Difference between revisions of "Hafnium"

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Hafnium is a d-block transition metal with the symbol Hf and atomic number 72. It is a hard, high melting point silvery metal, which is resistant to attack by most acids and alkalis. The most documented chemistry revolves around the halides. The principle uses of metallic hafnium are related to the nuclear industry.
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{{Infobox element
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==Properties==
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<!-- top -->
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|image name=Hafnium_2.jpg
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|image alt=
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|image size=300
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|image name comment=Hafnium crystal bar about 30mm long, but weighing over 200 grams by diddi
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|image name 2=
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|image alt 2=
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|image size 2=
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|image name 2 comment=
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<!-- General properties -->
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|name=Hafnium
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|symbol=Hf
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|pronounce=
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|pronounce ref=
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|pronounce comment=
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|pronounce 2=
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|alt name=
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|alt names=
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|allotropes=
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|appearance=Steel-gray
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<!-- Periodic table -->
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|above=[[Zirconium|Zr]]
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|below=Rf
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|left=[[Lutetium]]
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|right=[[Tantalum]]
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|number=72
 +
|atomic mass=178.49(2)
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|atomic mass 2=
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|atomic mass ref=
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|atomic mass comment=
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|series=
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|series ref=
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|series comment=
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|series color=
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|group=4
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|group ref=
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|group comment=
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|period=6
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|period ref=
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|period comment=
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|block=d
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|block ref=
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|block comment=
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|electron configuration=[Xe] 4f<sup>14</sup> 5d<sup>2</sup> 6s<sup>2</sup>
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|electron configuration ref=
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|electron configuration comment=
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|electrons per shell=2, 8, 18, 32, 10, 2
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|electrons per shell ref=
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|electrons per shell comment=
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<!-- Physical properties -->
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|physical properties comment=
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|color=Steel-gray
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|phase=Solid
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|phase ref=
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|phase comment=
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|melting point K=2506
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|melting point C=2233
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|melting point F=​4051
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|melting point ref=
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|melting point comment=
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|boiling point K=4876
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|boiling point C=4603
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|boiling point F=​8317
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|boiling point ref=
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|boiling point comment=
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|sublimation point K=
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|sublimation point C=
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|sublimation point F=
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|sublimation point ref=
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|sublimation point comment=
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|density gplstp=
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|density gplstp ref=
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|density gplstp comment=
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|density gpcm3nrt=13.31
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|density gpcm3nrt ref=
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|density gpcm3nrt comment=
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|density gpcm3nrt 2=
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|density gpcm3nrt 2 ref=
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|density gpcm3nrt 2 comment=
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|density gpcm3nrt 3=
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|density gpcm3nrt 3 ref=
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|density gpcm3nrt 3 comment=
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|density gpcm3mp=12
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|density gpcm3mp ref=
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|density gpcm3mp comment=
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|density gpcm3bp=
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|density gpcm3bp ref=
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|density gpcm3bp comment=
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|molar volume=
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|molar volume unit =
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|molar volume ref=
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|molar volume comment=
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|triple point K=
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|triple point kPa=
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|triple point ref=
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|triple point comment=
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|triple point K 2=
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|triple point kPa 2=
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|triple point 2 ref=
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|triple point 2 comment=
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|critical point K=
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|critical point MPa=
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|critical point ref=
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|critical point comment=
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|heat fusion=27.2
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|heat fusion ref=
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|heat fusion comment=
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|heat fusion 2=
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|heat fusion 2 ref=
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|heat fusion 2 comment=
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|heat vaporization=648
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|heat vaporization ref=
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|heat vaporization comment=
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|heat capacity=25.73
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|heat capacity ref=
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|heat capacity comment=
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|heat capacity 2=
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|heat capacity 2 ref=
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|heat capacity 2 comment=
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|vapor pressure 1=2689
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|vapor pressure 10=2954
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|vapor pressure 100=3277
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|vapor pressure 1 k=3679
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|vapor pressure 10 k=4194
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|vapor pressure 100 k=4876
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|vapor pressure ref=
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|vapor pressure comment=
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|vapor pressure 1 2=
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|vapor pressure 10 2=
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|vapor pressure 100 2=
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|vapor pressure 1 k 2=
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|vapor pressure 10 k 2=
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|vapor pressure 100 k 2=
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|vapor pressure 2 ref=
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|vapor pressure 2 comment=
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<!-- Atomic properties -->
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|atomic properties comment=
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|oxidation states='''4''', 3, 2, 1, −2
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|oxidation states ref=
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|oxidation states comment=(an amphoteric oxide)
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|electronegativity=1.30
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|electronegativity ref=
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|electronegativity comment=
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|ionization energy 1=658.5
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|ionization energy 1 ref=
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|ionization energy 1 comment=
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|ionization energy 2=1440
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|ionization energy 2 ref=
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|ionization energy 2 comment=
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|ionization energy 3=2250
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|ionization energy 3 ref=
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|ionization energy 3 comment=
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|number of ionization energies=
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|ionization energy ref=
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|ionization energy comment=
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|atomic radius=159
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|atomic radius ref=
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|atomic radius comment=
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|atomic radius calculated=
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|atomic radius calculated ref=
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|atomic radius calculated comment=
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|covalent radius=175±10
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|covalent radius ref=
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|covalent radius comment=
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|Van der Waals radius=
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|Van der Waals radius ref=
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|Van der Waals radius comment=
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<!-- Miscellanea -->
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|crystal structure=
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|crystal structure prefix=
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|crystal structure ref=
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|crystal structure comment= Hexagonal close-packed (hcp)
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|crystal structure 2=
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|crystal structure 2 prefix=
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|crystal structure 2 ref=
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|crystal structure 2 comment=
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|speed of sound=
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|speed of sound ref=
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|speed of sound comment=
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|speed of sound rod at 20=3010
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|speed of sound rod at 20 ref=
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|speed of sound rod at 20 comment=
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|speed of sound rod at r.t.=
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|speed of sound rod at r.t. ref=
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|speed of sound rod at r.t. comment=
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|thermal expansion=
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|thermal expansion ref=
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|thermal expansion comment=
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|thermal expansion at 25=5.9
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|thermal expansion at 25 ref=
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|thermal expansion at 25 comment=
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|thermal conductivity=23.0
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|thermal conductivity ref=
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|thermal conductivity comment=
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|thermal conductivity 2=
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|thermal conductivity 2 ref=
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|thermal conductivity 2 comment=
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|thermal diffusivity=
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|thermal diffusivity ref=
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|thermal diffusivity comment=
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|electrical resistivity=
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|electrical resistivity unit prefix=
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|electrical resistivity ref=
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|electrical resistivity comment=
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|electrical resistivity at 0=
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|electrical resistivity at 0 ref=
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|electrical resistivity at 0 comment=
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|electrical resistivity at 20=331·10<sup>-9</sup>
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|electrical resistivity at 20 ref=
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|electrical resistivity at 20 comment=
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|band gap=
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|band gap ref=
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|band gap comment=
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|Curie point K=
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|Curie point ref=
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|Curie point comment=
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|magnetic ordering=Paramagnetic
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|magnetic ordering ref=
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|magnetic ordering comment=
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|tensile strength=
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|tensile strength ref=
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|tensile strength comment=
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|Young's modulus=78
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|Young's modulus ref=
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|Young's modulus comment=
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|Shear modulus=30
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|Shear modulus ref=
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|Shear modulus comment=
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|Bulk modulus=110
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|Bulk modulus ref=
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|Bulk modulus comment=
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|Poisson ratio=0.37
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|Poisson ratio ref=
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|Poisson ratio comment=
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|Mohs hardness=5.5
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|Mohs hardness ref=
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|Mohs hardness comment=
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|Mohs hardness 2=
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|Mohs hardness 2 ref=
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|Mohs hardness 2 comment=
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|Vickers hardness=1520–2060
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|Vickers hardness ref=
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|Vickers hardness comment=
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|Brinell hardness=1450–2100
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|Brinell hardness ref=
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|Brinell hardness comment=
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|CAS number=7440-58-6
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|CAS number ref=
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|CAS number comment=
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<!-- History -->
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|naming=After Hafnia (Latin for Copenhagen), where it was discovered
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|predicted by= Dmitri Mendeleev
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|prediction date ref=
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|prediction date=1869
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|discovered by=
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|discovery date ref=
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|discovery date=
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|first isolation by=
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|first isolation date ref=
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|first isolation date=
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|discovery and first isolation by=Dirk Coster and George de Hevesy (1922)
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|named by=
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|named date ref=
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|named date=
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|history comment label=
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|history comment=
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<!-- Isotopes -->
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|isotopes=
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|isotopes comment=
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|engvar=
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}}
 +
'''Hafnium''' is a d-block transition metal with the symbol '''Hf''' and atomic number 72. It is a hard, high melting point silvery metal, which is resistant to attack by most acids and alkalis. The most documented chemistry revolves around the halides. The principle uses of metallic hafnium are related to the nuclear industry.
  
 +
==Properties==
 
===Chemical===
 
===Chemical===
−
The chemistry of hafnium is dominated by halides. Hafnium (and Zirconium) is essentially restricted to IV state which is due to the loss of the 2 d-electrons and the 2 s-electrons. Other oxidation states are rarely observed and generally accepted to be unstable. In native ores, hafnium occurs as the silicate. The oxygen is displaced in furnace conditions by carbon and replaced by chlorine gas to produce the halide HfCl4. Hafnium halides can be produced by exposing the metal to halide under heat. Most of the halides are volatile solids, but the fluoride is stable. The halides react rapidly to form the oxyhalides HfOX2 which are also stable. The volatility of the tetrahalides is exploited in the production of hafnium "crystal bar" (and also zirconium and titanium crystal bar). Crystal bar production is achieved by reducing the iodide on a platinum wire, resulting in a very high purity metal which forms the beautiful crystal structure.
+
The chemistry of hafnium is dominated by halides. Hafnium (and [[zirconium]]) is essentially restricted to IV state which is due to the loss of the 2 d-electrons and the 2 s-electrons. Other oxidation states are rarely observed and generally accepted to be unstable. In native ores, hafnium occurs as the silicate. The oxygen is displaced in furnace conditions by carbon and replaced by chlorine gas to produce the halide [[HfCl<sub>4</sub>]]. Hafnium halides can be produced by exposing the metal to halide under heat. Most of the halides are volatile solids, but the fluoride is stable. The halides react rapidly to form the oxyhalides HfOX<sub>2</sub> which are also stable. The volatility of the tetrahalides is exploited in the production of hafnium "crystal bar" (and also zirconium and titanium crystal bar). Crystal bar production is achieved by reducing the iodide on a platinum wire, resulting in a very high purity metal which forms the beautiful crystal structure.
  
−
Hafnium is capable of forming up to 8-coordinate bonding structures, but 7- and 6- coordinate are known as well. This means that complexes of HfX73- and HfX84- are known.
+
Hafnium is capable of forming up to 8-coordinate bonding structures, but 7- and 6- coordinate are known as well. This means that complexes of HfX<sub>7</sub><sup>3-</sup> and HfX<sub>8</sub><sup>4-</sup> are known.
  
−
The most important uses of hafnium are due to its nuclear behaviour. Hafnium is an excellent neutron absorber and almost all world production is to supply the nuclear industry with the all important control rods required to stop the runaway "melt down" condition where there are too many mobile neutrons in the reactor. Ironically, zirconium is almost transparent to neutrons and is the preferred metal for fuel rod casings. This presents the industrial problem of ensuring that the neutron transparent zirconium is completely free of the highly absorbing hafnium because their nuclear properties are so different.
+
The most important uses of hafnium are due to its nuclear behavior. Hafnium is an excellent neutron absorber and almost all world production is to supply the nuclear industry with the all important control rods required to stop the runaway "melt down" condition where there are too many mobile neutrons in the reactor. Ironically, zirconium is almost transparent to neutrons and is the preferred metal for fuel rod casings. This presents the industrial problem of ensuring that the neutron transparent zirconium is completely free of the highly absorbing hafnium because their nuclear properties are so different.[[File:Hafnium_3a.jpg|thumb|right|334px|Hafnium electrolytic "flower" by diddi]]
  
 
===Physical===
 
===Physical===
−
Hafnium shares a number of characteristics with its d2 cousins Zr and Ti which reside above it in the periodic table. It is quite hard (comparable with molybdenum, but not quite a refractory metal), and has a high melting point of about 2500K which is in the same range as Zr and Ti. In contrast, however, Hf It is very noticeably denser than Zr and even Pb, at about 13g/cm3. Hafnium, like its cousins, forms a very hard oxide layer which results in specimens have a beautiful shiny silvery surface, which is faintly blue compared pure silver, and about the same hue as cobalt. Hafnium also shares its crystalline structure with its cousins.
+
Hafnium shares a number of characteristics with its d<sup>2</sup> cousins Zr and Ti which reside above it in the periodic table. It is quite hard (comparable with molybdenum, but not quite a refractory metal), and has a high melting point of about 2500K which is in the same range as Zr and Ti. In contrast, however, Hf It is very noticeably denser than Zr and even Pb, at about 13 g/cm<sup>3</sup>. Hafnium, like its cousins, forms a very hard oxide layer which results in specimens have a beautiful shiny silvery surface, which is faintly blue compared pure silver, and about the same hue as cobalt. Hafnium also shares its crystalline structure with its cousins.
−
Availability
+
 
 +
==Availability==
 
Hafnium is predicted by investment speculators to be depleted in the environment within the next 10 years, and its price is rapidly increasing. The spot price tripled in the years 2007 to 2010 (U.S. Geological Survey) and the metal is increasingly more difficult to source at anywhere near spot prices in the domestic market. There are a number of varieties available including foils, bar, etc and two highly attractive forms, the electrolytic "flower" and the crystal bar, both of which attract a premium.
 
Hafnium is predicted by investment speculators to be depleted in the environment within the next 10 years, and its price is rapidly increasing. The spot price tripled in the years 2007 to 2010 (U.S. Geological Survey) and the metal is increasingly more difficult to source at anywhere near spot prices in the domestic market. There are a number of varieties available including foils, bar, etc and two highly attractive forms, the electrolytic "flower" and the crystal bar, both of which attract a premium.
−
Preparation
 
−
The industrial preparation of hafnium is performed by reduction of the principle ore, zircon (the same as the precious gemstone) ZrSiO4 with carbon.
 
−
Zirconium and hafnium have very similar atomic radii and as a result there is substitution of zirconium by hafnium in the matrix. Zirconium forms .013% of the Earth's crust (Wolfram Research) whilst hafnium is orders of magnitude scarcer at .00033%. The hafnium is separated from zirconium as a very valuable byproduct. There are no hafnium specific ores. Purification is by electrolytic processes or the crystal bar method.
 
  
 +
==Isolation==
 +
The industrial preparation of hafnium is performed by reduction of the principle ore, zircon (the same as the precious gemstone) ZrSiO<sub>4</sub> with carbon.[[File:Zr Zircon.jpg|thumb|206px|Zircon crystal by diddi]]
  
 +
Zirconium and hafnium have very similar atomic radii and as a result there is substitution of zirconium by hafnium in the matrix. Zirconium forms .013% of the Earth's crust (Wolfram Research) whilst hafnium is orders of magnitude scarcer at .00033%. The hafnium is separated from zirconium as a very valuable byproduct. There are no hafnium specific ores. Purification is by electrolytic processes or the crystal bar method.
 +
 +
Small amounts of hafnium can be dissolved out of plasma torch cutting elements, by using sulfuric acid and hydrogen peroxide over the course of several days to free it from the surrounding copper. When finished, each torch element yields a cylinder of hafnium approximately 0.5mm in diameter and 3mm long.
  
 
==Projects==
 
==Projects==
 +
*Dragon's breath
  
 +
==Handling==
 +
===Safety===
 +
Hafnium metal has similar properties to zirconium, and has little toxicity. Most of its compounds however have shown to be less benign.
 +
Hafnium is safe to store in air and suitable for element collector's displays without any precautions. It is nontoxic and poses no risks. Aldrich catalog states that the fine 325 mesh powder is a flammable solid and it is shipped under water. Sponge is not considered flammable.
  
−
==Safety==
+
===Storage===
−
Hafnium metal has similar properties to zirconium, and has little toxicity. Most of its compounds however have shown to be less benign. Hafnium is safe to store in air and suitable for element collector's displays without any precautions. It is nontoxic and poses no risks. Aldrich catalog states that the fine 325 mesh powder is a flammable solid and it is shipped under water. Sponge is not considered flammable.
+
−
Storage
+
 
Hafnium can be stored in air without any degradation for years, as noted by many elemental collectors.
 
Hafnium can be stored in air without any degradation for years, as noted by many elemental collectors.
−
Disposal
+
 
 +
===Disposal===
 
Hafnium and its compounds have little toxicity, though given its rarity, it's best to try and recycle them.
 
Hafnium and its compounds have little toxicity, though given its rarity, it's best to try and recycle them.
−
References
 
  
−
==Relevant Sciencemadness threads==
+
==References==
 +
<references/>
 +
===Relevant Sciencemadness threads===
 +
*[http://www.sciencemadness.org/talk/viewthread.php?tid=26651 Hafnium - Plasma Torch Electrode]
 +
 
 +
[[Category:Elements]]
 +
[[Category:Metals]]
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[[Category:Transition metals]]
 +
[[Category:D-block]]

Latest revision as of 21:39, 15 October 2017

Hafnium,  72Hf
Hafnium 2.jpg
Hafnium crystal bar about 30mm long, but weighing over 200 grams by diddi
General properties
Name, symbol Hafnium, Hf
Appearance Steel-gray
Hafnium in the periodic table
Zr
↑
Hf
↓
Rf
Lutetium ← Hafnium → Tantalum
Atomic number 72
Standard atomic weight (Ar) 178.49(2)
Group, block , d-block
Period period 6
Electron configuration [Xe] 4f14 5d2 6s2
per shell
 2, 8, 18, 32, 10, 2
Physical properties
Steel-gray
Phase Solid
Melting point 2506 K ​(2233 °C, ​​4051 °F)
Boiling point 4876 K ​(4603 °C, ​​8317 °F)
Density near r.t. 13.31 g/cm3
when liquid, at  12 g/cm3
Heat of fusion 27.2 kJ/mol
Heat of 648 kJ/mol
Molar heat capacity 25.73 J/(mol·K)
 pressure
Atomic properties
Oxidation states 4, 3, 2, 1, −2 ​(an amphoteric oxide)
Electronegativity Pauling scale: 1.30
energies 1st: 658.5 kJ/mol
2nd: 1440 kJ/mol
3rd: 2250 kJ/mol
Atomic radius empirical: 159 pm
Covalent radius 175±10 pm
Miscellanea
Crystal structure ​Hexagonal close-packed (hcp)
Speed of sound thin rod 3010 m/s (at 20 °C)
Thermal expansion 5.9 µm/(m·K) (at 25 °C)
Thermal conductivity 23.0 W/(m·K)
Electrical resistivity 331·10-9 Ω·m (at 20 °C)
Magnetic ordering Paramagnetic
Young's modulus 78 GPa
Shear modulus 30 GPa
Bulk modulus 110 GPa
Poisson ratio 0.37
Mohs hardness 5.5
Vickers hardness 1520–2060 MPa
Brinell hardness 1450–2100 MPa
CAS Registry Number 7440-58-6
History
Naming After Hafnia (Latin for Copenhagen), where it was discovered
Prediction Dmitri Mendeleev (1869)
Discovery and first isolation Dirk Coster and George de Hevesy (1922)
· references

Hafnium is a d-block transition metal with the symbol Hf and atomic number 72. It is a hard, high melting point silvery metal, which is resistant to attack by most acids and alkalis. The most documented chemistry revolves around the halides. The principle uses of metallic hafnium are related to the nuclear industry.

Properties

Chemical

The chemistry of hafnium is dominated by halides. Hafnium (and zirconium) is essentially restricted to IV state which is due to the loss of the 2 d-electrons and the 2 s-electrons. Other oxidation states are rarely observed and generally accepted to be unstable. In native ores, hafnium occurs as the silicate. The oxygen is displaced in furnace conditions by carbon and replaced by chlorine gas to produce the halide [[HfCl4]]. Hafnium halides can be produced by exposing the metal to halide under heat. Most of the halides are volatile solids, but the fluoride is stable. The halides react rapidly to form the oxyhalides HfOX2 which are also stable. The volatility of the tetrahalides is exploited in the production of hafnium "crystal bar" (and also zirconium and titanium crystal bar). Crystal bar production is achieved by reducing the iodide on a platinum wire, resulting in a very high purity metal which forms the beautiful crystal structure.

Hafnium is capable of forming up to 8-coordinate bonding structures, but 7- and 6- coordinate are known as well. This means that complexes of HfX73- and HfX84- are known.

The most important uses of hafnium are due to its nuclear behavior. Hafnium is an excellent neutron absorber and almost all world production is to supply the nuclear industry with the all important control rods required to stop the runaway "melt down" condition where there are too many mobile neutrons in the reactor. Ironically, zirconium is almost transparent to neutrons and is the preferred metal for fuel rod casings. This presents the industrial problem of ensuring that the neutron transparent zirconium is completely free of the highly absorbing hafnium because their nuclear properties are so different.
Hafnium electrolytic "flower" by diddi

Physical

Hafnium shares a number of characteristics with its d2 cousins Zr and Ti which reside above it in the periodic table. It is quite hard (comparable with molybdenum, but not quite a refractory metal), and has a high melting point of about 2500K which is in the same range as Zr and Ti. In contrast, however, Hf It is very noticeably denser than Zr and even Pb, at about 13 g/cm3. Hafnium, like its cousins, forms a very hard oxide layer which results in specimens have a beautiful shiny silvery surface, which is faintly blue compared pure silver, and about the same hue as cobalt. Hafnium also shares its crystalline structure with its cousins.

Availability

Hafnium is predicted by investment speculators to be depleted in the environment within the next 10 years, and its price is rapidly increasing. The spot price tripled in the years 2007 to 2010 (U.S. Geological Survey) and the metal is increasingly more difficult to source at anywhere near spot prices in the domestic market. There are a number of varieties available including foils, bar, etc and two highly attractive forms, the electrolytic "flower" and the crystal bar, both of which attract a premium.

Isolation

The industrial preparation of hafnium is performed by reduction of the principle ore, zircon (the same as the precious gemstone) ZrSiO4 with carbon.
Zircon crystal by diddi

Zirconium and hafnium have very similar atomic radii and as a result there is substitution of zirconium by hafnium in the matrix. Zirconium forms .013% of the Earth's crust (Wolfram Research) whilst hafnium is orders of magnitude scarcer at .00033%. The hafnium is separated from zirconium as a very valuable byproduct. There are no hafnium specific ores. Purification is by electrolytic processes or the crystal bar method.

Small amounts of hafnium can be dissolved out of plasma torch cutting elements, by using sulfuric acid and hydrogen peroxide over the course of several days to free it from the surrounding copper. When finished, each torch element yields a cylinder of hafnium approximately 0.5mm in diameter and 3mm long.

Projects

  • Dragon's breath

Handling

Safety

Hafnium metal has similar properties to zirconium, and has little toxicity. Most of its compounds however have shown to be less benign. Hafnium is safe to store in air and suitable for element collector's displays without any precautions. It is nontoxic and poses no risks. Aldrich catalog states that the fine 325 mesh powder is a flammable solid and it is shipped under water. Sponge is not considered flammable.

Storage

Hafnium can be stored in air without any degradation for years, as noted by many elemental collectors.

Disposal

Hafnium and its compounds have little toxicity, though given its rarity, it's best to try and recycle them.

References

Relevant Sciencemadness threads

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