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The Basics
x-axis is pH; usually 014, but sometimes
as low as 3, and sometimes up to 16
pH = log [H+]; change of 1.0 pH unit
changes [H+] by factor of 10
y-axis is electrode potential relative to
SHE (range varies); positive is oxidizing condition, negative is reducing
Assumes constant temperature, aH2O = 1
Diagram is divided into predominance regions, where one phase prevails
Requires definition of predominance in terms of chemical potential
For solids, activity = 1; for gases, set a partial pressure; for solutions, set an
activity
The Basics
Two lines shown here are present on
nearly all Eh-pH diagrams
Line (a) is for 2 H+ + 2 e = H2 (g)
Usually presumes pH2 = 1 atm
Since G = 0, applying Nernst equation,
E = 0 0.05915 pH
Result: E = 0 at pH = 0 (SHE), slope of
straight line = 0.05915
When conditions are below line, reduction reaction generates H2 (g); when
conditions are above line, H2 (g) oxidizes to H+
Line (b) is for 4 H+ + O2 + 4 e = 2 H2O; E = 1.23 0.05915 pH
Above line, oxidizing conditions generate O2; below line, reduction reaction
generates H2O
Most hydrometallurgical processes operate between the lines
Add A Metal
Eh-pH diagram shows CuH2O system
Dotted lines represent water stability
region; solid lines represent equilibria between copper species
Two aqueous species, Cu2+ and CuO22Oxidation state of Cu as Cu0 is 0
Oxidation state of Cu as Cu2O is +1
Oxidation state of Cu in Cu2+, CuO,
and CuO22- is +2
Lower oxidation states are stable at bottom, higher oxidation states at top
Activity of solid compounds = 1 when predominant; varies for aqueous species
(1 in this case, could be as low as 106)
Predominance activity determined by purpose, value of metal