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CH 411/511 Intro 1
Ch 14. Group 14
Elemental forms
2
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CH 411/511 Intro 2
Diamond structured metals
Eg /eV R/ cmg
C 5.5 insulator 1015
Si 1.1 semicon 50
Ge 0.6 semicon 30
Sn small metallic 10−5
3
Discovery of fullerenes
+
fullerenes
4From “Designing the Molecular World” by Phillip Ball, Princeton, 1994
www.chemistry.oregonstate.edu/courses/ch412/gobeavs/bucky.ppt
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CH 411/511 Intro 3
Icosahedral symmetry
C60 indicating reactive p-
5
reactive porbitals
Fullerenes
C60 soln C70 soln
6
FCC solid structure
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CH 411/511 Intro 4
C60 reduction
C li
7
Cyclicvoltammetry
Fullerene derivatives
8
(2C70fullerene)carbonylchlorobis(triphenylphosphine)iridium
Balch, Catalano, Lee, Olmstead, Parkin, JACS 113, 8953,1991.
[Pt(PPh3)2(C60)]
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CH 411/511 Intro 5
Carbon Nanotubes
9
Multi-walled nanotube (MWNT)End-closed Sm2O3 in nanotube
Bond enthalpies
10
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CH 411/511 Intro 6
Heavier congeners
11
Halides
CF4 not a LA
SiFSiF4
GeF4
SnF4
PbF4
ex SiF4 + 2HF H2SiF6
12
Note: PbF4 is a strong oxidant due to inert pair effect
All readily hydrolyze in air - except CF4
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CH 411/511 Intro 7
PbF4 and PbO
PbO
13
PbO
Carbides
CaCCaC2
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CH 411/511 Intro 8
Polyanion clusters
Zintl ions
Pb52
using Wades’ rules for e counting
# e pairs = ½ (5 (2) + 2) = 6 which is (n+1) or closo
Sn94
# e pairs = ½ (9 (2) + 4) = 11 which is (n+2) nido
15
# e pairs = ½ (9 (2) + 4) = 11 which is (n+2) nido
These are strong reducing agents, prepared in NH3
(anhyd, liq) or H2NCH2CH2NH2 (anhyd, liq)
Graphite structure
• C C in plane = 1 42 Å• C-C in-plane = 1.42 Å• Usually (AB)n hexgonal
stacking• Interlayer distance
= 3.354 Å
Graphite is a
16
Source: http://www.ccs.uky.edu/~ernst/
A
B
A
Graphite is a semi-metal, chemically stable, light, strong
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CH 411/511 Intro 9
Graphite Intercalation
Cx → Cx+ + e− E ~ −1.3 V
(so no Cx+An− compounds in aqu solution)
17
Cx + BF3 + ½ F2 CxBF4
Cx + AlCl3 + 1/2Cl2 CxAlCl4Domain structure
Some acceptor-type GIC’s
Blue: obsPink: calc
18
CxB(O2C2(CF3)4)2
Pink: calc
CxSO3C8F17
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CH 411/511 Intro 10
Graphite Lithiation
Graphite lithiation: approx 0.2-0.3 V vs Li+/Li
Expands about10% along z
19
Theoretical capacity:Li metal > 1000 mAh/gC6Li 370
Actual C6Li formation: 320 – 340 mAh/g reversible;20 – 40 irreversible
Lithium ion batteries
C th dCathode LiCoO2 Li1-xCoO2 + xLi+ + xe-
Anode6C + Li+ + e- C6Li
ElectrolyteOrganic solvent with LiPF6
20
g 6
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CH 411/511 Intro 11
Orthosilicates
Basic unit is SiO4 (Td) Si4+, O2−
MgxMnyFe2-x-ySiO4 (peridot)
green color from Fe(II)
Ortho = isolated SiO44− ions
21
hcp O array, Si in 1/8 Td sites and Mg,Fe,Mn in 1/2 Oh sites
Single chain metasilicates
22
NaAl(SiO3)2
Jadeite
(SiO32−)n
shared O has no chargeapical O has 1− charge
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CH 411/511 Intro 12
Double chain metasilicates
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Beryl structure
Si6O1812− = (SiO3
2−)6 ring
Be3Al2Si6O18 is beryl
Be3Al2−xCrxSi6O18 is emerald
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CH 411/511 Intro 13
Sheet silicates
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mica 2:1 clay minerals
Clays
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CH 411/511 Intro 14
Clay minerals
27
3D frameworks
-quartz varieties include amethyst, agate.
Also tridymite, cristobalite
SiO2
y ,
All corner sharing Td
MP ~1700 C
Due to slow rearrangement to crystallize, these readily form amorphous glass (vitreous silica)
Borosilicates – add Na2O B2O3 as network
28
Borosilicates add Na2O, B2O3 as network modifiers (Pyrex)
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CH 411/511 Intro 15
3D frameworks - aluminosilicates
Zeolite A
corner sharing Td with Al substitution for Si, which
Sodalite cages = (Al3Si)24O48
29
gives negative charge on framework
Nax[(AlO2)x(SiO2)] · δ H2O x < 1 (no Al-O-Al links)
Zeolite frameworks
30
Na2SiO3 (hyd) + NaAlO2 (hyd) → NaAlSiO4(hyd)
N(OEt)3
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CH 411/511 Intro 16
Siloxanes
Si + 2CH Cl (CH ) SiClSi + 2CH3Cl (CH3)2SiCl2
Controlled hydrolysis to [(CH3)SiO]n + 2 HCl
Si3O3(CH3)6 [(CH3)2SiO]n polydimethylsiloxane (silicone)
Some additives (CH3)3SiCl chain termination
31
Some additives (CH3)3SiCl chain termination
CH3SiCl3 crosslinker
(CH3)(C6H5)SiCl2 phenyl groups increasecrystallinity and modulus
Siloxanes
8 CH3SiCl3 + 12 H2O → cyclo-(CH3)8Si8O12 + 24 HCl
Cubic arrangement
32