Golongan Ivb_english Version

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GOLONGAN IVB

Titanium

Electrons per shell 2,8,10,2

Electron Configuration [Ar] 3d2 4s2

Ground state 3F2

Atomic Volume 10.64 cm3 mol-1

Electronegativity 1.54

Magnetic ordering No data

Mass magneticsusceptibility

4.01 x 10-8

Molar magneticsusceptibility

1.919 x 10-9

Speed of sound 5090 m s-1

Thermal Properties

Enthalpy of Atomization 468.6 kJ mol-1 @25C

Enthalpy of Fusion 20.9 kJ mol-1

Enthalpy of Vaporisation 425.5 kJ mol-1

Heat Capacity 25.060 J mol-1 K-1

Thermal Conductivity 21.9 W m-1 K-1

Thermal Expansion 8.6 m m-1 K-1

Hardness

Brinell hardness 716 MPa

Mohs hardness 6.0

Vickers hardness 970 MPa

Elastic Properties

Bulk modulus 110 GPa

Poisson ratio 0.32

Shear modulus 44 GPa

Young's modulus 116 GPa

Electrical Properties

Electrical resistivity 4.0 x 10-7 m

Electrical conductivity 0.0234 106/cm

Chemical Properties

ElectrochemicalEquivalent

0.4468 g Ah-1

Electron Work Function 4.33 eV

Valence Electron Potential(-eV)

95.2

Ionization Potential

First 6.82

Second 13.58

Third 27.491

Energy Levels

K1(intensity 100) 4.51084 KeVK2(intensity 50) 4.50486 KeV
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K 1(intensity 20.44) 4.93181 KeV

L1(intensity 100) 0.4522 KeV






Ll(intensity 140) 0.395 KeV

Atomic Radii

Empirical 140 pm

Bohr Radius 176 pm

Covalent Radius 136 pm

Van der Waals No data.

Triple covalent 108 pm

Metallic 147 pm

Oxidation States

Main Ti+4

Other Ti-1, Ti0, Ti+2, Ti+3

Ionisation Energies (kJ mol-1)

M - M+ 658

M+ - M2+ 1310

M2+ - M3+ 2652

M3+ - M4+ 4175

M4+

- M5+

9573M5+ - M6+ 11516

M6+ - M7+ 13590

M7+ - M8+ 16260

M8+ - M9+ 18640

M9+ - M10+ 20830

Vapour Pressure

P (Pa) 1 10 100 1K 10K 100K

T (K) 1982 2171 (2403) 2692 3064 3558

Crystal Structure

StructureHexagonal closeed

a = 295.08 pm

b = 295.08 pm

c = 468.55 pm

= 90

= 90

= 120
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Titanium Compounds

Titanium boride

Titanium carbide

Titanium dioxide

Titanium nitride

Titanium boride TiB2

An extremely hard ceramic material with excellent corrosion resistance at hightemperatures and very good wear resistance which does not occur naturally in earth.

Many TiB2 applications are inhibited by economic factors, particularly the costs ofdensifying a high melting point material. Current use of this material appears to belimited to specialized applications in such areas as impact resistant armour, cutting tools,

crucibles and wear resistant coatings.

Titanium carbide TiC

An extremely hard refractory ceramic material, similar to tungsten carbide. It is

commercially used in tool bits cutting tools. It is mainly used in preparation of cermets,which are frequently used to machine steel materials at high cutting speed.

Tool bits without tungsten content can be made of titanium carbide in nickel-cobalt

matrix cermet, enhancing the cutting speed and precision and smoothness of theworkpiece. This material is sometimes called high-tech ceramics and is used as a heatshield for atmospheric re-entry of space shuttles and similar vehicles. The substance

may be also polished and used in scratch-proof watches.

Titanium dioxide TiO2

Titanium dioxide is the most widely used white pigment because of its brightness andvery high refractive index, in which it is surpassed only by a few other materials. Whendeposited as a thin film, its refractive index and colour make it an excellent reflective

optical coating for dielectric mirrors. TiO2 is also an effective opacifier in powder form,where it is employed as a pigment to provide whiteness and opacity to products such aspaints, coatings, plastics, papers, inks, foods, and most toothpastes. In cosmetic andskin care products, titanium dioxide is used both as a pigment and a thickener, and inalmost every sunblock with a physical blocker, titanium dioxide is found both because ofits refractive index and its resistance to discolouration under ultraviolet light. Thisadvantage enhances its stability and ability to protect the skin from ultraviolet light.Titanium dioxide is used as a white food dye. In that use, its E number is E171.

Titanium nitride TiN

An extremely hard ceramic material, often used as a coating on titanium alloy, steel,

carbide, and aluminiumcomponents to improve the substrate's surface properties. Far

and away the most common use for TiN coating is for edge retention and corrosionresistance on machine tooling, such as drill bits and milling cutters, often improving theirlifetime by a factor of three or more.

Because of its metallic gold colour, it is used to coat costume jewellery and automotivetrim for decorative purposes. TiN is also widely used as a top-layer coating, usually withnickel or chromium plated substrates, on consumer plumbing fixtures and doorhardware.

Reactions of Titanium

Reactions with water

Titanium is coated with a thin oxide layer that under normal circumstances renders inertin air. However, titanium will react with steam to form titanium(IV) oxide andhydrogen.

Ti(s) + 2H2O(g) TiO2(s) + 2H2(g)

Reactions with air
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Titanium is coated with a thin oxide layer that under normal circumstances renders inertin air. However, once titanium starts to burn in air it burns with a bright white flame toform titanium oxide and titanium nitride. It will burn in pure nitrogento form titaniumnitride.

Ti(s) + O2(g) TiO2(s)

2Ti(s) + N2(g) TiN(s)Reactions with halogens

Titanium does react with the halogens upon warming to form titanium(IV) halides. Thereaction withfluorinerequires heating to 200C.

Ti(s) + 2F2(g) TiF4(s)

Ti(s) + 2Cl2(g) TiCl4(s)

Ti(s) + 2Br2(l) TiBr4(s)

Ti(s) + 2I2(s) TiI4(s)

Reactions with acids

Dilute aqueous hydrofluoric acid reacts with titanium to form the complex anion [TiF 6]3-

together withhydrogen.2Ti(s) + 12HF(aq) 2[TiF6]

3-(aq) + 3H2(g) + 6H

+(aq)

Titanium metal does not react with mineral acids at ambient temperature but does reactwith hot hydrochloric acic to form titanium(III) complexes.

Reactions with bases

Titanium does not appear to react wih alkalis under normal conditions, even when hot.

Reduction Potentials

Balanced half-reaction E0 / V

TiIV + e- TiIII -0.092

TiIV + 4e- Ti(s) -0.88

Ti3+ + e- Ti2+ -0.369

Ti2+ + 2e- Ti(s) -1.630

TiO22+ + H+ + 4e- HTiO2>sup> +1.303

TiO22+ + 2H+ + 2e- TiO2+ + H2O +1.800

TiO2(s) + 4H+ + e- Ti3+ + H2O -0.666

TiO2(s) + 4H+ + 2e- Ti2+ + H2O -0.502

TiO2+ + 2H+ + e- Ti3+ + H2O +0.099

TiO2+ + 2H+ + e- Ti3+ + H2O +0.04

TiO2+ + 2H+ + 2e- Ti2+ + H2O -0.135

HTiO2- + 5H+ + 2e- Ti2+ + 3H2O +0.362

TiF62- + 4e- Ti(s) + 6F

- -1.19

Occurrence and Production of Titanium

Occurrence

Titanium is always bonded to other elements in nature. It is the ninth-most abundantelement in the Earth's crust (0.63% by mass) and the seventh-most abundant metal. Itis present in most igneous rocks and in sediments derived from them (as well as in livingthings and natural bodies of water). In fact, of the 801 types of igneous rocks analyzed

by the United States Geological Survey, 784 contained titanium. Its proportion in soils isapproximately 0.5 to 1.5%.

It is widely distributed and occurs primarily in the minerals anatase, brookite, ilmenite(FeTiO3), perovskite, rutile (TiO2), titanite ( CaTiSiO5) (sphene), as well in many iron
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ores. Of these minerals, only rutile and ilmenite have any economic importance, yeteven they are difficult to find in high concentrations. Significant titanium-bearingilmenite deposits exist in westernAustralia,Canada,New Zealand,Norway, andUkraine.Large quantities of rutile are also mined in North America and South Africa and help

contribute to the annual production of 90,000 tonnes of the metal and 4.3 million tonnesof titanium dioxide. Total known reserves of titanium are estimated to exceed 600million tonnes.

Titanium is contained in meteorites and has been detected in the sun and in M-type

stars; the coolest type of star with a surface temperature of 3,200C (5792F). Rocksbrought back from the moon during the Apollo 17 mission are composed of 12.1% TiO 2.It is also found in coal ash, plants, and even the human body.

Titanium [Ti]

CAS-ID: 7440-32-6

An:22N:26

Am:47.867 g/mol

Group No: 4

Group Name: Transition metals

Block: d-block Period: 4

State: solid at 298 K

Colour: silvery metallic Classification: Metallic

Boiling Point:3560K (3287C)

Melting Point:1941K (1668C)

Superconducting temperature:0.40K (-272.7C)

Density: 4.506g/cm3

Discovery InformationWho:William Gregor

When: 1791

Where: England

Name Origin

Greek: titanos (Titans).

"Titanium" in different languages.Sources

Usually occurs in the minerals ilmenite (FeTiO3) or rutile (TiO2). Also in Titaniferousmagnetite (Fe3O4), titanite (CaTiSiO5), and iron ores. The primary deposits of titaniumore are inAustralia, Scandinavia, North America andMalaysia.

World wide production is around 99 thousand tons.

Abundance

Universe: 3 ppm (by weight)

Sun: 4 ppm (by weight)

Carbonaceous meteorite: 550 ppm

Earth's Crust: 6600 ppm

Seawater: 4.8 x 10-4 ppm

Uses

Titanium is well known for its excellent resistance to corrosion; it is almost as resistantas platinum, being able to withstand attack by acids, moist chlorine gas, and by
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common salt solutions.

Because of its high tensile strength (even at high temperatures), light weight,

extraordinary corrosion resistance, and ability to withstand extreme temperatures,titanium alloys are used in aircraft (a Boeing 737 contains around 18 tons, a 777around 58 tons), armour plating, naval ships, spacecraft and missiles. It is used in steel

alloysto reduce grain size and as a deoxidizer, and in stainless steel to reduce carboncontent. Titanium is often alloyed with aluminium (to refine grain size), vanadium,copper(to harden),iron,manganese,molybdenumand with other metals.

Because it is considered to be physiologically inert, the metal is used in jointreplacement implants such as hip ball and sockets and to make medical equipment and

in pipe/tank lining in food processing. Since titanium is non-ferromagnetic patients withtitanium implants can be safely examined with magnetic resonance imaging, whichmakes it convenient for long term implants and surgical instruments for use in image-guided surgery.

95% of titanium production is consumend in the form of titanium dioxide (TiO2), a whitepigment that covers surfaces very well, is used in paint, rubber, paper and many othermaterials. Also used in heat exchangers, airplane motors, bone pins and other things

requiring light weight metals or metals that resist corrosion or high temperatures.Titanium oxide is used extensively in paints and in suncreens.

Due to excellent resistance to sea water, it is used to make propeller shafts and riggingand in the heat exchangers of desalination plants and in heater-chillers for salt wateraquariums, and lately diver knives as well.

Titanium tetrachloride (TiCl4), a colourless liquid, is used to iridize glass and because itfumes strongly in moistairit is also used to make smoke screens and in skywriting.

History

Titanium was discovered combined in a mineral in Cornwall, England in 1791 byamateur geologist William Gregor, the then vicar of Creed village. He recognized thepresence of a new element in ilmenite (FeTiO3) when he found black sand by a stream

in the nearby parish of Manaccan and noticed the sand was attracted by a magnet.Analysis of the sand determined the presence of two metal oxides; iron oxide(explaining the attraction to the magnet) and 45.25% of a white metallic oxide he couldnot identify. Gregor, realizing that the unidentified oxide contained a metal that did notmatch the properties of any known element, reported his findings to the RoyalGeological Society of Cornwall and in the German science journal Crell's Annalen.

Around the same time, Franz Joseph Muller also produced a similar substance, but could

not identify it. The oxide was independently rediscovered in 1795 by German chemistMartin Heinrich Klaprothin rutile from Hungary. Klaproth found that it contained a newelement and named it for the Titans of Greek mythology. After hearing about Gregor's

earlier discovery, he obtained a sample of manaccanite and confirmed it containedtitanium.

The processes required to extract titanium from its various ores are laborious andcostly; it is not possible to reduce in the normal manner, by heating in the presence ofcarbon, because that produces titanium carbide. Pure metallic titanium (99.9%) wasfirst prepared in 1910 by Matthew A. Hunter by heating TiCl4 with sodium in a steelbomb at 700 - 800C in the Hunter process. Titanium metal was not used outside thelaboratory until 1946 when William Justin Kroll proved that it could be commercially

produced by reducing titanium tetrachloride withmagnesiumin what came to be knownas the Kroll process. Although research continues into more efficient and cheaperprocesses (FFC Cambridge, e.g.), the Kroll process is still used for commercial

production.

Titanium of very high purity was made in small quantities when Anton Eduard van Arkeland Jan Hendrik de Boer discovered the iodide, or crystal bar, process in 1925, by

reacting with iodineand decomposing the formed vapours over a hot filament to puremetal.
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Notes

Pure titanium is a lustrous white metal, as strong as steel, 45% lighter, 60% heavier

thanaluminium.

Titanium is Latin and refers to the Titans, the first sons of the earth in Mythology. Itwas discovered by Gregor in 1791 and named by Klaproth four years later. It was

nearly a hundred years later (1887) when impure titanium was first prepared by Nilsonand Pettersson. About 20 years later Hunter heated Titanium Chloride TiCl 4 withsodiumin a steel bomb and isolated 99.6% pure titanium. It is the ninth most abundantelementin the Earth's crust and is also found in meteorites and in the sun. It is found inthe ash of coal, in plants and even in the human body. It occurs in the minerals rutile

(TiO2), ilmenite (FeTiO3) and sphene (CaTiSiO5).

As a compound, it is found as Titanium dioxide TiO2 in star sapphires and rubies (it isTiO2 that gives them their asterism). It is also found as titanium chloride (TiCl4). When

it is red hot the metal combines withoxygen, and when it reaches 550C it combineswithchlorine. It also reacts with the otherhalogensand absorbshydrogen.

Hazards

As a powder or in the form of metal shavings, titanium metal poses a significant firehazard and, when heated in air, an explosion hazard. Water and carbon dioxide-basedmethods to extinguish fires are ineffective on burning titanium.

Titanium powder is harmful if inhaled and is also an eye irritant.

ZIRCONIUM

Zirconium

Electrons per shell 2,8,18,10,2

Electron Configuration [Kr] 4d2 5s2

Ground state 3F2




Mass magneticsusceptibility

1.66 x 10-8

Molar magneticsusceptibility

1.514 x 10-9


Thermal Properties
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Enthalpy of Atomization 598 kJ mol-1 @25C

Enthalpy of Fusion 23 kJ mol-1





Hardness

Brinell hardness 650 MPa

Mohs hardness 5.0


Elastic Properties

Poisson ratio 0.34



Electrical PropertiesElectrical resistivity 4.2 x 10-7 m


Chemical Properties


0.8509 g Ah-1


Valence Electron Potential(-eV)

80


First 6.84Second 13.13

Third 22.99

Incompatibilities Potassium nitrate(KNO3), oxidizers.

Flammability

Combustible

Energy Levels

K1(intensity 100) 15.7751 KeV


K1(intensity 16.6) 17.6678 KeVK2(intensity 3.2) 17.9663 KeV

K3(intensity 7.9) 17.6501 KeV




L2(intensity 1.8) 2.2194 KeV





Ll(intensity 6) 1.7906 KeV
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Atomic Radii

Empirical 155 pm

Bohr Radius 206 pm


Van der Waals No data.Triple covalent 121 pm

Metallic 160 pm

Oxidation States

Main Zr+4

Other Zr0, Zr+1, Zr+2, Zr+3


M - M+ 660

M+ - M2+ 1267

M2+

- M3+

2218M3+ - M4+ 3313

M4+ - M5+ 7860

M5+ - M6+ 9500

M6+ - M7+ 11200

M7+ - M8+ 13800

M8+ - M9+ 15700

M9+ - M10+ 17500

Vapour Pressure

P (Pa) 1 10 100 1K 10K 100K

T (K) 2639 2891 3197 3575 4053 4678

Crystal Structure

Structure Hexagonal close packed

a = 323.2 pm

b = 323.2 pm

c = 514.7 pm

= 90

= 90

= 120

Zirconium Compounds

Zirconium carbide

Zirconium dioxide

Zirconium(IV) hydroxide

Zirconium nitride

Zirconium carbide ZrC

An extremely hardrefractoryceramic material, commercially used in tool bits for cuttingtools. It is usually processed by sintering. It has the appearance of a gray metallicpowder with cubic crystal structure. It is highly corrosion resistant. Zirconium carbide

reacts with water and acids and ispyrophoric.

Hafnium-free zirconiumcarbideandniobiumcarbidecan be used asrefractorycoatings
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in nuclear reactors. It is also used as an abrasive, in metal cladding, in cermets,incandescent filaments and cutting tools.

Zirconium dioxide ZrO2

Sometimes known as zirconia, is a white crystalline oxide of zirconium. Its mostnaturally occurring form, with a monoclinic crystalline structure, is the rare mineral,

baddeleyite. The high temperature cubic crystalline form, called 'cubic zirconia', is rarely,if ever, found in nature, but is synthesized in various colours for use as a gemstone andis the best-known diamond simulant.

Zirconium dioxide is one of the most studied ceramic materials. Pure ZrO2 has amonoclinic crystal structure at room temperature and transitions to tetragonal and cubic

at increasing temperatures.

It is used as arefractorymaterial, in insulation, abrasives, enamels and glazes.Stabilized zirconia is used inoxygensensors and fuel cell membranes because it has a

unique ability to allow oxygen ions to move freely through the crystal structure at hightemperatures. This high ionic conductivity (and a low electronic conductivity) makes itone of the most useful electroceramics.

Zirconia is one of few compounds that actually becomes conductive at high

temperatures, and more conductive, as its temperature increases. Zirconia starts outwith a very high resistance at room temperature, greater than 1 trillion ohm-cm. As thetemperature increases it has less than 20,000 ohm-cm at 500 degrees Celsius, to having

less than 1,000 ohm-cm of resistance at 1,000 degrees Celsius. It loses nearly all of itsresistance around 2,000 degrees Celsius, and becomes a very good conductor.

Zirconium(IV) hydroxide Zr(OH)4

Zirconium hydroxide is primarily used as in intermediate for the manufacture ofzirconium compounds. It is used in pigments, glass and dyes.

Zirconium nitride ZrN

It is hard andrefractory. It has been used recently as an alternative totitaniumnitridefor coating drill bits. Both coatings are supposed to keep the bit sharper and cooler

during cutting. It is also used in refractories, cermets and laboratory cruibles.

Reactions of Zirconium


Zirconium does not react with water under normal conditions.

Reactions with air

Zirconium is coated with an oxide layer that usually renders it inactive. However zirconium

does burn in air if provoked to form zirconium(IV) oxide, ZrO2.

Zr s + O2 ZrO2 s

Reactions with halogensZirconium does react with the halogens, upon warming, to form zirconium(IV) halides.

Zr(s) + 2F2(g) ZrF4(s)

Zr(s) + 2Cl2(g) ZrCl4(s)

Zr(s) + 2Br2(g) ZrBr4(s)

Zr(s) + 2I2(g) ZrI4(s)

Reactions with acids

Zirconium metal is coated with an oxide layer that usually renders it inactive. Most coldmineral acids have little effect. Zirconium does dissolve in hydrofluoric acid, HF, presumablyto form fluoro complexes.

Reactions with basesZirconium does not appear to react wih alkalis under normal conditions, even when hot.
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Reduction Potentials

Balanced half-reaction E0 / V

Zr4+ + 4e- Zr(s) -1.539

H2ZrO3(s) + H2O + 4e

-

Zr(s) + 4OH

-

-2.36HZrO3

- + 5H+ + 4e- Zr(s) + 3H2O -1.276

ZrO2+ + 2H+ + 4e- Zr(s) + H2O -1.570

ZrO2(s) + 4H+ + 4e- Zr(s) + 2H2O -1.456

ZrO2.H2O(s) + 4H+ + 4e- Zr(s) + 3H2O3 -1.53

ZrO2.2H2O + 4H+ + 4e- Zr(s) + 4H2O -1.553

Occurrence and Production of Zirconium

Occurrence

Zirconium is never found in nature as a free metal. The principal economic source ofzirconium is the zirconium silicate mineral, zircon (ZrSiO4), which is found in deposits

located inAustralia,South Africaand theUnited States, reports the British GeologicalSurvey. (It is extracted as a dark sooty powder, or as a gray metallic crystallinesubstance). Zirconium andhafniumare contained in zircon at a ratio of about 50 to 1and are difficult to separate. Zircon is a coproduct or byproduct of the mining andprocessing of heavy-mineral sands for thetitaniumminerals, ilmenite and rutile, ortinminerals. Zirconium is also in 30 other recognized mineral species including baddeleyite.This metal is commercially produced by reduction of the Zirconium(IV) chloride withmagnesiumin the Kroll process, and through other methods. Commercial-quality

zirconium still has a content of 1 to 3% hafnium.

This element is also abundant in S-type stars and has been detected in the sun andmeteorites. Lunar rock samples brought back from several Apollo program missions tothe moon have a very high zirconium oxide content relative to terrestrial rocks.

Zirconium [Zr]

CAS-ID: 7440-67-7

An:40N:51

Am:91.224 (2) g/mol

Group No: 4

Group Name: Transition metals

Block: d-block Period: 5

State: solid at 298 K

Colour: silvery white Classification: Metallic

Boiling Point:4682K (4409C)

Melting Point:2128K (1855C)

Superconducting temperature:0.61K (-272.54C)

Density: 6.52g/cm3

Availability: Zirconium is available in many forms including foil, nanosized activatedpowder, powder, rod, sponge, bar, sheet, and wire.

Discovery Information

Who:Martin Klaproth

When: 1789

Where: Germany
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Name Origin

From the mineral zircon

"Zirconium" in different languages.Sources

Zirconium is never found in nature as a free metal. Found in many minerals such aszircon (ZrSiO4) and baddeleyite (ZrO2). Annual production of zircon is around 1.2 milliontonnes.

Primary producers areAustralia,Brazil,Sri Lankaand theUSA.

Abundance

Universe: 0.05 ppm (by weight)

Sun: 0.04 ppm (by weight)

Carbonaceous meteorite: 6.7 ppm

Earth's Crust: 130 ppm

Seawater: 9 x 10-6 ppm

Human:50 ppb by weight

3 ppb by atoms

Uses

Used inalloyssuch as zircaloy which is used in nuclear applications since it does notreadily absorbneutrons. Also used incatalyticconverters, percussion caps and furnacebricks. Baddeleyite is used in lab crucibles. Zirconiumnitride(ZrN) has been used morerecently as an alternative totitaniumnitridefor coating drill bits. Both coatings aresupposed to keep the bit sharper and cooler during cutting.

Extensively used by the chemical industry for piping in corrosive environments.

Because human tissues can easily tolerate this metal it is suitable for biocompatible

implants, eg. some artificial joints and limbs.

Whenalloyedwithniobium, zirconium becomes superconductive at low temperatures

and is used to make superconductive magnets with possible large-scale electrical poweruses.

History

Although it was discovered in 1789 byMartin Heinrich Klaprothit wasn't isolated until1824, byJns Jakob Berzelius.

The zirconium-containing mineral zircon, or its variations (jargon, hyacinth, jacinth, orligure), were mentioned in biblical writings. The mineral was not known to contain a new

element untilKlaprothanalyzed a jargon from Ceylon in the Indian Ocean. He named thenew element Zirkonertz (zirconia). The impure metal was isolated first by Berzelius by

heating a mixture ofpotassiumandpotassium-zirconium fluoride in a smalldecomposition process conducted in an iron tube. Pure zirconium wasn't prepared until

1914.

The crystal bar process (or Iodide process), discovered by Anton Eduard van Arkel andJan Hendrik de Boer in 1925, was the first industrial process for the commercial

production of pure ductile metallic zirconium. It was superseded by the Kroll process.

Notes

This element has been detected in the sun and meteorites. Lunar rock samples broughtback from several Apollo program missions to the moon have a very high zirconiumoxide content relative to terrestrial rocks.

Hazards

Compoundscontaining zirconium are not noted for toxicity. The metal dust can ignite in
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airand should be regarded as a major fire and explosion hazard.

HAFNIUM

HafniumElectrons per shell 2,8,18,32,10,2

Electron Configuration [Xe] 4f14 5d2 6s2

Ground state 3F2




Mass magnetic

susceptibility5.3 x 10-9

Molar magnetic

susceptibility

9.46 x 10-10


Thermal Properties

Enthalpy of Atomization 703 kJ mol-1 @25C

Enthalpy of Fusion 25.5 kJ mol-1





Hardness

Brinell hardness 1700 MPaMohs hardness 5.5


Elastic Properties

Bulk modulus 110 GPa

Poisson ratio 0.37



Electrical Properties

Electrical resistivity 3.0 x 10-7 m

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Chemical Properties


1.6649 g Ah-1


Valence Electron Potential

(-eV) 81


First 6.65

Second 14.925

Third 23.32

Incompatibilities Strong oxidizers,chlorine.

Flammability

Explosive in powder form

Energy Levels








L 1(intensity 44) 9.0227 KeV




L 1(intensity 7.5) 10.5158 KeV



Ll(intensity 5.5) 6.9583 KeV

Atomic Radii

Empirical 155 pm

Bohr Radius 208 pm


Van der Waals No data.Triple covalent 122 pm

Metallic 159 pm

Oxidation States

Main Hf+4

Other Hf+1, Hf+2, Hf+3


M - M+ 642

M+ - M2+ 1440

M2+ - M3+ 2250M3+ - M4+ 3216
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Vapour Pressure

P (Pa) 1 10 100 1K 10K 100K

T (K) 2689 2954 3277 3679 4194 4876

Crystal Structure

Structure Hexagonal close packeda = 319.64 pm

b = 319.64 pm

c = 505.11 pm

= 90

= 90

= 120

Hafnium Compounds

Hafnium diboride

Hafnium(IV) oxide

Hafnium diboride HfB2

Hafnium diboride is an ultra-high temperature ceramic. It has a melting temperature ofabout 3250 degrees Celsius. It is an unusual ceramic, having relatively high thermal and

electrical conductivities. It is a grey, metallic looking material. Hafnium diboride has ahexagonal crystal structure, a molar mass of 200.11 grams per mole, and a density of10.5 grams per cubic centimeter.

Hafnium diboride is often combined withcarbon,boron,silicon, silicon carbide, and/ornickelto improve the consolidation of the hafnium diboride powder (sintering). It iscommonly formed into a solid by a process called hot pressing, where the powders arepressed together using both heat and pressure.

The material has potential for use in hypervelocity reentry vehicles such as ICBM heat

shields or aerodynamic leading-edges, due to its strength and thermal properties. Unlikepolymer and composite material, HfB2 can be formed into aerodynamic shapes that willnot ablate during reentry.

Hafnium diboride is also investigated as a possible new material for nuclear reactorcontrol rods.

Hafnium(IV) oxide HfO2

It is used in optical coatings, and as a high-k dielectric in DRAM capacitors. Hafniumbased oxides are currently leading candidates to replacesiliconoxide as a gate insulatorin field effect transistors.

Reactions of Hafnium


Hafnium does not react with water under normal conditions.

Reactions with air

Hafnium is coated with an oxide layer that usually renders it inactive. However hafnium willburn in air if provoked to form hafnium dioxide. Finely divided hafnium ispyrophoricmaking

it a fire hazard.

Hf(s) + O2(g) HfO2(s)

Reactions with halogens

Hafnium does react with all the halogens upon warming to form hafnium(IV) halides.

Hf(s) + 2F2(g) HfF4(s)
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