Kuliah Metalurgi Ekstraksi

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

Department of Metallurgy and Materials Faculty of Engineering University of Indonesia Depok, 17 September 2010
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Metallurgical Engineering
Metallurgical engineering or metallurgy is the study of metals and is the oldest sciences devoted to the study of engineering materials.

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.

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.

Extractive Metallurgy

Benefication, mineral dressing, pyrometallurgy, hydrometallurgy, and electrometallurgy.

Mechanical Metallurgy
Mechanical metallurgy is the study of the techniques and mechanical forces that shape or make finished forms of metal.

Physical Metallurgy
Physical metallurgy is the study of the effect of structure on the properties of metals. The two structures studied in physical metallurgy are the crystal structure and micro structure. See figure 1-4 The crystal structure is the arrangement of atoms in the metal. An atom is the smallest building block of matter that can exist alone or in combination. It cannot be divided without changing its basic character. The crystal structure is shown through modeling. The microstructure is the microscopic arrangement of the components, or phases, within a metal. The technology of heat treatment of steels is based on a specific crystal structure and microstructure change that occurs when steel is rapidly cooled from a high temperature. These changes lead to hardening and strengthening of steels.

Ceramic Engineering
Ceramic engineering, or ceramics, is the study of the development and production of products made from nonmetallic, inorganic materials by firing at high temperatures. Ceramic materials are divided into four groups:

Ceramic Engineering Cont.

Clay-based materials Refractories Glasses Inorganic cements

Polymer Engineering
Polymer engineering or polymer is the study of the development and production of synthetic organic materials. Polymer are divided into two groups:

Polymer Engineering Cont.

Thermoplatics Thermosets Polymer are used In applications such as adhesives, building products, fibers sporting goods, and automotive and aerospace components.

Composite Engineering
Composite engineering, or composites, is the study of the applicability of combinations of materials. Composites are used to strengthen metals, ceramics, or polymers and improve their structural usefulness.

Materials Engineering
Materials engineering, which crosses the boundaries of all the branches of materials sciences, is the study of the evaluation of the characteristic properties of all materials.

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.
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Gambar 1. Mineral dan ikutannya

Evolution of metals

Copper Gold

Iron Bronze

Steels Cast Iron

Super Alloy Alloys Steels Light Ti-, ZrAlloys Alloys

Special Steels and New superalloys

Glassy Metals

Stone age

Bronze age

Iron age

Steel technologies

Age of advanced materials

Occurrence and Distribution of Metals

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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.
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Occurrence and Distribution of Metals

Minerals

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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).

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Metallurgy: introduction
Extractive metallurgy

Material sciences
Electrometallurgy Hydrometallurgy

Mining & Enrichment

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

Thermodynamics Reaction kinetics

Mass transfer Heat transfer Fluid dynamics

Pyrometallurgy

Theory

Transport phenomena

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

Pyrometall. pretreatment

Leaching

Impurity removal

Metal recovery

Hydrometallurgical metal production

e.g. zinc nickel

e.g. Roasting

Methods

Solvents

Similar methods

Electrowinning Cementation

Water

Acidic

Basic

Organic

Chemical Solvent precipitation Ion extraction exchange Blast furnace Converters Casting (LD/AOD/...) Sulphur Ladle removal treatments Electric furnaces Pyrometallurgical metal production

Iron and steel Sulphideores (e.g. Cu)

Sintering Coking Flash smelting

Converters (PS)

e.g. iron/steel copper

(...)

How to choose a process?

Transport Energy Raw materials Markets Production chain

Products

Water needed

Pyromet. unit operations Hydromet. unit operations Electro-chem. unit operations

Residues

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

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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

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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 Companies Raison d'tre

1.Survival 2.Profitability:

Stable earnings Earnings growth Disposals

3.Growth

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

Raw materials
Raw material pretreatments Thermal pretreatment
Drying
Sintering Pelletizing Coking

Production of metals
Metal extraction Reduction and oxidizing Metal refining

Products

Metal raffination

Temperature control Composition control

Roasting Reduction of oxides

Matte production

Calcination

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.
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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.
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Pyrometallurgy
The Pyrometallurgy of Iron

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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.

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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.

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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.
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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.

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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.

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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)
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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.
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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).
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Electrometallurgy
Electrometallurgy of Sodium
At the cathode (iron): 2Na+(aq) + 2e- 2Na(l) At the anode (carbon): 2Cl-(aq) Cl2(g) + 2e-

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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.
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Electrometallurgy
Electrometallurgy of Aluminum

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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.

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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.
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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.

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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.

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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).
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Metallic Bonding
Electron-Sea Model for Metallic Bonding

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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.
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Metallic Bonding
Molecular-Orbital Model for Metals

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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.

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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).

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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).

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Alloys

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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.
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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).

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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.
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Transition Metals
Physical Properties

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Transition Metals
Physical Properties

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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.
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Transition Metals
Physical Properties

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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).
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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),
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Transition Metals
Electron Configurations and Oxidation States

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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.

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