Kuliah Metalurgi Ekstraksi

1
Prof. Dr. Ir. Johny Wahyuadi Soedarsono, DEA

Department of Metallurgy and Materials

Faculty of Engineering
University of Indonesia
Depok, 2 September 2016
1

Metallurgy
Metallurgy is the science and
technology of metal. It is the oldest
of the sciences devoted to the study
of engineering materials.
Metallurgy has evolved into three
separate groups: extractive,
mechanical, and physical.

Metallurgical Engineering
Metallurgical engineering or metallurgy
is the study of metals and is the oldest
sciences devoted to the study of
engineering materials.

Extractive Metallurgy

Benefication, mineral dressing,

pyrometallurgy,
hydrometallurgy, and
electrometallurgy.

Typical Beneficiation Steps

Beneficiation: the enrichment of ores and separation of unwanted gangue
minerals so subsequent treatment to get the metals is more efficient. Uses only
mechanical, physical, and physico-chemical methods. Can be divided into two
distinct steps.
Liberation: rock is broken down by mechanical means so that the individual mineral
components become independent of each other, i.e., each is detached or liberated.
Separation: valuable minerals are separated from the rest by means of physical and
physico-chemical methods making use of differences in specific gravity, magnetic
properties, etc.

Mineral Processing Methods =

beneficiation + extractive metallurgy

Extractive Metallurgy
Extractive metallurgy is the study of the
extraction and purification of metals from their
ores.
Extracting a metal from its ore is conducted in
several process steps.
For example, the extraction route from ore to
refined metal includes any or all of the
following process steps.

Metallurgy
Concentration.
Separate ore from waste rock.

Roasting.
Heat to a high temperature to form the oxide.

Reduction.
Commonly use carbon as coke or powdered coal.

Refining.
Metals must be purified.

Occurrence and Distribution of Metals

Early history is divided into the Stone Age, Bronze
Age, and the Iron Age.
If we consider a jet engine, there are 7 metals present.
Fe is not.
A modern jet engine consists mostly of Ti and Ni with
decreasing amounts of Cr, Co, Al, Nb and Ta.
The solid portion of the earth is called the lithosphere.
Concentrated metal deposits are found beneath the
earths surface.
Ore: deposit that contains enough metal that we can
extract economically.
10

Gambar 1. Mineral dan ikutannya

Evolution of metals

Copper
Gold

Stone age

Iron
Bronze

Bronze
age

Iron
age

Steels
Cast Iron

Super
Alloy
Alloys
Steels Light
Ti-, ZrAlloys
Alloys

Steel technologies

Special
Steels and
New
superalloys

Glassy
Metals

Age of advanced materials

Occurrence and Distribution of Metals

13

The Iron Triad: Iron, Cobalt and Nickel

Iron
annual worldwide production over 500 million tons.
Most important metal in modern civilization.
4.7% natural abundance.

Cobalt
0.0020% natural abundance.
Deposits are reasonably concentrated.
Primarily used in alloys, Co5Sm makes a good
magnet.

Nickel
24th most abundant element.
Primarily used in alloys, but also for electroplating.

Occurrence and Distribution of Metals

Minerals
Ore: deposit that contains enough metal that we can
extract economically.
Most metals are found in minerals.
Names of minerals are usually based on the location
of their discovery.
Other minerals are named after their colors:
malachite comes from the Greek malache (the name
of the tree with very green leaves).
Most important ores are oxide, sulfide and carbonate
minerals.
15

Occurrence and Distribution of Metals

Minerals

16

Occurrence and Distribution of Metals

Metallurgy
Metallurgy is the science and technology of extracting
metals from minerals.
There are five important steps:
Mining (getting the ore out of the ground);
Concentrating (preparing it for further treatment);
Reduction (to obtain the free metal in the zero oxidation
state);
Refining (to obtain the pure metal); and
Mixing with other metals (to form an alloy).

17

Metallurgy
In preliminary treatment, the ore is concentrated in
its metal-containing mineral.
The worthless portion of an ore is called gangue
(pronounced gang).
To separate the useful mineral from the gangue,
both physical and chemical methods may be used.

Metallurgy
In preliminary treatment, the ore is concentrated in
its metal-containing mineral.
Flotation is a physical method of separating the
mineral from the gangue by using the differences
in their wettabilities in a liquid solution.
Sulfide ores, such as those of copper, lead, and zinc,
are concentrated using flotation.

Figure 13.7: Flotation process for concentrating certain ores.

Metallurgy:
introduction

Mining &
Enrichment

Properties of
metals
Physical
metallurgy
Hot and cold
rolling
(...)

Material
sciences
Extractive
metallurgy

Electrometallurgy

Thermodynamics
Reaction
kinetics

Hydrometallurgy
Pyrometallurgy

Ores
Mining
Enrichment
Crushing
Screening
Mechanical
separation
(...)

Theory

Pyrometall.
pretreatment

e.g. Roasting

Water

Iron and
steel
Sulphideores (e.g. Cu)

(...)

Impurity
removal

Leaching

Methods

Metal
recovery
Similar
methods

Solvents

Transport
phenomena

Hydrometallurgical
metal production

Mass
transfer
Heat
transfer
Fluid
dynamics

e.g.
zinc
nickel

Electrowinning
Cementation

Acidic

Basic

Organic

Sintering
Coking
Flash
smelting

Chemical
Solvent
precipitation Ion extraction
exchange
Blast
furnace

Converters
(PS)

Converters
Casting
(LD/AOD/...)
Sulphur
Ladle
removal
treatments
Electric
furnaces

Pyrometallurgical
metal production

e.g.
iron/steel
copper

How to choose a process?

Transport
Energy
Raw materials
Water needed

Markets
Production chain

Products
Residues

Pyromet. unit operations

Hydromet. unit operations
Electro-chem. unit operations

Metallurgy
the mineral must first be separated from the
surrounding ore material by physical means
extractive metallurgy are the chemical
processes that separate a metal from its
mineral
refining are the processes that purify the metal
for use

23

Separation
first step is to crush the ore into small particles
the mineral is then separated from the gangue by
physical means
using cyclonic winds to separate by density
froth flotation in which the mineral is treated with a
wetting agent to make it more attracted to the froth

24

Alternative Methods
Many ores contain several metals and it is not
always necessary to separate them.
Fe(CrO2)2 can be reduced to ferrochrome and can be
added directly to iron to produce steel.
V2O5 and MnO2 are also added to iron to produce
other types of steel.

Titanium cannot be produced by reduction

with C.
In the Kroll process Mg is used.

Mining Basics - Theory

Turnings rock in the ground into
profits!
The fundamental value of a mineral
deposit ultimately depends entirely on its
capacity to support an economically
viable mining operation in the future

Pyrometallurgical Processes
The roasting reduction process is known as
pyrometallurgy.
Large quantities of waste material is produced
in concentrating low grade ore.
High energy consumption.
Gaseous emission must be controlled.

Pyrometallurgical unit operations

Production of
metals

Raw materials
Raw material
pretreatments
Thermal
pretreatment
Drying
Sintering
Pelletizing

Coking

Calcination

Products

Metal
extraction

Metal
refining

Reduction
and
oxidizing

Metal
raffination

Roasting Reduction
of oxides

Matte
production

Temperature
control
Composition
control

Impurity removal

Drying
Dangerous to charge wet materials to the high
temperature processes
The moisture that is allowed depends on the further
processing

Mechanical moisture removal prefered

Thermal drying requires a lot of energy

Counter-current drum-driers are common in

the drying of metallurgical raw materials
Utilisation of the process waste heat streams

Sintering
Problems in processing fine materials
Gas permeability
Dusting

Thermal agglomeration
Partial melting
Minimisation of the surface energy
as a driving force for agglomeration

Chemical and mineralogical changes in material

Drum-, batch- or belt-sintering
Pretreatment: Micropelletising

Pelletizing
Feeding of concentrates, binding materials and
water into the rotating and sloped pelletising drum
or plate
Capillar forces caused by moisture as cohesive
force
Aftertreatments in order to achieve wanted
properties
Sintering
Shaft furnace

Small pellets are fed back to

the process

Calcination
Thermal disintegration of a compound (which
leads into a formation of gaseous product)
Thermal conductivity (endothermic reactions)
Removal of gas from the reaction surface

e.g. calcination of limestone to produce burned

lime
Use of lime in iron and steelmaking slags
CaCO3 = CaO + CO2
HR >> 0
Counter-current shaft furnace or rotating drum

Other examples
Disintegration of CaMg(CO2)2 or Al(OH)2

Coking
Pyrolysis of coal in order to modify it to be more
suitable for metallurgical processes
Removal of water and volatile components
Agglomeration of coal particles
Porous coke as a result

Dry or wet quenching

Several by-products
Reducing gas (H2, CO)
Raw materials for chem. industry

Roasting
A process in which an anion of a solid compound
is changed without changing the valency of the
cation
High temperature processing of the sulphide ores
without agglomeration
Often used as a pretreatment for the
hydrometallurgical processes

Examples
Oxidising roasting
Sulphating roasting
Chlorine/Fluor/Alkalines/...

Oxidising roasting
Difficulties to reduce sulphide ores using carbon
e.g. 2 ZnS + C = 2 Zn + CS2 or ZnS + CO = Zn + COS
Equilibrium is strongly on the reactants side

Roasting of sulphides into the oxides

MeS + 3/2 O2 = MeO + SO2
Used e.g. in the production of lead, copper, zinc, cobalt,
nickel and iron when using sulphide ores as raw
materials
SO2 SO3 H2SO4

Fluidized bed, sintering or shaft furnace roasting

Products are either fine material or porous agglomerates

Sulphating roasting
Used in separation of metals from complex
materials
Some metals react to sulphates that are soluble to water
MeS + 3/2 O2 = MeO + SO2
SO2 + 1/2 O2 = SO3
MeO + SO3 = MeSO4

Some are left as oxides (non-soluble)

A pretreatment for hydrometallurgical processes

Usually fluidized bed roasting
Often used to remove iron from more valuable
metals (Cu, Ni, Zn, Co)
When T > 600 C Ferrisulphate is not stable

Reduction of oxides
MeO + R = Me + RO
Me is a metal
R is a reducing
component (an
element or a
compound which
forms an oxide which
is more stable than
MeO in the
considered
temperature)

Reduction of oxides
Carbo-thermal reduction
MeO + C = Me + CO
In practice:
MeO + CO = Me + CO2
C + CO2 = 2 CO (= Boudouard reaction)

Metallothermal reduction
MeO + M = Me + MO

Gas reduction
Usually H2 and CO (separately or as a mixture)
MeO + H2 = Me + H2O
MeO + CO = Me + CO2

Reduction of oxides
Specific and total CO2-emissions
of the Finnish steel industry
The largest industrial CO2-emissions
in Finland and Sweden (Mt)

Matte production
Separation of metals from the sulphides
Worthless metal is oxidised Oxidic slag
Wanted metal is still as a sulphide Matte

Matte is further refined Metal

Used e.g. in the production of copper, nickel and
lead
2 CuS + O2 = Cu2S + SO2
FeS2 + O2 = FeS + SO2
2 FeS + 3 O2 + SiO2 = Fe2SiO4 + 2 SO2

Removal of impurities (from iron/steel)

Carbon removal (hot metal crude steel)
To achieve wanted properties
Decarburization in BOF-converters
Removal of other oxidising impurities/elements (Si, Mn, P)
Oxygen blowing Oxide formation Slag/Gases
Temperature is increased
Scrap melting

Vacuum treatment
Burning of carbon is more efficient
in lowered pressure
Partial pressure of CO can also be
lowered using inert gases

Removal of impurities (from iron/steel)

Deoksidation / Oxygen removal
Solubility of oxygen in steel melt is appr. 0,2 % (T > 1500
C)
Solubility decreases when temperature is decreased
Causes CO formation, oxidation of alloying elements, etc.

Alloying, diffusion or vacuum deoxidation

Gas removal
Solubilities of gases decrease when T is decreased (cf. O)
Gas removal is based on decreasing the partial pressure of
the concerned element in the gas phase (vacuum, inert gas)

Sulphur removal
Formation of CaS Into the slag

Composition control (Steel)

Alloying of steel is made mainly in the BOFconverters after the blowing
More accurate alloying in the steel ladle
Lumps
Powder injection
Wire injection

Stirring
Inductive
Using an inert gas

Temperature control
Increased significance due to continuous
casting
Optimisation of a tap temperature
Inductive heating
Use of fuels
Plasma heaters
Chemical heating (Al, Si)
Electric arcs
Insulation
Scrap cooling
Stirring

Pyrometallurgy
Pyrometallurgy: using high temperatures to obtain
the free metal.
Several steps are employed:
Calcination is heating of ore to cause decomposition and
elimination of a volatile product:

PbCO3(s) PbO(s) + CO2(g)

Roasting is heating which causes chemical reactions
between the ore and the furnace atmosphere:

2ZnS(s) + 3O2(g) 2ZnO(s) + 2SO2(g)

2MoS2(s) + 7O2(g) 2MoO3(s) + 4SO2(g)
Smelting is a melting process that causes materials to
separate into two or more layers.
47

Pyrometallurgy
Slag consists mostly of molten silicates in addition to
aluminates, phosphates, fluorides, and other inorganic
materials.
Refining is the process during which a crude, impure metal
is converted into a pure metal.

The Pyrometallurgy of Iron

Most important sources of iron are hematite Fe2O3
and magnetite Fe3O4.
Reduction occurs in a blast furnace.
The ore, limestone and coke are added to the top of
the blast furnace.
Coke is coal that has been heated to drive off the
volatile components.
48

Pyrometallurgy
The Pyrometallurgy of Iron

49

Pyrometallurgy
The Pyrometallurgy of Iron
Coke reacts with oxygen to form CO (the reducing
agent):
2C(s) + O2(g) 2CO(g), H = -221 kJ
CO is also produced by the reaction of water vapor in
the air with C:
C(s) + H2O(g) CO(g) + H2(g), H = +131 kJ
Since this reaction is endothermic, if the blast furnace
gets too hot, water vapor is added to cool it down
without interrupting the chemistry.

50

Pyrometallurgy
The Pyrometallurgy of Iron
At around 250C limestone is calcinated (heated to
decomposition and elimination of volatiles).
Also around 250C iron oxides are reduced by CO:
Fe3O4(s) + 4CO(g) 3Fe(s) + 4CO2(g), H = -15 kJ
Fe3O4(s) + 4H2(g) 3Fe(s) + 4H2O(g), H = +150 kJ
Molten iron is produced lower down the furnace and
removed at the bottom.
Slag (molten silicate materials) is removed from above
the molten iron.

51

Pyrometallurgy
The Pyrometallurgy of Iron
If iron is going to be made into steel it is poured
directly into a basic oxygen furnace.
The molten iron is converted to steel, an alloy of iron.
To remove impurities, O2 is blown through the molten
mixture.
The oxygen oxidizes the impurities.

Formation of Steel
Steel is an alloy of iron.
From the blast furnace, the iron is poured into a
converter.
52

Pyrometallurgy
Formation of Steel
A converter consists of a steel shell encasing a
refractory brick liner.
After treatment in the blast furnace, there are
impurities in the iron, which must be removed by
oxidation.
Air cannot be present in the converter because the
nitrogen will form iron nitride (causes the steel to be
brittle).
Oxygen diluted with Ar is used as the oxidizing agent.

53

Steel
Three fundamental changes from pig iron.
Reduction of the C content.
3-4% in pig iron
0-1.5% in steel.

Removal, through slag formation, of:

Si, Mn, P (about 1% in pig iron)
Other minor impurities.

Addition of alloying elements.

Cr, Ni, Mn, V, Mo, and W.
Give the steel its desired properties.

Pyrometallurgy
Formation of Steel

When oxygen emerges

from the converter,
then all the impurities
have been oxidized
and the iron is poured
into a ladle.

55

Impacts of smelting
acid rain. The smelting of sulfide ores results in the emission of sulfur
dioxide gas, which reacts chemically in the atmosphere to form a
sulfuric acid . As this acid rain falls to the earth, it increases the acidity
of soils, streams, and lakes, harming the health of vegetation and fish
and wildlife populations.

* Copper and selenium, for example, which can be released from copper
smelters, are essential to organisms as trace elements, but they are toxic
if they are overabundant.
*

These metals can contaminate the soil in the vicinity of smelters,

destroying much of the vegetation. In addition, particulate matter
emitted from smelters may include oxides of such toxic metals as
arsenic (cumulative poison), cadmium (heart disease), and mercury
(nerve damage).

Solutions
Older smelters emitted most of the sulfur
dioxide generated, and now almost all of it is
captured prior to emission using new
technologies, such as electrostatic precipitators,
which capture dust particles and return them
to the process.
Raw material substitution or elimination, such
as recycling lead batteries and aluminum cans,
decreases the need to process ore, which
reduces pollution.

Hydrometallurgical Processes
Leaching: Metal ions are extracted from the ore
by a liquid.
Acids, bases and salts may be used.
Oxidation and reduction may also be involved.

Purification and concentration.

Adsorption of impurities on activated charcoal or by
ion exchange.

Precipitation.
Desired ions are precipitated or reduced to the free
metal.
Electroanalytical methods are often used.

Hydrometallurgy
Hydrometallurgy is the extraction of metals from ores
using water.
Leaching is the selective dissolution of the desired
mineral.
Typical leaching agents are dilute acids, bases, salts,
and sometimes water.
Gold can be extracted from low-grade ore by
cyanidation:
NaCN is sprayed over the crushed ore and the gold is
oxidized:
4Au(s) + 8CN-(aq) + O2(g) + 2H2O(l) 4Au(CN)2-(aq) + 4OH(aq)
59

Hydrometallurgy
The gold is then obtained by reduction:
2Au(CN)2-(aq) + Zn(s) Zn(CN)42-(aq) + 2Au(s)

The Hydrometallurgy of Aluminum

Aluminum is the second most useful metal.
Bauxite is a mineral that contains Al as Al2O3.xH2O.
Bayer process:
The crushed ore is digested in 30% NaOH (by mass) at 150 230C and high pressure (30 atm to prevent boiling).
Al2O3 dissolves:
Al2O3.H2O(s) + 2H2O(l) + 2OH-(aq) 2Al(OH)4-(aq)
The aluminate solution is separated by lowering the pH.
The aluminate solution is calcined and reduced to produce
the metal.
60

Electrometallurgy
Electrometallurgy of Sodium
Electrometallurgy is the process of obtaining metals
through electrolysis.
Two different starting materials: molten salt or
aqueous solution.
Sodium is produced by electrolysis of molten NaCl in
a Downs cell.
CaCl2 is used to lower the melting point of NaCl from
804C to 600C.
An iron screen is used to separate Na and Cl (so that
NaCl is not re-formed).
61

Electrometallurgy
Electrometallurgy of Sodium

At the cathode (iron):

2Na+(aq) + 2e- 2Na(l)
At the anode (carbon):
2Cl-(aq) Cl2(g) + 2e-

62

Electrometallurgy
Electrometallurgy of Aluminum
Hall process electrolysis cell is used to produce
aluminum.
Al2O3 melts at 2000C and it is impractical to perform
electrolysis on the molten salt.
Hall: use purified Al2O3 in molten cryolite (Na3AlF6,
melting point 1012C).
Anode: C(s) + 2O2-(l) CO2(g) + 4e Cathode: 3e- + Al3+(l) Al(l)
The graphite rods are consumed in the reaction.
Bayer process: bauxite (~ 50 % Al2O3) is concentrated
to produce aluminum oxide.
63

Electrometallurgy
Electrometallurgy of Aluminum

64

Electrometallurgy
Electrometallurgy of Aluminum
To produce 1000 kg of Al, we need 4000 kg of bauxite,
70 kg of cryolite, 450 kg of C anodes and 56 109J of
energy.

65

Electrometallurgy
Electrorefining of Copper
Because of its good conductivity, Cu is used to make
electrical wiring.
Impurities reduce conductivity, therefore pure copper
is required in the electronics industry.
Slabs of impure Cu are used as anodes, thin sheets of
pure Cu are the cathodes.
Acidic copper sulfate is used as the electrolyte.
The voltage across the electrodes is designed to
produce copper at the cathode.
The metallic impurities do not plate out on the
cathode.
66

Electrometallurgy
Electrorefining of Copper
Metal ions are collected in the sludge at the bottom of
the cell.
Copper sludge provides about 25 % of US silver
production and 13 % of US gold production.

67

Metallic Bonding
Physical Properties of Metals
Important physical properties of pure metals:
malleable, ductile, good conductors, and feel cold.
Most metals are solids with the atoms in a close
packed arrangement.
In Cu, each atom is surrounded by 12 neighbors.
There are not enough electrons for the metal atoms to
be covalently bonded to each other.

68

Metallic Bonding
Electron-Sea Model for Metallic Bonding
We use a delocalized model for electrons in a metal.

The metal nuclei are seen to exist in a seal of electrons.

No electrons are localized between any two metal atoms.
Therefore, the electrons can flow freely through the metal.
Without any definite bonds, the metals are easy to deform
(and are malleable and ductile).

Problems with the electron sea model:

As the number of electrons increase, the strength of bonding
should increase and the melting point should increase.
But: group 6B metals have the highest melting points
(center of the transition metals).
69

Metallic Bonding
Electron-Sea Model for Metallic Bonding

70

Metallic Bonding
Molecular-Orbital Model for Metals
Delocalized bonding requires the atomic orbitals on
one atom to interact with atomic orbitals on
neighboring atoms.
Example: graphite electrons are delocalized over a
whole plane, benzene molecules have electrons
delocalized over a ring.
Recall: the number of molecular orbitals is equal to
the number of atomic orbitals.
In metals there is a very large number of orbitals.
As the number of orbitals increase, their energy
spacing decreases and they band together.
71

Metallic Bonding
Molecular-Orbital Model for Metals

72

Metallic Bonding
Molecular-Orbital Model for Metals
The number of electrons do not completely fill the
band of orbitals.
Therefore, electrons can be promoted to unoccupied
energy bands.
Since the energy differences between orbitals are
small, the promotion of electrons occurs at low energy
costs.
As we move across the transition metal series, the
antibonding band starts becoming filled.

73

Metallic Bonding
Molecular-Orbital Model for Metals
Therefore, the first half of the transition metal series
have only bonding-bonding interactions, the second
half has bonding-antibonding interactions.
We expect the middle of the transition metal series to
have the highest melting points.
The energy gap between bands is called the band gap.
The electron sea model is a qualitative interpretation
of band theory (molecular-orbital model for metals).

74

Alloys
Alloys have more than one element with
characteristics of metals.
Pure metals and alloys have different physical
properties.
In jewelry an alloy of gold and copper is used (the
alloy is harder than soft gold).
Solution alloys are homogeneous mixtures.
Heterogeneous alloys: components are not dispersed
uniformly (e.g. pearlite steel has two phases: almost
pure Fe and cementite, Fe3C).

75

Alloys

76

Alloys
There are two types of solution alloy:
substitutional alloys (the solute atoms take the positions of
the solvent);
interstitial alloys (the solute occupies interstitial sites in the
metallic lattice).

Substitutional alloys:
atoms must have similar atomic radii,
elements must have similar bonding characteristics.

Interstitial alloys:
one element must have a significantly smaller radius than
the other (in order to fit into the interstitial site), e.g. a
nonmetal.
77

Alloys
Interstitial alloys:
The alloy is much stronger than the pure metal (increased
bonding between nonmetal and metal).
Example steel (contains up to 3 % carbon).

78

Transition Metals
Physical Properties
Transition metals occupy the d block of the periodic
table.
Almost all have two s electrons (exceptions group 6B
and group 1B).
Most of these elements are very important in modern
technology.
Physical properties of transition metals can be
classified into two groups: atomic properties (e.g. size)
and bulk properties (e.g. melting point).
The atomic trends tend to be smooth for the transition
metals.
79

Transition Metals
Physical Properties

80

Transition Metals
Physical Properties

81

Transition Metals
Physical Properties
Most of the trends in bulk properties are less smooth
than the atomic properties.
The trends in atomic properties of the transition
metals can be exemplified with atomic radius.
Atomic radius decreases and reaches a minimum
around group 8B (Fe, Co, Ni) and then increases for
groups 1 and 2.
This trend is again understood in terms of effective
nuclear charge.
The increase in size of the Cu and Zn triads is
rationalized in terms of the completely filled d orbital.
82

Transition Metals
Physical Properties

83

Transition Metals
Physical Properties
In general atomic size increases down a group.
An important exception: Hf has almost the same radius as
Zr (group 4B): we would expect Hf to be larger than Zr.
Between La and Hf the 4f shell fills (Lanthanides).
As 4f orbitals fill, the effective nuclear charge increases and
the lanthanides contract smoothly.
The Lanthanide Contraction balances the increase in size
we anticipate between Hf and Zr.
The second and third series are usually about the same size,
with the first series being smaller.
Second and third series metals are very similar in their
properties (e.g. Hf and Zr are always found together in ores
and are very difficult to separate).
84

Transition Metals
Electron Configurations and Oxidation States
Even though the (n - 1)d orbital is filled after the ns
orbital, electrons are lost from the orbital with highest
n first.
That is, transition metals lose s electrons before the d
electrons.
Example: Fe: [Ar]3d64s2, Fe2+: [Ar]3d6.
d-Electrons are responsible for some important
properties:
transition metals have more than one oxidation state,
transition metal compounds are colored (caused by
electronic transitions),
85

Transition Metals
Electron Configurations and Oxidation States

86

Transition Metals
Electron Configurations and Oxidation States
transition metal compounds have magnetic properties.

Note all oxidation states for metals are positive.

The 2+ oxidation state is common because it
corresponds to the loss of both s electrons.
(Exception: Sc where the 3+ oxidation state is
isoelectronic with Ar.)
The maximum common oxidation state is +7 for Mn.
For the second and third series, the maximum
oxidation state is +8 for Ru and Os (RuO4 and OsO4).

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Transition Metals
Magnetism
Magnetism provides important bonding information.
There are three types of magnetic behavior (shown
here in order):
Diamagnetic (no atoms or ions with magnetic moments);
Paramagnetic (magnetic moments not aligned outside a
magnetic field);
Ferromagnetic (coupled magnetic centers aligned in a
common direction).

Electron spin generates a magnetic field with a

magnetic moment.

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Transition Metals
Magnetism

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Transition Metals
Magnetism
When two spins are opposing the magnetic fields
cancel (diamagnetic).
Diamagnetic substances are weakly repelled by external
magnetic fields.

When spins are unpaired, the magnetic fields do not

cancel (paramagnetic).
Generally, the unpaired electrons in a solid are not
influenced by adjacent unpaired electrons. That is,
the magnetic moments are randomly oriented.
When paramagnetic materials are placed in a
magnetic field, the electrons become aligned.
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Transition Metals
Magnetism
Ferromagnetism is a special case of paramagnetism
where the magnetic moments are permanently aligned
(e.g. Fe, Co and Ni).
Ferromagnetic oxides are used in magnetic recording
tape (e.g. CrO2 and Fe3O4).

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Chemistry of Selected Transition Metals

Chromium
In the absence of air, Cr reacts with acid to form a
solution of blue Cr2+:
Cr(s) + 2H+(aq) Cr2+(aq) + H2(g)
In the presence of air, the Cr2+ readily oxidizes to
Cr3+:
4Cr2+(aq) + O2(g) + 4H+(aq) 4Cr3+(aq) + 2H2O(l)
In the presence of Cl-, Cr3+forms the green
Cr(H2O)4Cl2+ ion.

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Chemistry of Selected Transition Metals

Chromium
In aqueous solution, Cr is usually present in the 6+
oxidation state.
In base chromate, CrO42-, is the most stable ion.
In acid dichromate, Cr2O72-, is the most stable ion.
Chromate is a much darker yellow than dichromate.

Iron
In aqueous solution iron is present in the +2 (ferrous)
or +3 (ferric oxidation states).
Iron reacts with nonoxidizing agents to form Fe2+(aq).
In the presence of air, Fe2+ is oxidized to Fe3+.
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Chemistry of Selected Transition Metals

Iron
As with most metal ions, in water iron
forms complex ions, Fe(H2O)6n+.
In acidic solution Fe(H2O)63+ is stable, but
in base Fe(OH)3 precipitates.
If NaOH is added to a solution of Fe3+(aq)
and the brownish Fe(OH)3 precipitate is
formed.

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Chemistry of Selected Transition Metals

Copper
In aqueous solution copper has two dominant
oxidation states: +1 (cuprous) and +2 (cupric).
Cu+ has a 3d 10electronic configuration.
Cu(I) salts tend to be white and insoluble in water.
Cu(I) disproportionates:
2Cu+(aq) Cu2+(aq) + Cu(s)
Cu(II) is the more common oxidation state.
Blue vitriol is CuSO4.5H2O.

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Chemistry of Selected Transition Metals

Copper
In aqueous solution, four water molecules are
coordinated to the Cu and one is hydrogen bonded to
the sulfate.
Water soluble copper(II) salts include Cu(NO3)2,
CuSO4, and CuCl2.
However, Cu(OH)2 is insoluble and can be
precipitated by adding NaOH to a solution containing
Cu2+ ions.

96