TERMODINAMICA EN

HIDROMETALURGIA
 Y
DIAGRAMAS DE
POURBAIX
LOS DIAGRAMAS DE POURBAIX…
Inventados en 1930 por Marcel
Pourbaix (Belga)

Nace un 16 de septiembre 1904 en  

Óblast de Tula, Rusia
Muere en 1998 en Uccle, Bélgica
La ecuación de Nernst…
Walther Hermann
Nernst Görbitz 

Nace en Briesen, Prusia el

25 de junio de 1864,
 † Ober-Zibelle,
Alemania, 18 de
noviembre de 1941, fue
 Premio Nobel de
Química en 1920.
 Add A Metal
Eh-pH diagram shows Cu–H2O system
Dotted lines represent water stability
region; solid lines represent equi-libria
between copper species
Two aqueous species, Cu2+ and CuO22-
Oxidation 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 10–6)
Predominance activity determined by purpose, value of metal
 More on Metal – H2O Diagrams
Type of stable ion depends on pH
For CuO + 2 H+ = Cu2+ + H2O, low pH
drives reaction to right
Simple ions like Cu2+ are stable at low pH
For CuO + H2O = 2 H+ + CuO22–, high pH
drives reaction to right
Oxyions like CuO22– are stable at high pH

Solid oxides, hydroxides most stable in center of diagram

 More on Metal – H2O Diagrams
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/reduc-tion);
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
(No curved lines in most diagrams.)
 Why Does This Matter? (Part I)
Diagram at bottom left is Cu–H2O system
Presence of stability region between lines for Cu and ions shows that Cu can be
produced hydrometallurgically
Diagram at bottom right is Au–H2O system
No stability region for gold ions between lines; can’t dissolve Au in aqueous solutions (for
now)
The Effect of Ion Activity
Diagram shows Co–H2O system
Tiny 0, –2, –4, –6 represent base-10 log of
ion activity (Co2+, HCoO2–)
As required activity of ions decreases,
predominance area for ions grows
(sideways and vertically)
Easier to “produce” ions if desired
concentration isn’t as high
Easier to reduce ions to metal is con-
centration of ions is higher
 The Effect of Temperature
Partial Eh-pH diagrams below show Cu–H2O system at 25° (left) and 100°C
(Use log aCu(2+) = 0 lines for low–temperature diagram)
Notice slight change in slope of diagonal lines
Cu2+ region shrinks (unusual), Cu2O region is smaller, CuO and Cu regions ↑

Water stability region also moves

Can use changes in temperature to our
advantage
Eh-pH Diagrams for Anions
Diagram shows S–H2O system at 25°C
H2S is dissolved in solution, not gas
Can do this for other anions as well
Matters because pure oxide minerals are
uncommon, and anions are used for
leaching, precipitation; need the right one!
 Why This Matters (Part II)
Diagrams below show Au–H2O and Au–CN–H2O diagrams at 25°C
Diagram at left shows why we can’t dissolve gold; diagram at right shows how we can
(This is why cyanide is used)
Notice vertical line at bottom for H+ + CN– = HCN (g); impacts other lines
Also notice curvature of lines; reflects changing activity coefficients
 Add An Anion And Another Metal
(Hope you’re taking notes!)
Diagram shows Cu–Fe–S–H2O sys-tem at
25°C
Requires setting activity for aqueous Cu,
Fe, and S species
CuFeS2 is chalcopyrite, main copper
mineral
Cu5FeS4 is bornite
FeS2 is pyrite; FeS is pyrrhotite
Notice separate predominance regions for
several species; impact of changing
predominant S species
 Why This Matters (Part III)
Chalcopyrite contains copper ($3/lb) and
iron ($0.08/lb). How to separate?
Could smelt, oxidize iron to slag; re-
quires energy, flux, slag disposal
Why not leach?
Where on this diagram can I put Cu into
solution and leave Fe behind?
 Limitations of Eh-pH Diagrams
• Doesn’t include impact of kinetics
• Presumes only one predominant species (sometimes activities of ions are nearly
equal)
• Depends on accurate thermodynamic data (not always available for complex
compounds)
 CASOS DE ESTUDIO

Diagramas de Pourbaix
Lixiviación de convertidores catalíticos
Lixiviación de chatarra electrónica:
FIN