Lecture 11

Elements, allotrops, physical protperties of the carbon-group elements. Hybridization, stereochemistry,

occurence in the nature. Isolation/preparation/production of the allotrops. Radiocarbon clock. Practical
applications.

Hydrides, halides of carbon-group elements. Physical properties, chemical reactions, characteristics,

stabilities, chemical reactions, preparation and production, practical applications.
 Occurence of the elements, and their allotropes
Carbon: in the elemental state, as well as in compounds
allotropes: graphite
diamond
fullerene,
carbon nanotube (CNT)
graphene

silicone: in compounds only

allotrope: gray only

Germanium: in compounds only Si

allotrope: gray only
Ge
Tin: in compounds only
allotropes: β-tin, metallic tin, white tin, above 13,2 °C
α-ón, gray tin, below 13,2 °C
Sn
Lead: in compounds only
allotrope: metallic,
face centered cubic cell
Pb
 Allotropes of carbon
Graphite
It is the most abundant allotrope having a layered
covalent solid structure. It conducts heat and electricity
very well. Carbon atoms are arranged in monoatomic
layers with a hexagonal symmetry, containing carbon
atoms in the sp2 hybride state. The last electrons of the
carbon atoms remain on the atomic orbitals and form a
delocalized electron cloud above and below of each layer.
The layers are connected to each other by secondary
chemical bonds only, thus they can slide away fairly
easily. (That’s how a pencil works.)

Graphite can be melted only under a very high

pressure. Mp. 3727 °C, Bp. 4830 °C. It is insoluble in
solvents. Can be machined easily. Heat and electric Phase diagram of carbon. Cross-hatched
areas indicate metastable regions where
conductivities are different depending on the tho phases may be present
orientation of the crystal layers. Conductivities are simultaneously.
much lower perpendicular to the layer, then parallel
with the layer.
Diamond
Diamond is the allotrope of carbon which is stable at high temperatures. At room
temperature, diamond is unstable and may be transformed into graphite in many
million years. It has a very symmetrical, tetrahedral structure and forms a very
stron covalent solid material. Diamond is the hardest natural material (Mohs
hardness: 10). Chemically absolute inert, it has no solvents. Diamond is formed
very deep in the Earth’s crust and gets to the surface (or near the surface) by
tectonic activities. Refractive index of diamond is very high, optical dispersion is
high – diamond is excellent for making jewelry.
Diamond is a perfect electric insulator, and a perfect heat conductor. – Practical
uses in the semiconductor industry, in computer superchips, in cutting tools.

Jewelry grade diamond,

Natural diamond octahedron Structure of diamond in the solid state
cut and polished
Fullerenes: Their structure is resembling a football or soccer ball. Fullerenes form
molecular solids, which do not conduct electricity. They consist of a single layer of carbon
atoms in pentagonal and hexagonal arrangements. The first fullerene, the C60 , was
synthetized in 1985. Fullerenes are named after the architect Buckminster Fuller who
designed unique buildings showing the same structural elements that fullerenes have.
Fullerenes are soluble in organic solvents. They are not inert materials, many derivatives
have been prepared. The most stable representatives are C60 és C70. The carbona toms
are in a streched and bent sp2 hybride state in the molecule. Fullerenes are prepared in an
electric arc between two graphite electrodes immersed in an aromatic solvent.

Toluol solution of C70 and C60 Crystalline C60

Eden Project, 2001- Designed by Buckminster Fuller

Carbon nanotubes (CNTs)
Their structure can be derived from the structure of
fullerenes and graphene, just by elongating or
rolling-up the carbon monolayers to form a tube.
The ends can be opened or closed. Single-wall and
multiple-wall CNTs exist. Each layer is made of one
graphene layer. Typical diameter is a few nm, their
length may reach the micron level. CNTs are
produced by the CVD process on metal (iron)
surfaces. CNTs can be spun to form a thread, the
tensile strength of which exceeds that of the steel.
Graphene (Nobel prize, 2010)
It is made of a single layer of carbon atoms connected to each other in a
hexagonal symmetry. They be considered either as infinitely extended polycyclic
aromatic hydrocarbons (with hydrogen atoms on the edges), or as a sigle layer of
graphite. The very first graphene was prepared by a Scotch tape, pulling one
layer of graphite down from a graphite crystal. Graphene can be prepared by a
strong ultrasound treatment of graphite powder in water. Layers of grapene are
transparent and strong, and found practical applications in many fields including
composites.

Although the structure was first described in 1962, they have received significant
attention only in 2005, when scientists discovered that the 2D electron cloud
behaves like as if it were imaginary pairs of weakly interacting and weightless
elementary particles (so called quasi-particle).

Grafén réteg transzmissziós

elektronmikroszkópos felvétele.
 Demo video: Demonstration of electric conductivities of carbon allotropes

silicone, germanium, lead: They have only one stable allotrope.

Si, Ge: high mp and bp. Rigid materials, crystallize in the form of covalent solids.
silicone is a nearly inert material, it can withstand many agressive chemicals. Si
has only a few materials that can dissolve it in chemical reactions.

Pb: low mp, it forms a metallic solid. It is a soft metal. Pb withstands of oxidation
by oxygen or air, can be dissolved in strong oxidizing acids like cc. HNO3 or cc.
H2SO4. Although moderately, it is soluble in high CO2-content water (beware of old
lead pipes in the buildings).
Tin allotropes
Tin is known for several tousands of years. Mp is
low, boiling point is high. It can withstand the
oxygen rather well when heated. Tin is a non-toxic
metal. Mechanical properties are good, it is a
rather soft metal that can be rolled to thin foil. It is
frequently alloyed with copper to make bronze.

Tin is produced by a simple carbon reduction of its

mineral cassiterite (SnO2). Tin and its alloys are
White tin (β-tin) Gray tin (α-tin)
widely used in tool making, food industry (canned
food, tin boxes), low melting alloys.
Demo video: Transformation of white tin to gray tin (tin pest)

β-Tin, white tin, metallic tin: good

mechnical properties, forms a tetragonal
metallic solid. Stable above 13,2 °C. In
the cold, it may transforme into the gray
tin allotrope, especially when it is
contacted with a tiny grain of gray tin
(called: tin pest, tin disease, tin leprosy)

α-Tin, gray tin: stable below 13,2 °C,

poor mechanical properties, fragile,
powderized easily. It forms a tetrahedral
covalent solid (similar to diamond).
 Electronic structure, hybridization
Electronic structure: ns2 np2
No d subshell in carbon. Other elements have empty d subshell and orbitals.
Highest oxidation numbers: C +4(2) → Pb +2(4) (downwards the column: high
tendency to keep an inert electron pair)
C, Si, Ge, Sn: mainly covalent compounds, Pb: covalent and ionic compounds

Stereostructure of the compounds, binding modes, hybridization

Pls. check your organic chemistry lecture slides and handouts.
Carbon: sp, sp2, sp3, no d subshell

sp3 - 4б ●

sp2 - 3б, 1π sp - 2б, 2π ═●═ CO2, CS2

- ⅓ graphite, CO32ˉ ●
–●≡ HC≡CH

- ½ benzene ● 1n, 1б, 2π :●≡ CO, CNˉ, C22ˉ

- H2CO3, COCl2, etc.

H2C=CH2 ●
Silicone, germanium: (sp2), sp3, sp3d2
sp3: [SiO2(OH)2]2ˉ
- Quartz, SiO2, tetrahedral 3D
O covalent solid structure
Si -
HO O
OH

In contrast to carbon compounds, there is no sp hybride state with silicone. The

analogous molecular formuli with silicone have sp3 hybride state in lieu of sp:
CO2 sp ↔ SiO2 sp3

sp3d2: SiF62ˉ
octahedral

Ar Ar
Although sp2 hybrid state is extremely rare, most recently a Si Si
new compound containing an sp2 silicone atom has been Ar Ar
prepared
Tin, lead: in most of the cases sp3 is the dominant, but sp3d2 may also occur
With tin, a very rare coordination number of 3 may occur in a few complexes.
 Isotopes of carbon
12C 98.9%, stable
13C 1.1%, stable, not radioactive (used in medical diagnostics)
14C 10-10 %, radioactive (beta emitter), halflife t½ = 5730 years

In contrast to its permanent decomposition, the concentration of carbon-14 in the

atmosphere is constant. How is that possible? The answer is that it is not just
decomposing, but also forming in the upper atmosphere by the nuclear reaction
of nitrogen-14 with the high energy neutrons of cosmic rays, and the end is an
equilibrium.
14 N + 1 n → 14 C + 1 H
7 0 6 1

Radiocarbon dating (clock)

C-14 content of all living organisms is in equilibrium with

the atmospheric C-14 concentration. When the organism
dies, all exchange with the environment is stopped. From
that very moment, the radioactivity of the remains is
decreasing following the law of radioactive decay. From the
activity value, the age of a sample can be calculated. The
method can be reliably used for the last 50000 years.
Production of graphite Why do we produce graphite, when it is a mineral?
Because natural graphite is not pure enought for most of the modern
applications in the technology and electronics.

Acheson process (1899) Coke and sand is heated in electric furnaces. At

lower temperature, carbon reduces silicone dioxide to silicone, and forms
silicone carbide immediately with the excess of carbon. In the second step,
silicone carbide is heated up to a much higher temperature, where it
decomposes to carbon (in the form of graphite) and silicone, which distills off
the furnace. The remaining matrial is graphite.
SiO2 + 3C(coke) = SiC + 2CO
SiC = C(graphite) + Si (2600 °C)

Modern production of graphite

It is made from petroleum coke and coal tar pitch. The mixture is
pressed in forms to get different shapes. Then, it is heated up to
1600 °C in an oxygen-free atmosphere to get graphite. Artificial
graphite is used in metallurgy, for making molds, crucibles, and
electrodes. High-purity graphite is used to cover the inner walls of
3 m long graphite
nuclear reactors. electrodes
 Synthetic diamond
HPHT (high pressure, high temperature)
process: it is good for industrial scale
production of jewelry-grade colorless and
colored diamonds, as well as for the correction
of color problems in natural diamonds. A little
diamond seed is placed in the chamber and
covered with a mixture of a special Fe-Ni alloy
and graphite powder. The chamber is put under
high pressure, and heated up (5-10 GPa = 50-
100 kbar) (1500-2500 °C). Graphite dissolves
in the metal and recrystallizes on the surface of
the seeding diamond crystal. By this process,
diamonds of 25 carats (5 g) can be grown. Due
to economic considerations, the process is
stopped at the 1-1.5 carat size. A full cycle
requires 1-6 weeks. Adding metal ions make
the diamonds colored.

BARS (1990) instrument: and its cross section view.

High temperature is reached by heting filaments
embedded in the press form. БАРС = Беспрессовая
Аппаратура высокого давления "Разрезная
Сфера" (press-free high-pressure setup "split
sphere")
CVD (chemical vapour deposition) process: fits the needs of the
semiconducting industry to produce thin artificial diamond slices. Also capable
of producing jewelry-grade diamonds. Thin and polished diamond plates are
placed on a heated table in vacuum, then a mixture of hydrogen and methane
is introduced at 800 °C temperature in the plasma state. In the plasma atomic
hydrogen is generated, which then reacts with methane forming CH3 radicals.
The radicals bind to the diamond surface and then loose hydrogen atoms. The
process requires two weeks to produce large pieces of diamond. The same
process is used to make diamond layer on a silicone or aluminum surface.

H2 = 2H
H + CH4 = CH3 + H2
„C” + CH3 = C-CH3
C-CH3 = „C-C” + 3/2H2

Artificial diamond, after polishing.

Demo video: Making artificial diamond by the CVD process
Production of raw silicone For technical or metallurgical applications, raw silicone
is quite satisfactorily. It is produced by the carbon reduction of sand (SiO2) at or
above1900 °C. In order to avoid the formation of SiC, a slight excess of sand is
used:
SiO2 + 2C = Si + 2CO

Raw silicone can be produced by thereaction of SiC (prepared by the Acheson

process) and sand:
2SiC + SiO2 = 3Si + 2CO

Production of pure silicone is produced by the thermal decomposition of silane or

hydrogen reduction of silicone tetraiodidei:
SiH4 → Si + 2H2 SiI4 + H2→ Si + 4HI

Production of high-purity silicone

For the semiconducting industry, having very high

purity silicone is the starting point for other
operations. Polycrystalline silicone is prepared by
the thermal decomposition of silicone chloroform
HSiCl3 on the surface of a heated thin Si rod.
Polycrystalline
2HSiCl3 → Si + 2HCl + SiCl4 (1150 °C) silicone
Zone crystallization – the Czochralski process (CZ-Si)
Molten silicone is gradually crystallized in the form of a single-crystalline
monolithic ingots, initiated by the use of a single crystal of silicone as the
seed. The monolith is continuously formed as the seed crystal is pulled out
very slowly from the melt. All the inpurities is getting concentrated and remain
in the bottom residue of the process

Melting Seed crystal is Crystallization is

polycrystalline getting in toch initiated by Removal of the high-
silicone with the pulling out the Slow crystal purity silicone ingot
surface seed crystal pulling

Production of amorphous silicone

Amorphous silicone has an irregular covalent solid structure with lots of
dislocations and lattice errors, leading to anomalous electric properties. It can be
used very well in making fotovoltaic cells, and the production costs are much
lower.
The classical production technology uses sodium hexafluorosilicate (the
byproduct of a fertilizer making process) and reduces it by metallic sodium. The
product needs additional purification before use.

Na2SiF6 + 4Na → Si + 6NaF

The modern technology is using SiH4 silane to produce silicone. This method
allows the formation of silicone layers even on the surface of plastics. SiH4 silane
is excited by a radio frequency electromagnetic wave at a 10-1000 Pa pressure
(vacuum), which results in the decomposition of silane and the formation of a
silicone layer. This technology is used to produce transparent windows which
work also as a fotovoltaic cell. Doping with p or n type can be done by adding
diborane or phospine to silane, respectively.

RF excitation
SiH4 Si + 2H2
vacuum

Photovoltaic cell prepared from amorphous silicone

Germanium: semiconducting material
It is prepared by carbon reduction of the
oxide.
GeO2 + 2C → Ge + 2CO
For semiconductor applications it is purified
by the zone melting process, in which a
narrow region of a crystal is melted, and this
molten zone is moved along the crystal. The
molten region melts impure solid at its
forward edge and leaves a wake of purer
material solidified behind it as it moves
through the ingot.

Tin, lead
Prepared by the carbon reduction of their
oxides. Sulfide ores are roasted to oxides, if
necessary.
SnO2 + 2C = Sn + 2CO
Zone melting process in action
2PbS + 3O2 = 2PbO + 2SO2
PbO + C = Pb + CO
Hydrides of carbon-group elements

EnH2n+2
C: nmax >150 Catenation property:
Si: nmax 15 C C C Min. 150
Ge:nmax 9
Sn: nmax 2
Si O Si O Si ∞
C O C O C Max. 4-5
Pb: 1
Si Si Si Si Max. 8-10
Silanes
Thermal
Oxidative ... stability is low
Hydrolytic

SinH2n+2 25˚C nSi+(n+1)H2

(n>2)

Oxidative: the ignite spontaneously in air, combustion products are SiO2+H2O

Hydrolysis (takes place readily even with water):

SiH4 + (2+n)H2O = SiO2·nH2O + 4H2
The process is catalyzed by an infinite amount of a base. In a system using
quartz flask and ultrapure water, the hydrolysis does not take place..
Preparation of silicone hydrides (silanes):
technical grade: Mg2Si + 4HCl = SiH4 + 2MgCl
high purity: SiCl4 + LiAlH4 = SiH4 + LiCl + AlCl3

Hydrides of Ge, Sn, and Pb: SnH4, GeH4, PbH4

(germane, stannane, plumbane)
They are unstable gases (plumbane is especially unstable, it barely exists)

Hydrides of nearly all of the elements (not only Sn, Ge, Pb) can be prepared
by the following reaction:
LiAlH4 LiX+AlX3
E X + or E H+ or X=halogen, E= element
NaBH4 NaX+BX3

Alkyl and aryl derivatives

RnEH4-n , thermal stability is incresing with the increase of ‘n’

ie. SiH4 Si(Me)4

labile stable

PbH4 Pb(Et)4
very labile very stable (it was used as a fuel additive in automotives)
 Halides of carbon

CnX2n+2 nmax
F: 5
Cl, Br: 2 Stability is decreasing downwards
I: 1
Hidrolytic stability: F (Cl) stable
(Cl), Br, I may hydrolyze, (especially under basic
conditions and at elevated temperatures

CBr4 + 2H2O = CO2 + 4HBr

F
Poly(tetrafluoro ethylene, ptfe, Teflon®,
C Resistant to temperatures up to 300˚C
F
n
PTFE is a non-stick material.

It is stuck to the rough internal

surface of the pans in the molten
state (and not by a glue).
Mixed halides
Freons CF2Cl2 The most infamous freon: Freon 12
Chemically very inactive materials, inert solvents.
UV light can split the C-Cl bond resulting in the free radical Cl,
which is responsible for the depletion of the ozone layer

Production: CCl4 + 2SbF3 = CF2Cl2 + 2SbClF2

Halides of silicone
SinX2n+2
F: nmax 14
Cl: 6
Br, I: 1

silicone can form halogeno complexes with the coordination number of 6, due to
the presence of the empty d orbitals. i.e. [SiF6]2ˉ

Hydrolytic stability of silicone halides: low (due to the presence of d orbitals, which
allow the nucleophylic attack on the silicone atom), The hydrolysis takes place in a
stepwise process beginning with the coordination of a water molecule, followed by
splitting off a hydrogen halide. Silanols loose water and give hydrated silicone
dioxide as the final product.
SiX4+H2O X3Si-OH + HX SiO2·nH2O
SiF4 hydrolyzes differently, because the liberated fluoride ions give fluoro complex
with the rest of SiF4.
3SiF4 + (2+n)H2O = SiO2·nH2O + 2H2SiF6

Most important Si-halides: SiF4, SiCl4, SiHnX4-n

Production of halogenosilanes:
SiF4: SiO2 + 2CaF2 + 2H2SO4 + 2H2O = SiF4 + 2CaSO4·2H2O

SiCl4: SiO2 + 2C + 2Cl2 heat. SiCl4 + 2CO

SiH2Cl2, SiHCl3, SiRyHXn, stb:

Si + 3HCl 350 ˚C SiHCl3 + H2
Si + 2MeCl Cu catal. MeSiHCl2 + H2 + C
300 ˚C

Why halogenosilanes are much more reactive then the corresponding carbon
compounds?
Si atom is larger, molecule is larger (more frequent collisions)
Polarity of the Si-X bond is higher
the presence of low-energy empty d orbitals
easy of adduct formation (lowers the activation energy barrier)
Hydrolysis of halogenosilanes

i.e. SiH3Cl + H2O → SiH3OH + HCl

The Si-OH silanol group is unstable in aqueous solutions. It looses water in a

condensation reaction with another silanol group, forming Si-O-Si bonds. The
hydrolysis and condensation steps continue until all Si-X is hydrolyzed.

2SiH3OH H3Si-O-SiH3
-H2O disiloxane
H H
+2nH2O n SiH2(OH)2 Si O Si O
nSiH2Cl2
-2nHCl -nH2O
Silane diol H H
n
2
Polysiloxane chain
polymer

Halogenosilanes containing alkyl or aryl groups are

important building blocks of silicone resins and
silicone oils, which are widely used in almost all
fields of the everyday life.
Silicone resin
Halides of Ge, Sn, and Pb
EX2 are more stable, the stability increases downwards in the column
EX4 exist only with the most electronegative halides (F, and maybe Cl)
when the metal ion in the +4 oxidation state cannot oxidize the halide ion
Ge
Ge: minden halogenid létezik, komplex halogenidek is léteznek [GeX6]2ˉ (X=F,Cl)

300˚C hev. 70˚C Cl2

Előállítás:
-H2 -HCl
Ge+3HCl GeHCl3 GeCl2 GeCl4
Heat +HCl

yellow colorless

GeCl2 hydrolize readily. Ge-hydroxide is not stable and trasformed into the oxide.

GeCl2 + 2H2O = Ge(OH)2 + 2HCl

Ge(OH)2 = GeO + H2O
Sn
SnX2 - due to the presence of Sn(II) ions, they are all reducing agents.
SnX4 – stable, it has no oxidation power

Anhydrous SnCl2 is a Lewis acid (Sn) and a lewis base (Cl) simultaneously. It can
form adducts with a variety of molecules:

Being a Lewis acid, it forms adduct with the Lewis base NH3:
SnCl2 + NH3 → NH3·SnCl2
Being a Leis base, it forms adduct with a lewis acid BF3: bázis:
SnCl2 + BF3 → Cl2Sn·BF3
Important derivatives:
SnCl2 important reagent in the analytical chemistry, reducing agent, making tin layers
SnF2: fluoride source in fluoride tooth pastes (remember: tin is non-toxic)

Pb
PbX2 all exist PbF2 soluble in water White
PbCl2
PbBr2 Precipitates in water
PbI2 Golden yellow

PbX4 Exists only if X=F, Cl (explanation: Pb(+4) is a strong oxidizer)

PbI2