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Chapter 14

Group 14 Elements

Occurrence, extraction and uses

Physical Properties

Elements

Hydrides, halides, carbides, hydroxides, oxoacids

Silicones

Sulfides

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Relative abundances of the group 14 elements in the Earth’s crust. • Data are on a logarithmic scan

and units of abundance are ppm.

Occurrence

Extraction

Uses

http://www.abrasivediamond.com/

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Uses of natural graphite in the US in 2009.

http://en.wikipedia.org/wiki/File:Activated_Carbon.jpg http://www.koenigsegg.com/models/ccxr/

The declining use of leaded fuels in motor vehicles.

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Physical properties of the group 14 elements, M, and their ions.

Physical properties of the group 14 elements, M, and their ions.

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Experimental covalent bond enthalpy terms (kJ mol1)

C-C bonds are strong

mes =

Si-Si double bond Si-Si triple bond

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-graphite proposed structure of CFn for n = 1

Allotropes

element's atoms are bonded together in a different manner

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Structure of the fullerene C60; the approximately spherical molecule is composed of fused 5- and 6-membered rings of carbon atoms.

Structure of C70

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Halogenation reactions of C60

C60Br24 C60F18 C60Cl30

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+

structure of C62(C6H4-4-Me)2

K3C60 and Rb3C60

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Methane hydrates

tetraidecahedral dodecahedral

share a pentagonal face

Boiling points of the straight-chain silanes, SinH2n2, and hydrocarbons CnH2n2.

Synthesis:

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Representative reactions of SiH3Cl

Zintl ions

Sn NaSn1.0-1.7 [Na(crypt-222)]2[Sn5]Na in liquid NH3 2,2,2-crypt in

1,2-ethanediamine

Example preparation

[Sn9]4-[Ge9]3-

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[(Ge9)2]6

arachno-[Sn8]6 Rb4Li2Sn8

[Sn12]12

Wade’s Rules

[(Ge9)3]6-

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[Pt@Pb12]2 [Pd2@Ge18]4

Stabilization of large cage Zintl phases with an interstitial atom.

Selected physical properties of the carbon and silicon tetrahalides.

Propose a method to dry halogenated solvents (e.g. CCl4)

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CFCs

trans-[SiCl2(MeIm)4]2

[SiF6]2 [SiF5]

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[SnCl2F] [Sn2F5]

Halides of tin

[Pb3I10]4 [Pb5I16]6

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Selected properties of CO and CO2

Selected low-temperature baths involving dry ice.†

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Transition temperatures between polymorphs of SiO2

Ionic radii of selected ions involved in silicates

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Silicates

[Si8O20]8 [Si12O30]12

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Part of one of the double chains of general formula [Si4O11]n6n present in the mineral tremolite

H-ZSM-5 zeolite is typical of a zeolite in possessing cavities which can accommodate guest molecules.

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Two views (a) from the side and (b) from above of a part of one layer of the SnO and red PbO lattices. Colour code: Sn, Pb, brown; O, red.

Part of the network structure of Pb3O4 (i.e. 2PbO•PbO2) showing the interconnected chains of octahedral {Pb(IV)O6}-units and trigonal pyramidal {Pb(II)O3}-units. Colour code: Pb, brown; O, red.

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Selected properties of ES2 (E = C, Si, Ge, Sn).