Cu Reaction involves oxidation/reduction, but no H+; independent of pH Third type of line is diagonal: Cu2O + 2 H+ + 2 e = 2 Cu + H2O Reaction involves both oxidation/reduction and H+ exchange, so line is a function of E and pH Presence of stability region between lines for Cu and ions shows that Cu can be produced hydrometallurgically

POURBAIX DIAGRAM OF GOLD

Golds Pourbaix diagram explains why it is the most immune substance known. It is immune in all regions in which cathodic reactions can take place. So gold never* corrodes in an aqueous environment. Immunity of aluminium only occurs at lower potentials. Therefore, unless under conditions that cause it to passivate, it is much more susceptible to corrosion than gold or zinc. * provided that the water is pure; that no ion complexes are present to provide a cathodic half cell reaction that occurs at a potential higher than +1.5 V(SHE).

POURBAIX DIAGRAM OF TITANIUM

The Pourbaix diagram in the image shows that titanium is actually thermodynamically a very reactive metal. However, it is slow to react with water and air, because it forms a passive and protective oxide coating that protects it from further reaction. When it first forms, this protective layer is only 12 nm thick but continues to slowly grow; reaching a thickness of 25 nm in four years.

Titanium readily reacts with oxygen at 1,200 C (2,190 F) in air, and at 610 C (1,130 F) in pure oxygen, forming titanium dioxide.[7] As a result, the metal cannot be melted in open air since it burns before the melting point is reached. Melting is only possible in an inert atmosphere or in a vacuum. At 550 C (1,022 F), it combines with chlorine.[3] It also reacts with the other halogens and absorbs hydrogen.[4]

APPLICATIONS:::: It is frequently useful in considering what combinations of potential and pH allow the stable existence of a particular species. This information is most usefully expressed by means of Pourbaix diagram. H2 -H2 O- O2 line is used to determine the stable form of a metal.

We can identify when the metal will undergo reduction or oxidation.

REFERENCES:::
1) http://www.chem1.com/acad/webtext/elchem/ec4.html 2) en.wikipedia.org/wiki/ 3) www.wou.edu/las/physci/ch412/pourbaix.htm 4) Corrosion-doctors.org/Corrosion.../Potential-pH-diagram-iron.htm 5) www.doitpoms.ac.uk/tlplib/pourbaix/pourbaix_example.php