CH 20 Properties of The 3d Transition Metal

Properties of the 3d
Transition Metals
Chapter 20
“Read in the name your God who created “ )I( Inorganic Chemistry 3 )I( Dr. Miftahul Khair, M.Sc (miftah@fmipa.unp.ac.id)
http://kimia.unp.ac.id
http://kimia.fmipa.unp.ac.id
Ronald Nyholm, brought inorganic chemistry to life again:
• it was the nature of the ligand that determined much of
metal ion behavior.
• together with Gilespie he devised VSEPR method of
predicting molecular shape.
• inorganic chemistry involved the understanding of
molecular structure, not just memorization of formulas.
20.1 Overview of the 3d Transition Metals
All are hard (except copper), dense, and

high m.p.
Compounds
¨ Transition metal compounds display both ionic and covalent
character.
· MnO mp 1785 C.
· Mn2O7 boils at r.t. and is highly explosive.
¨ Often occur as polyatomic cations or anions.
· VO2+, MnO4-,and Cr2O72- .
Catalysis
¨ Catalysis plays an essential aspect in about 90% of all chemical
manufacturing.
¨ Ni and Pt are very heterogeneous catalysts.
¨ Pt, Rh, and Pd are used in catalytic converters.
¨ V2O5 is used in conversion of SO2 to SO3.
¨ Polyethylene is formed catalytically.
Metallurgy
1. Concentration.
Separate ore from waste rock.
2. Roasting.
Heat to a high temperature to
form the oxide.
3. Reduction.
Commonly use carbon as coke or
powdered coal.
4. Refining.
Metals must be purified.
Principles of Extractive Metallurgy
The Vanadium-Chromium-Manganese Triad
VCrMn triad
Oxidation States
VCrMn triad
1. form oxo-anions
(vanadate, VO43-; chromate, CrO42-; and
permanganate, MnO4-)
2. tetrahedral ions
that exist both in solution and in solid ionic
compounds.
Similarities between the (n) and (n + 10) elements :
V≈P Cr ≈ S :
a. VO43- ≈ PO43- ; H3VO4 ≈ H3PO4 chromic acid ≈ sulfuric acid.
b. intermediate acid anions : [HVO4]2- and

[H2VO4]-. Mn ≈ Cl:
permanganate ≈ perchlorate
c. solid-state oxyanion [VO3]- ≈ [PO3]-
The Iron-Cobalt-Nickel Triad
FeCoNi triad,
have similarities in their chemistry;

1. all ferromagnetic
2. identical m.p (between 1455° and 1535°C).
The difference between the triad :

• The highest ox.st is no longer that of the d0 configuration (Ti4+, V5+,
Cr6+ Mn7+).
Each of the three Fe-Co-Ni triad metals has a common oxidation state of
+2, and they all form the hexaaqua ions, [M(OH2)6]2+, and the tetrahedral
tetrachloro ions, [MCl4]2–.
Color and Magnetism
20.2 Group 4: Titanium
• Hard, silvery white metal, is the least dense (4.5 g/cm3) of the
transition metals.
• Use for defence industry:
Extraction of Titanium
Ti pure metal is difficult
to obtain from the most
common titanium ore,
TiO2, (rutile).
Kroll process
dissolved out by using dilute acid
Electrolytic Production of Ti
TiO2 - Titanium (IV) Oxide
- Use as paint (white) pigment with high refractive index.
- found as the impure dioxide (rutile).

Purification :
Rutile and anatase
Bright white paint TiO2
• “white lead,” Pb3(CO3)2(OH)2 was used bofore TiO2, but it is toxic,
and give black lead(II)sulfide to air.
• TiO2 is very low toxicity, highest refractive index, As a result of this
high light-scattering ability, it covers and hides previous paint layers
more effectively.
Rutile, as a large band-gap semiconductor,
TiO2 as Photocatalyst
TiO2 as a photocatalyst for water breaking.
Schematic Water Splitting Cell using TiO2 as photocatalyst:
20.3 Group 5: Vanadium
• None of the Group 5 metals has any great usefulness,
• four different ox.st : +5, +4, +3, and + 2 ( d0, d1, d2,
and d3 electron conf).
+2 +3 +4 +5
20.4 Group 6: Chromium
• Important industrial metal present in earth crust at 0.0122%.
• Chromite Fe(CrO2)2.
• Hard, maintains a bright surface, corrosion resistant.
Cr metal
dissolved
in HCl to Oxidation of Cr2+
give Cr2+ to Cr3+ occurs
in solution. rapidly in air.
Chromium
2+ Cr(H2O)62+, blue
3+ (acidic) Cr(H2O)63+, blue (basic) Cr(OH)4-, green
6+ (acidic) Cr2O72-, orange (basic) Cr2O42-, yellow
CrO Cr2O3 CrO3
basic amphoteric acidic
Chromates and Dichromates
Permanganates
KMnO4, is an extremely powerful oxidizing agent.
20.5 Group 7: Manganese
-3rd most abundant transition metal after Fe and Ti.
- found mainly as a silicate mineral, braunite, 3Mn2O3.MnSiO4.
- as an additive in speciﬁc types of steel.
Manganese Oxidation States
• KMnO4 reagent in redox titrations, but not a suitable primary standard,
because its purity cannot be guaranteed 
• Samples of the substance contain some manganese(IV)oxide, and
aqueous solutions slowly deposit brown manganese(IV) oxide on
standing.
Manganese(II) Compounds
• Under acid conditions, is the most thermodynamically stable

• Very pale pink ion, [Mn(OH2)6]2+
Manganese(II) chloride crystals –

The only way an electron can absorb energy in the
the pale pink color of Mn (II) salts visible spectrum is by inverting its spin and pairing
is due to a spin-forbidden 3d with another electron during the excitation
transition, which is rare.  little visible light is absorbed
20.6 Group 8: Iron
Factors for Iron dominance in our society :
1. 2nd most abundant metal in the Earth’s crust.
2. The ore can be easily processed thermochemically.
3. malleable and ductile.
4. the m.p (1535°C) is ‘low’.
5. can form alloys
Weakness of iron:
easy oxidation to form rust.
Sources of iron :
ores : Fe3O4 (magnetite), Fe2O3 (hematite) , and Fe2O3.1½H2O (limonite)
Production of Iron
Fe2O3(s) + 3 CO(g) → 2 Fe(l) + 3 CO2(g)
Alloy of Iron Alloy is a mixture or
metallic solid solution
composed of two or more
elements.
Why is steel stronger than iron?
• Pure iron is too soft for many uses.
• Steels are alloys.

Pure iron
• The different sized atoms added

distort the layers in the structure of
the pure metal, making it more
difficult for them to slide over each
other, and so alloys are harder. steel
steel
Iron(VI) Compounds
• d0 3d transition metals do not form
compounds .
• Fe+3 is very difficult to prepare.
• The ferrate ion, [FeO4]2–,  d2 ; ox state +6 ,
= very rare
Iron(III) Compounds
• The iron(III) ion is small and sufficiently polarizing

and exhibit covalent character.
E.g : iron(III) chloride is a redblack, covalent solid with a
network covalent structure.
• When heated to the gas phase, it exists as the dimeric species

Fe2Cl6,
• Iron(III) chloride can be made by heating iron in the presence of

dichlorine.
Fe3+ and Al3+ : A Case of Similarities between (n +5) and (n + 10)
Fe3+ and Al3+
Similarity :
a. Charge density >>
b. Form covalent chlorides of the form
M2Cl6
Dissimilarity :
Fe3+ = basic, Al3+ = ampoter
Iron(II) Compounds
• All the common hydrated iron(II) salts contain

the pale green [Fe(OH2)62+ ions,
Mohr’s salt : (NH4)2Fe(SO4)2.6H2O
• used as a standard for redox titrations

(determining the concentration of KMnO4
solutions)
The Rusting
Process
The green precipitate formed is then oxidised

further to form a brown precipitate of Fe2O3.xH2O.
Iron Oxides
3 common oxides :
1. iron(II) oxide, FeO;
2. iron(III) oxide,Fe2O3; and
3. iron(II) iron(III) oxide, Fe3O4
Black FeO :
• is a nonstoichiometric compound, (Fe0.95O),
which results from “missing” iron(II) ions
in some of the octahedral lattice sites while
some iron(III) ions occupy
20.7 Group 9: Cobalt
• bluish white, hard, ferromagnetic, unreactive.
• common ox.st +2 and +3.
Cobalt(III) Compounds
• All complexes are octahedral, and kinetically

inert
Cobalt(III) Compounds
• Na3[Co(NO2)6] and K3[Co(NO2)6]
water-soluble insoluble
Insoluble  due to the relative ion

sizes.
• size of K+ = size of the polyatomic anion;
•  balance of lattice energy and
hydration energies favors a lower
solubility for the compound.
Altering the ligands produces dramatic changes in Eo values, which in turn
affects the stabilities of the various ox.sts.
• Eg: the oxidation of the hexaamminecobalt(II) ion is much more
thermodynamically feasible than that of the hexaaquacobalt(II) ion:
Coupling with the reduction of dioxygen:
enables [Co(NH3)6]2+ to be oxidized to [Co(NH3)6]3+ in aqueous solution.
Overal :
We can synthesize variety cobalt(III) with NH3 and Cl- ligands:
The number of ions is identiﬁed with conductivity measurements,

Cl- ion can be quantitatively precipitated with silver ion.
• By comparing the electron configurations in an octahedral field, we can
see why ligands causing a larger crystal field splitting would enable
cobalt(II) to be readily oxidized.
• For cobalt(II), nearly all the complexes are high spin, whereas
cobalt(III), with its higher charge, is almost always low spin.
• Thus, the oxidation results in a much greater CFSE.
• The higher the ligands in the spectrochemical series, the greater the
oct value and the greater the CFSE increase obtained by oxidation.
Cobalt(II) Compounds
Silica gell with CoCl2 ;

• blue : an effective drying agent,
• pink : water-saturated and must be heated
to expel the absorbed moisture.
20.8 Group 10: Nickel
• Silvery white metal, uncreative.
Nikel
• Nickel plating is sometimes used to
protect iron.
• The only common oxidation number is

+2.
• Most Ni complexes have an octahedral
Aluminium bronze
geometry, few tetrahedral and square-
planar.
kuningan
Extraction of Nickel
To separate the Ni from the other metals (e.g

Co,Fe):
1. electrolytic process :
- impure nickel is cast into anodes and,
- electrolyte : solutions of NiSO4 and NiCl2,
pure nickel is deposited at the cathode.
2. Mond process.
Nickel(II) Compounds
squareplanar
Octahedral versus Tetrahedral Stereochemistry
Complexes :
• Cobalt(II)  tetrahedral,
• Nickel(II)  octahedral; few are square
planar, and very few are tetrahedral.
• Factors for the choice of stereochemistry:

CFSE.
• Because tet is 4/9 that of oct, the CFSE for a tetrahedral

environment will always be less than that of the isoelectronic
octahedral environment.
• CFSE energies are greatest for the high-spin d3 and d8 cases, and
these are the electron configurations for which we find the fewest
tetrahedral complexes
20.9 Group 11: Copper
• Yellow, or reddish due to thin coating of Cu2O.
• Cu is one of the two common yellow metals (the other being Au),
although a thin coating of Cu2O, makes copper look reddish.
• The color of Cu is caused by the filled d band in the metal being

only about 220 kJ/mol lower in energy than the s-p band.
The ores are :
• chalcopyrites and copper pyrites Copper(I) iron(III)

sulfide, CuFeS2
CuAl6(PO4)4(OH)8.4H2O, is the valued blue gemstone turquoise.
The extraction of copper
• Ore CuFeS2,
• using either a thermal or an aqueous process.
• pyrometallurgical process: the concentrated ore is heated (a process called
roasting) in a limited supply of air. This reaction decomposes the mixed sulfide
to give iron(III) oxide and copper(I) sulfide:
Sand is added:
Air is again added :
The mixture of copper(I) oxide and copper(I) sulfide then undergoes redox
reaction :
thermal process =pyrometallurgy

aqueous process= hydrometallurgy.
Metallurgy of Copper
• Concentration of sulfide ore is done by

floatation.
• Smelting at 800 C converts CuS to CuO.
• Copper matter contains CuO/FeS.
◄ Slag (Fe, Ca, Al and Si).
• FeO(s) + SiO2(s) → FeSiO3(l) for example.
• Conversion (blow air through molten matte)
and form iron slag.
• Blister copper contains SO2 bubbles and can
be used where high purity is not essential (or
purify electrochemically).
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.
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.
Waste Solution from a Leaching Operation
Biological Aspects
Vanadium
1. the tunicates, or sea squirts : utilizes very high
levels of vanadium in its blood plasma for O2
transport.
2. mushroom Amanita muscaria,  V role not

well understood
Chromium
• We need small quantities of Cr3+ in our diet.
• Insulin and the Cr3+ regulate blood glucose levels.
Manganese
• element in plant and animal enzymes.
Iron
Fe-containing macromolecules: hemoglobin, ferritin, and the ferredoxins
The End
Supplementary topics
• TiO2 is desirable for photocatalysis due to its inertness, stability, low
cost, self regenerating and recyclable.
Rutile/Anatase Band Alignment
• TiO2 – most widely used oxide for

photocatalysis.
• TiO2 has two main polymorphs:

• Anatase - 3.2 eV band gap, good
photocatalyst.
• Rutile – 3.0 eV band gap, poor
photocatalyst.
• Mixed phase anatase/rutile samples show
improved performance.
Its redox potential of the H2O/*OH
couple (-2.8 eV) lies within the
band gap.
However, its large band gap
(Eg=3.2 eV) only allows
absorption the UV of solar
spectrum.
An absorber in the visible range is
desired.
Absorption in the visible range can
be improved by dye sensitization,
doping , particle size modification,
and surface modification by noble
metals.
PROBLEM OF TiO2 FOR HARVESTING SOLAR ENERGY
• Band Gap of TiO2 is ~3.4 eV So it absorbs only the UV Part of Solar

Spectrum (~5% of Total Energy)
An Ideal Solar
AM Absorber
O should be
Black!
IDEAL ABSORBER
AM
1
CRYSTAL STRUCTURES OF TiO2
• THE COMMON FORMS OF TIO2

ARE RUTILE, ANATASE & STRUCTURE OF ANATASE
BROOKITE. Conventional Primitive Unit Cell
• RUTILE IS THE MOST STABLE Tetragonal Unit Cell
BUT THE RUTILE & ANATASE

STRUCTURES ARE QUITE
SIMILAR.
• IN BOTH STRUCTURES THE TI IS
SURROUNDED BY 6 O ATOMS TO
FORM OCTAHEDRALS. IN
ANATASE THE OCTAHEDRALS
SHARE ONLY EDGES. IN RUTILE
THE OCTAHEDRALS SHARE SMALL CIRCLES: Ti
BOTH EDGES AND CORNERS. LARGE CIRCLES: O
• THE POINT GROUP SYMMETRY

IS D4H. THE SPACE GROUP
SYMMETRY OF ANATASE IS:
How to decrease the Bandgap TiO2?
 RESULTS: TiO2 band gap is reduced to
• Doping with impurities
• H, N, METAL IONS VISIBLE producing blue, yellow or ditry
TiO2.
• Induced intrinsiv
defects.  Natural Crystal of Rutile and Anatase are
• O VACANCIES oftne colored but transparent.
• DECREASE VALENCE
OF Ti FROM 4 TO 3
Red rutile mined in Switzerland Anastase grown in Lab
Nov 2012
INTRODUCTION TO TiO2: ELECTRONIC STRUCTURE
• Valence Band of Anatase consists mainly of 3 regions [M.Emori

et al. Phy. Rev. B 85, 035129 (2012)].
• Top region (a):O (2pp)
• Middle region (b): O (2pp) hybridized with Ti 3d (t2g)
• Lowest region (c): O(2ps) hybridized with Ti 3d (eg)
(a)
(b)
(c)
TiO2 as a photocatalyst for water breaking.
Schematic Water
Splitting Cell using
TiO2 as photocatalyst:
The valence band of TiO2 can

be raised by >2eV without
affecting its photocatalytic
ability
PHOTOCATALYST SELF- CLEANING and
HYDROPHILIC ANTIFOGGING functions
RUTILE ANATASE
Density: 4,2 g/cc

Refractive Index: 2,76
rutile and anatase
TITANIUM DIOXIDE
White pigment in paints, cosmetics and foodstuffs.

Semiconductor transparent in the visible region of the
spectrum.
Low costs material.
Chemically inert, non-toxic, biocompatible.
SELF-CLEANING SURFACE
TO REALIZE SELF-CLEANING MATERIAL SURFACES

THERE ARE THREE PRINCIPAL WAYS :
Super-hydrophobicity.
Photocatalysis.
Super-hydrophilicity and hydrophilicity
HYDROPHOBICITY
• Hydrophobic materials ("water hating") have little or no tendency
to adsorb water and water tends to "bead" on their surfaces (i.e.,
discrete droplets).
• Hydrophobic materials possess low surface tension values and
lack active groups in their surface chemistry for formation of
"hydrogen-bonds" with water.
CONTACT ANGLE
For a given droplet on a solid surface: the contact angle is a

measurement of the angle formed between the surface of a solid
and the line tangent to the droplet radius from the point of contact
with the solid.
SUPER-HYDROPHOBICITY
The LOTUS EFFECT
PHOTOCATALYSIS
WHAT IS IT?
The acceleration of the rate of a photoreaction by

the presence of a catalyst (semiconductor particle).
WHAT IS a SEMICONDUCTOR SOLID?
HOW DOES PHOTOCATALYTIC
SEMICONDUCTOR WORK?
TiO2 AS PHOTOCATALYST
TiO 2  h   h  e 
D  h D  
H2O  h   OH  H
 
A  e  A  
O2  e   O
 -
2
OXIDATION-REDUCTION REACTION
ON THE SURFACE OF TIO2
IT IS COMPETITIVE BECAUSE:
A low-cost material is used as photocatalyst.

The reaction is quite fast at mild operating conditions
(room temperature, atmospheric pressure).
A wide spectrum of organic contaminants can be
converted to water and CO2.
No chemical reactants must be used and no side
reactions are produced.
PRACTICAL APPLICATIONS
HYDROPHILICITY
Also called hydrophilic, is a characteristic of materials
exhibiting an affinity for water. Hydrophilic literally means
"water-loving" and such materials readily adsorb water. The
surface chemistry allows these materials to be wetted
forming a water film or coating on their surface.
MECHANISM OF PHOTO-INDUCED HYDROPHILICITY
SUPER-HYDROPHILICITY
SUPER-HYDROPHILICITY
SCHEMATIC DIAGRAM OF
SUPER-HYDROPHILICITY MECHANISM
STEP 3
14
2
SELF-CLEANING WINDOWS
Magnetism
• What are magnetic domains?
• Magnetic substances like iron,
cobalt, and nickel are composed
of small areas where the groups
of atoms are aligned like the
poles of a magnet. These regions
are called domains. All of the
domains of a magnetic substance
tend to align themselves in the
same direction when placed in a
magnetic field. These domains
are typically composed of billions
of atoms.
What causes iron, nickel, and cobalt to
be attracted to magnets, but not other
metals?
• The magnetic properties of a material are governed entirely by the
configuration of the electrons in that material.
• Each electron, in addition to having charge, also has a “magnetic
moment” which is a fancy way of saying that it’s a tiny bar magnet.
• However, sometimes (in iron, nickel, and cobalt for example) you’ll have
one or more un-paired electrons. The magnetic fields of these electrons
aren’t canceled out by another, oppositely-oriented, electron. As such
they lend an overall magnetic field to the atom they inhabit.
• Ferromagnetic materials are what we refer to by the term
"permanent magnet".
• Indeed, the strongest magnets are not made of either iron, cobalt or
nickel, but from neodymium and other rare-earth metals. Its electron
structure features 7 electrons with parallel spin within each atom.
That's a huge number. Atoms within a crystal stack up, so that all of
their electrons are parallel.
• Paramagnetic materials, on the other hand, don't have an
ordered structure in the absence of a magnetic field. When it is
applied, though, their electrons align, so that the spin of all
their atoms are parallel. You obtain essentially the same picture.
Introducing paramagnetic material in a magnetic field, you can
magnetize it. When the source of the magnetic field is turned
off, entropy takes over and rearranges the spins in a random,
chaotic way, just as they were before the outside disturbance.
• Diamagnetics
• The third category of materials are diamagnetics.
• Their atoms don't have electrons with parallel spin, so even in very
strong magentic fields, the atoms can't arrange in a particular way, so
they can't be attracted to magnets.
Metal to Ligand and Ligand to Metal
Charge Transfer Bands
• In the field of inorganic chemistry, color is commonly associated with
d–d transitions.
• If this is the case, why is it that some transition metal complexes show
intense color in solution, but possess no d electrons?
• In transition metal complexes a change in electron distribution
between the metal and a ligand gives rise to charge transfer (CT)
bands when performing UV-visible spectroscopy experiments.
• For complete understanding, a brief introduction to electron transfer
reactions and Marcus-Hush theory is necessary.
Outer Sphere Charge Transfer Reactions
Electron transfer reactions (charge transfer) fall into 2 categories:

• Inner- sphere mechanisms– electron transfer occurs via a
covalently bound bridging ligand.
Figure 1. Intermediate formed in

the reaction between [Fe(CN)6]3-
3-

CH 20 Properties of The 3d Transition Metal

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CH 20 Properties of The 3d Transition Metal

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Properties of the 3d

All are hard (except copper), dense, and

b. intermediate acid anions : [HVO4]2- and

have similarities in their chemistry;

The difference between the triad :

• Use for defence industry:

dissolved out by using dilute acid

- Use as paint (white) pigment with high refractive index.

- found as the impure dioxide (rutile).

Rutile and anatase

Schematic Water Splitting Cell using TiO2 as photocatalyst:

3+ (acidic) Cr(H2O)63+, blue (basic) Cr(OH)4-, green

6+ (acidic) Cr2O72-, orange (basic) Cr2O42-, yellow

CrO Cr2O3 CrO3

basic amphoteric acidic

KMnO4, is an extremely powerful oxidizing agent.

• Under acid conditions, is the most thermodynamically stable

Manganese(II) chloride crystals –

Fe2O3(s) + 3 CO(g) → 2 Fe(l) + 3 CO2(g)

• Pure iron is too soft for many uses.

• Steels are alloys.

• The different sized atoms added

• The iron(III) ion is small and sufficiently polarizing

• When heated to the gas phase, it exists as the dimeric species

• Iron(III) chloride can be made by heating iron in the presence of

Fe3+ and Al3+

• All the common hydrated iron(II) salts contain

Mohr’s salt : (NH4)2Fe(SO4)2.6H2O

• used as a standard for redox titrations

The green precipitate formed is then oxidised

• All complexes are octahedral, and kinetically

• Na3[Co(NO2)6] and K3[Co(NO2)6]

Insoluble  due to the relative ion

Coupling with the reduction of dioxygen:

enables [Co(NH3)6]2+ to be oxidized to [Co(NH3)6]3+ in aqueous solution.

The number of ions is identiﬁed with conductivity measurements,

Silica gell with CoCl2 ;

• The only common oxidation number is

To separate the Ni from the other metals (e.g

• Factors for the choice of stereochemistry:

• Because tet is 4/9 that of oct, the CFSE for a tetrahedral

• The color of Cu is caused by the filled d band in the metal being

• chalcopyrites and copper pyrites Copper(I) iron(III)

CuAl6(PO4)4(OH)8.4H2O, is the valued blue gemstone turquoise.

Air is again added :

thermal process =pyrometallurgy

• Concentration of sulfide ore is done by

• The roasting – reduction process is known as pyrometallurgy.

• Leaching: Metal ions are extracted from the ore by a liquid.

• Purification and concentration.

2. mushroom Amanita muscaria,  V role not

• TiO2 – most widely used oxide for

• TiO2 has two main polymorphs:

• Band Gap of TiO2 is ~3.4 eV So it absorbs only the UV Part of Solar

• THE COMMON FORMS OF TIO2

BUT THE RUTILE & ANATASE

BOTH EDGES AND CORNERS. LARGE CIRCLES: O

• THE POINT GROUP SYMMETRY

Red rutile mined in Switzerland Anastase grown in Lab

• Valence Band of Anatase consists mainly of 3 regions [M.Emori

The valence band of TiO2 can

Density: 4,2 g/cc