Thermodinamika dan kinetika

dalam metalurgi ekstraksi

1. Termodinamika
2. Aplikasi pada pirometalurgi (Cu)
3. Eh-pH
4. Kinetika
1 THERMODYNAMICS IN
EXTRACTIVE METALLURGY
 References
1. M. A. Rhamdhani, Appplication of
Thermodynamics to Industrial Processes,
Workshop materials, Swinburne Univ. of
Technology, 2012
2. C. K. Gupta, Chemical Metallurgy: Principles
and Practices, Willey-VCH, 2003
3. M. Bahrens, Solid State Kinetics, Lecture
materials, Fritz Haber Institute, 2012
 Content
• Thermodynamics Fundamentals
– Definitions and Basics Concepts
– Energy, Energy Transfer and general energy
analysis
– 0th law, 1st law, 2nd law and 3 rd law of
thermodynamics
– Ellingham Diagram
 Content
• Solid state Kinetics Fundamentals
– Basics kinetic
– Solid defects
– Solid reactivity
• Decomposisition reactions, sintering
• Solid – gas reaction
• Solid – solid reaction
• Solid –liquid reaction
 Thermodynamics
• Thermodynamics → Science of “energy”
– Therme: heat and dynamis: power

• All activities and processes in nature involve

some interaction between energy and matters

(source: Ref [1])

 Thermodynamics
• Classical thermodynamics:
– A macroscopics approach to the study of
thermodynamics that does not require a knowledge
of the behavior of individual particles
– It provides a direct and easy way to the solution of
engineering problems
• Statistical thermodynamics:
– A microscopic approach, based on the average
behavior of large groups of individual particles
– More “difficult” but potentially better for predicting
behavior of a system.

(source: Ref [1])

 Definitions
• The theory assume that Universe consist of
system and surroundings,i.e.
• Universe = System + Surroundings
System: a quantityof matter or a region in
space chosen study
Surroundings
Surroundings: the region outside the system

Boundary: “surface” that separates the

system from its surroundings (can be real or
imaginary, fixed or movable) System

Boundary

(source: Ref [1])

Closed, open, and Isolated Systems
• Closed (control mass):
No mass enter or leave the system.
Energy may cross the boundaries.

• Open (control volume):

Mass and energy can enter/leave the
system.

• Isolated: No mass and energy

can enter/leave the system.

(source: Ref [1])

 Other Definitions
• Property → any characteristics of a system.
– Example: pressure P*, temperature T*, volume V and mass m
• Thermal: thermal conductivity, thermal expansion
• Electrical: electrical conductivity
• Physicochemical: viscosity, surface energy, density
• Mechanical: modulus of elasticity, strenth
– Note: *In thermodynamic calcualtion, always use absolute
temperature and pressure

• State → definition of a system (has certain properties)

• Process → when property(ies) change thus change of state

(source: Ref [1])

 Energy
• Various forms: Thermal, Mechanical, Kinetic, Potential,
Electrical, Magnetic, Chemical, Nuclear
• In SI system → in Joule (J) or kJ
sometimes express per unit mass (J/g) or unit time
(J/s=watt)

Can be classified:
• Macroscopic → Those a system posseses a whole with
respect to some outside reference frame, e.g. PE, KE
• Microscopic → related to the molecular structures and
activities → internal energy (U)

(source: Ref [1])

 Internal Energy, U
• Sensible energy: the internal
energy associated with the
kinetic energies of the
molecules.
• Latent energy: the internal
energy associated with the
phase of a system.
• Chemical energy: : the internal
energy associated bonds in a
molecule.
• Nuclear energy: the
tremendous amount of energy
associated with the strong
bonds within the nucleus of
atom itself.
Thermal = sensible + latent
(source: Ref [1])
Internal = sensible + latent + chemical + nuclear
(source: Ref [1])
(source: Ref [1])
(source: Ref [1])
(source: Ref [1])
(source: Ref [1])
(source: Ref [1])
1st law in terms of enthalpy
Enthalphy change for a substance with
temperature
Enthalphy change for a substance with
temperature
(source: Ref [1])
ELLINGHAM DIAGRAM
 Ellingham
diagram
There are three main uses of the
Ellingham diagram:
1. Determine the relative ease of
reducing a given metallic oxide
to metal;
2. Determine the partial
pressure of oxygen that is in
equilibrium with a metal oxide
at a given
temperature; and
3. Determine the ratio of carbon
monoxide to carbon dioxide that
will be able to reduce the oxide
to metal at a given temperature.
Ellingham diagram
Ellingham diagram
 Termodinamika
dalam
Copper
SMELTING AND
CONVERTING
Special Thanks to: Prof Doug Swinbourne, RMIT
Lauri Pesonen, Peter Bjorklund, Outotec - Espoo
Eh-pH Diagrams

(www.tms.org)
 What Are These Things Again?
Eh–pH diagram: aka Pourbaix diagram, potential-pH diagram, electro-chemical phase diagram
Invented in 1930’s by Marcel Pourbaix (Belgian)
Used in lots of places: extractive metallurgy, corrosion (their original purpose), environmental
engineering, geochemistry
Closely tied to aqueous thermodynamics
 The Basics
x-axis is pH; usually 0–14, 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 oxidiz-ing 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 ΔG° = 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 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)
SIMULASI THERMODINAMIKA