Unit 7

Elements of group 15: carbono, silicon

• General Characteristics of Group 14
•Carbon study:
- Isotopes
- Allotropes
•Natural State
•Combinations with oxygen

- CO
- CO2
•Carbonates and hydrogencarbonates
•Silicon: silicates 2
Element C Si Ge Sn Pb
Abundance
180
272.000
71,6 2,1 13
*Second Element (O) E.C.
EC (ppm) * 3
 General characteristics of the group

1.- Elements of the group: C, Si, Ge, Sn, Pb

2.- Electronic Configuration: ns2np2
• maximum bond
number = 4
C, abscence of d orbitals • highest kinetic stability
against hydrolysis

3.- Metallic character variation:

• C, Si are nonmetallic elements
• Ge intermediate behaviour
• Sn and Pb are metals
4
 General characteristics of the group

4.- Scarce (nule) anionic chemistry ( E-4 “difficult to

reach”).
5.- Cationic chemistry increases going down in
the group: Sn(II) and Pb(II).
6.- Oxidation state (II) stability when decreasing in
the group. Inert part effect.
7.- Covalent chemistry (C, Si): the most
representative one
8.- C tendency to form pπ-pπ bonds
9.- High catenation ability: C
5
 Isótopos del C

Natural carbon present 3 isotopes:

12 13 14
C C C
98,89 % 1,11 % trazas
12C : Base for the determination of the atomic mass(u.m.a.)
13C : nucleus with active nuclear spin ⇒ 13C NMR studies
14C (radioactive): Carbon dating: t1/2 = 5730 years
14 1 14 1
• Formation process: 7 N + 0n → 6C + 1H
14 14 0
• Desintegration process: 6C → 7N + -1e (β)
Allows dating objects between 1000 and 20,000
years old.
6
 Carbon: allotropy
Graphite Diamond

• Two forms: α (ABAB) y β (ABC)

• 3D network
• Laminar structure in both form
• C tetraédrico
• dC-C (within the layer) = 1.41 Å
• dC-C = 1.54 Å.
•pπ-pπ bond. Bond Order = 1.3
• Single bond.
• dC-C (entre láminas) = 3,35 Å
• m.p. = 4000°C , hardness = 10
• Exfoliable (hardness= 1.5) and
• Insulator ( e- involved in the bond)
electrical conductor
• Denser: d = 3.5 g/cc
• Low density: d = 2.2 g/cc
•sp3 Hybridization. CCC = 109,5°
•sp2 Hybridization . CCC = 120° 7
 Carbon: allotropy. Diamond

C(graphite) ⇄ C(diamond)
ΔG (25 ºC)= + 2.9 kJ
1940, General Electric Company
diamantes artificiales

• Thermodynamically stable form: graphite

• Endothermic reaction (diamond presents higher energetic
content). During the process, a volumen reduction is
produced. High pressures and high temperatures shift
the balance to the right.
• Work conditions: 1600ºC, 50000 atm
• Catalysts: Fe, Cr, Ni, Pt.
8
 Carbon: allotropy. Fullerenes
Fullerenes: Carbon atoms organized in a spherical or ellipsoidal structure.
5 and 6 member rings. C36 C60 - > C100 (only even numbers)

• Discovery: Kroto, Smalley, Curl. (1985). 1996: Chemistry Nobel Prize

In 1985 Robert Curl, Richard Smalley and Harold Kroto irradiated a surface of
graphite with laser pulses so that carbon gas was formed. When the carbon gas
condensed, previously unknown structures with 60 and 70 carbon atoms were
formed. The most common structure had 60 carbon atoms arranged in a sphere with
five and six edges. The structures were called fullerenes in honor of architect
Buckminster Fuller, who worked with this geometric shape.
9
 Carbon: allotropy. Fullerenes
Fullerenes: Carbon atoms organized in a spherical or ellipsoidal structure.
5 and 6 member rings. C36 C60 - > C100 (only even numbers)

• Preparation: laser-induced graphite vaporization (>10.000°C ) at inert atmosphere.

• C60 (buckminsterfullerene): 32 faces; 20 hexagons and 12 pentagons.
• All carbons are equivalent (all have the same environment, same signal 13C).
• Carbons: Trigonal coordination, sp2, not totally planar.
• Double localized bonds (not conductive) d = 1.5 g/cc
• Solubles in non polar solvents

C60 C70
10
 Carbon: allotropy. Fullerenes
Fullerenes: Carbon atoms organized in a spherical or ellipsoidal structure.
5 and 6 member rings. C36 C60 - > C100 (only even numbers)

11
 Carbon: allotropy. Carbon nanotubes
• Discovered in 1991
• Nanoparticles and nanotechnology: materials with dimensions in the
range of 10-9 m.
• Current reasearch field due to their semiconductor properties and due
to their tensile strenght.
•Preparation: electric dischrages between graphite carbon electrodes.
• They can be open or closed systems.
• In the closed-ones, the ends are C60 units.

12
Carbon: allotropy. Carbon nanotubes

13
 Carbon: allotropy. Graphene

Flat laminar structure,

one atom thick

2010 Physics Nobel Prize

Andre Geim and Konstantin Novoselov

http://www.youtube.com/watch?v=-YbS-YyvCl4&feature=player_embedded 14
 Carbon: allotropy. Graphene
Properties
• High thermal and electrical conductivity (e- can move freely)
• High elasticity and hardness
• Strenght 200 times harder than steel
• It is very light, like carbon fiber, but more flexible
• It heats up less when driving electrons
• Consumes les electricity for the same task than silicon
• It can reacts with other subtances to form compounds with
different properties
It is almost transparent and is very
dense

http://www.youtube.com/watch?v=-YbS-YyvCl4&feature=player_embedded 15
Carbon:
•The two best known crystalline allotropes of carbon,
diamond and graphite, are found in nature, as is
"amorphous carbon" (for example in coal)
•In the atmosphere, as CO2 (0.04% v/v): it is not an
important source of carbon (it is for the plants!)

Silicio:
•It is not found in nature in elemental state
•It is present in the form of oxides and silicates
16
The term active carbon, or activated carbon, refers to
materials consisting essentially of carbon, which have
been treated to achieve a high specific surface area.
Specific surface area: 1400 m2 / g (area greater than that
of an Olympic pool - 1250 m2-). The crystalline structure
is similar to graphite, carbonized hexagonal ring layers,
but irregularly superimposed, forming cavities (pores).
Applications:
• In tertiary treatment of sewage or industrial water (coal
retains dissolved organic compounds, resistant to
biological treatment).
• It is also used in filters to purify drinking water (and
eliminate, among other things, excess chlorine).
• Gas protective masks ... 17
 Carbon Reactivity
Both graphite and especially diamond are not very
reactive at room temperature, due to both the high
energy of the C-C bond and the "lack of empty
orbitals of low energy" (kinetic causes). At high
temperature they become more reactive but resist the
attack of non-oxidizing acids and alkalis.
Carbon reacts with oxygen to give its oxides. The
diamond burns slowly in the air at high temperature
(800 °C) and quickly in pure oxygen:
C(d) + O2(g) → CO2(g) ΔH = -395 kJ/mol

18
 Carbon Reactivity
Some reactions of graphite:
Carbides: CO2 no
Binary compounds
CO + H2 H+ H+
no

x.
with elements less

no o
ox. −
electronegative H2O OH
than C
carburos M,Si,B O2
ionics, covalents −
C22 , C4
− C CO, CO2
and metalics. H2
F2 S8
HF hidrocarburos
Acetylide or dicarbide ion CF4
no CS2

Diamond is less reactive and, for example, does not

react even with fluorine at room temperature.
Most reactions only take place, at an appreciable
rate, at high temperature. 19
Carbon, like other nonmetals, has a
medium-low electron affinity (I, S, P, B)
behave chemically:
• As soft reductants (C is strong
reductant, at high temperature
−Ellingham diagram−).
• As soft-weak oxidants againts strong
reductants.

20
21
 CO

Colorless, odorless and very toxic gas (high affinity

for hemoglobin with the formation of a very stable
complex). Neutral oxide.

ØObtention:
a) C or hydrocarbons combustion with O2 defect
2 C(s) + O2(g) → 2 CO(g)
C7H16(g) + 15/2 O2(g) → 7 CO(g) + 8 H2O(l)

b) Industrially: reaction of “water gas”

C(s, red-hot) + H2O(g) 1000º
→ CO(g) + H2(g)
22
 A Look at Heteronuclear Diatomic Molecules

B.O.= 3

FIGURE 11-27
The molecular orbital diagram of CO
Slide 23 of 57
General Chemistry: Chapter 11 Copyright © 2011 Pearson Canada Inc.
 Carbon Monoxide Reactivity
CO2 (g)

½ O2

Ni (s) MxOy(s)
Ni(CO)4(g) Δ
CO(g) Δ
M(s/l) + CO2(g)
hν Cl2

+ −

M σ C O
COCl2 (g) Carbonyl chloride (phosgene)
− + “Among the chemical agrents used in the war
(WWI), phosgene was responsable for the highest
number of deaths” (Wikipedia)

“Strong” reducing agent (at “high” temperatures)

Δ
Fe2O3(s) + 3 CO(g) 2 Fe(l) +3 CO2(g)
NiO(s) + CO(g) Δ
Ni(s) + CO2(g) 24
 CO: Toxicity

Carbon monoxide shifts the

oxygen-dissociation curve to
CO bound to hemoglobin the left (wikipedia).

25
• Colorless, odorless and non-toxic gas, denser than
the air, which it displaces. Does not burn or sustain
combustion: application in fire extinguishers.

• “Moderately” soluble in water.

O2 CO2 NH3
KH (20 ºC, mM/atm) 1.3 ¡23/34! 62500

In the atmosphere: Average CO2 concentration:

0.03% v/v
10 L (4×2.5 L) of air “contains” 3 mL de CO2
26
ØObtention:
•C or hydrocarbons combustion with O2 excess
C(s) + O2(g) → CO2(g) ΔH = - 405 kJ/mol
CH4(g) + 2 O2(g) → CO2(g) + 2 H2O(l)
• Carbonates thermal decomposition:
CaCO3(s) Δ
CaO(s) + CO2(g) (↑ 1000 ºC)
• In the laboratory:
CaCO3(s) + 2 H+(aq) → Ca2+(aq) + CO2(g) + H2O(l)

27
 σ σ •dbond = 116.3 pm
ØBond: O O
C •Ebond = 531.4 kJ/mol
π π •µ = 0

Cooling agent (laboratories) m.p. = -56°C (5.1 atm)

- At the pressure of 1 atm it has no liquid f.p. = -78°C
phase. A gas cooling below 5.1 atm causes the
steam to pass directly to solid. When a CO2
bottle is opened, the expansion of the gas
produces its cooling down to -78 ° C which, at
ambient pressure, assumes that it is collected
as a solid: DRY ICE
-The pills obtained are easy to store. When
used to cool, CO2 passes directly from solid to
gas, leaving no liquid residue.
-78

28
 CO2 Reactivity: Water behaviour
In the process of dissolving carbon dioxide in water,
several chemical or physical-chemical processes take
place that are described below, and generate a series
of species:
• Carbon dioxide gas is partially soluble in water:
CO2(g) + H2O(l) → CO2*(aq) KH= 3.4×10-2 M/atm

• Carbon dioxide combines, like other covalent oxides,

with water to give carbonic acid:

CO2(aq) + H2O(l) ⇄ H2CO3(aq) K = 2.0.10-3

29
 CO2 Reactivity: Water behaviour
In solution there ends up being a mixture of hydrated
dioxide and carbonic acid:
CO2*(aq) ≡ CO2(aq) + H2CO3(aq)
Although the acid in this case is very unstable (it
has not been possible to isolate) and is the minority
species in these solutions: only 0.37% is carbonic acid:
[CO2(aq)] = 650 [H2CO3(aq)]

• The processes do not end here, because carbonic

acid interacts with water (behaving like a weak acid):

30
 CO2 Reactivity: Water behaviour

H2CO3(aq) + H2O ⇄ HCO3-(aq) + H3O+(aq) Ka1’= 2.15.10-4

The acidity constant that appears in the tables is an

apparent constant:
“H
“CO CO (ac)”
*(aq)”
2 2 3 + H 2 O ⇄ HCO 3
-(aq) + H O+ (aq) Ka = 4.3.10-7
3 1

It is the combination of the two previous processes:

CO2(aq) + H2O ⇄ H2CO3(aq) K = 2.0.10-3

H2CO3(aq) + H2O ⇄ HCO3-(aq)+ H3O+(aq) Ka1’ = 2.15.10-4

• Bicarbonate hidrolizes partially (barely nothing):

HCO3-(aq) + H2O ⇄ CO32-(aq) + H3O+(aq) Ka2= 4.7.10-11

31
 CO2 Reactivity: Water behaviour

• These last two balances move in the presence of

bases: OH- OH-

CO2(aq) HCO3-(aq) CO3 2-(aq)

That is, being an acid oxide, carbon dioxide reacts
with bases to give carbonates. The presence of an
excess of carbon dioxide causes the formation of
hydrogen carbonates (bicarbonates):
2 KOH (aq) + CO2(aq) → K2CO3(aq) + H2O
K2CO3(aq) + CO2(aq) + H2O→ 2 KHCO3(aq)

32
 pH ranges and predominant species
In acidic media: CO2 (aq), “[H2CO3]”
Slightly basic media: HCO3-
Strong basic media: CO32-

C. Orozco, A. Pérez, M. N. González, F. J. Rodríguez y J. M. Alfayate; “Contaminación ambiental. Una visión desde la
química”, Thomson Editores/Paraninfo, Madrid, 2003.
Why does CO2 turn indicators such as
phenolphthalein, litmus or thymolphthalein?

Because it is an acid oxide and therefore

reacts with bases such as NaOH:

CO2(g) + NaOH(aq) ⇄  HCO3-(aq) + Na+ (aq)

pHinitial= 10 ààpHfinal≈ 8

34
CARBONATES & HYDROGENCARBONATES
H2O H2O
CO2 + H2O ⇄ [H2CO3] H3 O+ + HCO3 - 2 H3O+ + CO32-
• Temperature sensitive equilibria: if the temperature increases, the
equilibrium shifts to the left and increases the CO2 concentration.
• If an acid is added, the balances shift to the left.
• If a base is added, the balances shift to the right.
• carbonates and hydrocarbonates are basic in aqueous solutions:
CO32- + H2O ⇄ HCO3- + OH-
HCO3- + H2O ⇄ H2CO3 + OH-
•The hydrogen carbonate reacts with acids to give CO2 and H2O; and
with the bases to give carbonates.
•Insoluble carbonates and hydrogencarbonates dissolve in acids
CaCO3 + 2 HCl → CaCl2 + CO2 + H2O
“Stone disease”
35
 H −
O
C: hybridization sp2
ØHydrogenocarbonates: BO = 1 and 1.5 C
O O

• Only those of the alkaline elements (except lithium) can be isolated.

Even them, they decompose by heating:
Δ
2 NaHCO3(s) Na2CO3(s) + CO2(g) + H2O(g)
• Some alkaline earth hydrogen carbonates originate in solution where they
are soluble : Ca(HCO3)2
CaCO3(s) + CO2(g) + H2O ⇄ Ca+2(aq) + 2 HCO3-(aq)
In alkaline soils, soluble hydrogen carbonates become insoluble
carbonates: stalactites and stalagmites.
• Hydrogencarbonates are all soluble but the sodium one.
• “Hard” water: Waters containing Ca2+ and Mg2+ ions. They create industrial
and domestic problems by producing solid deposits. By heating:
Ca+2(aq) + 2 HCO3-(aq) ⇄ CaCO3(s) + CO2 (g)↑ + H2O(l)
2NaHCO3(s) Δ
Na2CO3(s) + CO2(g) + H2O(g)

Wikipedia: Sodium bicarbonate

https://en.wikipedia.org/wiki/Sodium_bicarbonate

For this reason in the lab classes, to

dry it, we used a temperature below
50 ºC!
 Δ
2 NaHCO3(s) Na2CO3(s) + CO2(g) + H2O(g)
ΔHfº* -951 kJ/mol -1131 -394 -242 (g)
Sº** 102 J/mol.K 135 214 189 (g)
70 (l)

∆H° = ∑νp∆Hf°(products) - ∑νr∆Hf°(reactants)

ΔHºr≈ + 135 kJ ΔSºr≈ + 334 J/K

 Δ
2 NaHCO3(s) Na2CO3(s) + CO2(g) + H2O(g)
ΔHfº* -951 kJ/mol -1131 -394 -242 (g)
Sº** 102 J/mol.K 135 214 189 (g)
70 (l)

∆H° = ∑νp∆Hf°(products) - ∑νr∆Hf°(reactants)

ΔHºr≈ + 135 kJ ΔSºr≈ + 334 J/K

ΔGºr= 0 (K=1) at 131 ºC

 O 2−
C: hybridization sp2
ØCarbonates: BO = 1.33 C
O O

Solubility: Carbonates are less soluble

than the corresponding bicarbonates,
except Na2CO3 which is more soluble than
NaHCO3 (The majority of carbonates are
insoluble).
CaCO3 + CO2 + H2O ⇄ Ca(HCO3)2
insoluble soluble
Soluble carbonates: Group 1 elements,
Tl(I), NH4+.
Average Bond Order

average bond order =

(1 + 1 + 2) bonds/(3) structures = 4/ 3 = 1 ⅓
 CaCO3
Water solubility: 0.013 g/L (25 °C)

Kps= 3.3×10−9
Wikipedia: https://en.wikipedia.org/wiki/Calcium_carbonate

“Ca(HCO3)2”
Water solubility: 166 g/L (20°C)
Wikipedia:
https://en.wikipedia.org/wiki/Calcium_bicarbonatehttps://
en.wikipedia.org/wiki/Calcium_carbonate
 What hard water is?
Rayner–Canham, G. “Química Inorgánica Descriptiva” 2ª Ed.; Pearson Educación, 2000.

The domestic water supply that comes from regions where there
is limestone contains calcium hydrogen carbonate.
In chemistry, limestone or hard water - as opposed to soft
water - is one that contains a high level of minerals,
particularly magnesium and calcium salts. Sometimes it is
given as a limit to designate a water as hardness greater than
120 mg CaCO3 / L.
In the total water hardness a distinction can be made between
temporary hardness (or carbonates) and permanent
hardness (or non-carbonates) generally of sulfates and
chlorides.
It is convenient to know if the water is hard water, since the
hardness can cause deposits of carbonates in washing
lines, heaters, and boilers or in the irons.
Wikipedia: https://es.wikipedia.org/wiki/Agua_dura
Formation of stalactites and stalagmites
CaCO3(s) + H2O(l) + CO2(g) Ca(HCO)2(aq)

Cuevas del Drac, Mallorca

El Soplao, Cantabria
Na2CO3. Soda Solvay. Industrial production product.
Solvay process; Starting products must be abundant in
nature: limestone and common salt. Global equation:
CaCO3+2NaCl -> Na2CO3+ CaCl2
Reaction in sequential steps:
Δ
a) CaCO3 (s) à CaO (s) + CO2 (g)
b) CO2 (g) + NH3(aq) à HCO3- (aq) + NH4+(aq)
c) HCO3- (aq) + Na+ (aq) + Cl-(aq) à NaHCO3(s)↓ + Cl-(aq)
d) 2 NaHCO3(s) à Na2CO3(s) + CO2(g) + H2O(g)
Δ

Recycling:
i) CO2
ii) CaO (s) + H2O àCa+ (aq) + 2 OH-(aq)
iii) NH4+ (aq) + OH- (aq) àNH3 (aq)
Solvay Conference

Ernest Solvay (1838-1922)

Belgium Chemical Engineer

1st Solvay Conference, 1911

 The combustion of fossil fuels and the decomposition of
Efecto invernadero

limestone in cement plants has significantly increased the

concentration of carbon dioxide in the atmosphere, with the
consequent heating.
CO2 and H2O are capable of absorbing much of the
electromagnetic radiation from the infrared region
The non-existence of this effect would suppose temperatures of
the order of 18ºC inferior to the present ones.

48
 The greenhouse effect is a natural process that warms the
Efecto invernadero

Earth’s surface. When the Sun’s energy reaches the Earth’s

atmosphere, some of it is reflected back to space and the rest is
absorbed and re-radiated by greenhouse gases.
Greenhouse gases include water vapour, carbon dioxide,
methane, nitrous oxide, ozone and some artificial chemicals
such as chlorofluorocarbons (CFCs).

49
The atmosphere reabsorbs infrared radiation emitted by
the earth's surface ⇒ It stabilizes the Earth's temperature,
preventing the tremendous temperature variations and
extreme temperatures that take place on other planets (or on
our satellite, the Moon) that lack atmosphere or is very poor.

atmosphere Average Surface temperatures

During the day During the night

Mars Poor atmospher 25 ºC -65 ºC
Moon Nearly abscence 120 ºC -150 ºC
of atmosphere
In the absence of atmosphere, the average temperature of the
Earth would be 255 K (-18 ºC1). The current average
temperature is 15 ºC
1R. M. Harrison y S.J. Mora, “Introductory Chemistry for the Environmental Sciences”, 2ª Ed., Cambridge
University Press, 1996. 50
 Enanced Greenhause effect
Efecto invernadero

https://www.environment.gov.au/climate-change/climate-science-data/climate-
science/greenhouse-effect 51
 Si

-27% in mass in the Earth´s crust (2nd

most abundant after O)
- not in the elemental form, always
combined with O.
-Minerals containing Si are ca. 40%
- ≈ nonmetal (semimetal?): low
electrical conductivity
Silicon Silicon
- m.p. 1420 ºC
(polycristalline) (powder)
-Hardness: 6.5-7
Applications:
-Metal alloys (5.105 T)
-Silicones
-Electronic Industry
-Manufacture of glass, varnishes, enamels, cement and
porcelain (silica and silicates)
-Na2SiO3: amorphous solid: glass: sand+NaCO3 at high T.
52
ØObtention: Metallurgical Silicon (98% purity)
∆
• SiO2 (l) + 2C (s) 2000 ºC
Si (l) + 2CO (g)
∆
• 3SiO2 (l) + 4Al(Mg) (s) 3Si (l) + 2Al2O3 (s)

ØPurification:

Physical methods:
Zone refinig method
ultrapure crystals
(impurities are more
soluble in the liquid
phase tan in the solid
phase)
53
ØReactivity (is poorly reactive, mainly due
to kinetic reasons):
Room temperature
Si(s) + 2F2(g) → SiF4(g)
• Remember: Si (s) + 6 HF (aq) → H2SiF6 (aq) + 2 H2O (l)
It reacts with HNO3, H2SO4 and HCl until the SiO2 formation inhibit
the reaction

High temperature
• Si (s) + 2X2 > 300 ºC SiX4
SiF4 = gas; SiCl4 y SiBr4 = liquid; SiI4 = solid

• Si(s) + O2 (g) 400 ºC

SiO2(s)
It also reacts with N2 to form Si3N4 54
 Silicon Valley

The Silicon Valley, in

California, is named
because there are
multiple companies
working with
semiconductors and
electronics industry.

55
 Quarz
Tridymite

Cristobalite 56
 Silica gel
Hydrated form of SiO2: SiO2.xH2O
(dehydrating agent)
https://en.wikipedia.org/wiki/
Silica_gel

Aerogels
IUPAC definition
Aerogel: Gel comprising a microporous solid in
which the dispersed phase is a gas.[1][2]
Note 1: Microporous silica, microporous glass, and
zeolites are common examples of aerogels.
Note 2: Corrected from ref.,[3] where the definition is a
repetition of the incorrect definition of a gel followed by
an inexplicit reference to the porosity of the structure

https://en.wikipedia.org/wiki/Aerogel57
Silica (SiO2) Nanoparticles
Ordered Mesoporous Silica (OMS)

Adv. Mater. 2012, 24, 1504–1534 58

 Diatoms
Major group of algae, specifically microalgae, found in the oceans,
waterways and soils of the world.
A unique feature of diatom anatomy is that they are surrounded by
a cell wall made of silica (hydrated silicon dioxide), called
a frustule

https://en.wikipedia.org/wiki/Diatom

59
Simple silicate anion
60
 “Simple” Oxoanions XO4n- of elements for the third period
Silicate phosphate sulphate perchlorate

Charge -4 -3 -2 -1
“Valence” e- 32 32 32 32
Number of - 4 2 4
resonance forms
- charge/O atom -1 -¾ -½ -¼
basicity “very high” “high” low Very low
Poly-ate ions? Yes: many Yes: various yes: NO
varieties (polyphosphate S2O72-
(Si2O7)6-... s)
61
 Silicates types
a) Silicates with discrete units

Neosilicates/ortosilicates Sorosilicates/pyrosilicates

(SiO44-) (Si2O76-)

- From the olivine family hemimorphite

(Mg2+ Fe2+ )2 SiO4 Zn4 (OH)2 (Si2O7 )⋅H2O
- From the garnet family lawsonite
(M32+ M23+ )(SiO4 )3 Al2Ca (OH)2 (Si2O7 )⋅H2O
M2+ = Mg, Fe, Ca, Mn
M3+ = Fe, Al, Cr

62
 cyclosilicates (SiO3 )n2n-

(Si3O96-)

(Si4O128-)

beryl Be3 Al2 (SiO3 )6

Emerald dark green Cr3+

Aquamarine blue-green blue: Fe2+, green: Fe3+
Pink beryl pink to red Mn2+
(Si6O1812-) 63
b) Silicates with anions in chains or layers ∝

inosilicates

Simple chains piroxenes

(SiO3)n2n- Enstatite
(Mg,Fe)(SiO3)

Double chains amphiboles

(Si4O11)n6n-
Tremolite
Ca2Mg5Si8O22(HO)2

64
phyllosilicates (Si2O5 )n 2n-

capa t

65
 Eschematic representation

t-o layer t-o-t layer

Mg3(OH)2 (Si4O10 ) Talc

t-o-t layer
¼ of Si replaced by Al

MICA family

KAl2(OH)2 (AlSi3O10 ) Muscovite

KMg3(OH)2 (AlSi3O10 ) Phlogopite

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c) 3D silicates
•Without substitutions quarz SiO2
tectosilicates
•With substitions up to 50% (Al)

Feldspars
Zeolites
Ultramarines

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 Quarz (ccc) Tridymite (hcc) Cristobalite (ccc)

870°C 1470°C 1710°C

quarz tridymite cristobalite melted
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 Silicates types: summary
a) Silciates with discrete units

nesosilicates sorosilicates cylosilicates

b) Silicates with anions in chains or layers ∝

inosilicates phyllosilicates

c) Silicates with 3D networks

tectosilicates
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Zeolites and ultramarines

Zeolitas

Structural units

Ultramarines
Zeolites

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 Silicones (polysiloxanes)
Silicones constitute a huge family of
polymers and all of them contain a chain of
alternating Si and O atoms. Si atoms are
also linked to pairs of organic groups (for
example, the methyl group).

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