 The element with the most compounds known

 Most of the compounds are considered to be

organic
 What defines an organic compound?
 Compound is made by an organism and found
in nature as part of an organism or stemming
from an organism
 Inorganic carbon compounds
 The electronic structure of Carbon:
 1s22s22p2
 The C4+ ion does not exist
 A unique feature of Carbon is its self binding
properties.
 It can form single, double and triple bonds, and
forms stable chains.
 The C_C bond is thermodynamically very
stable and strong.
 Chemistry and Physical Properties of Diamond,
Graphite, Fullerenes, adn Carbides

 Diamond – Graphite: differ in their properties

because of the differences in the arrengement and
bonding
 Density of Diamond is higher, graphite is more
stable
 Graphite can be transformed into Diamond at
3000K adn pressures above 125kbar. AS catalysts
Cr, Fe or Pt.
 Chemial reactivity of Diamond is lower then
graphite or amorphous carbon.
 Graphite:
 Amorphous carbon: many forms are
microcrystalline forms of graphite.
 Physical properties of these materials are
mainly determined by their surface area.
 The large surface forms:
 Absorb large amounts of gases and solutes.
Carbon, doted with Pd, Pt are uysed as
industrial catalysts.
 Fullerenes:
 C60 Buckminster fullerene or Buckyball
fullerene.
 Birch reduction:
 Unsaturation of C60 by Li in NH3/t-BuOH
 The other chemistry of fullerenes is with
organic molecules (we are not going through
this).
 C60 can react towards transition metals an η2
connection to Pt or Ir is made by the π electrons
of a C=C group
 Partial Halogenation can be achieved with
reaction with Cl2 or Br2
 C60 + Br2 C60Br2 or C60 Br4
 At 150 deg C Br2 can be recovered
 C60 + Cl2  C60Cln (n=24 at average)
 At t>400deg C dechlorinate.
 Alkali metals results in black materials
(K+)3C603-.
 Films of C60 doped with K,Rb or Cs metal
vapor are superconducting. RbnC60 is 30 K.
 Carbides
 Solid compounds with elements other than H
are generally called carbides.
 Classification of Carbides:
 Ionic Carbides
 Alkali and alkaline earth metals and Al.
 Interstitial Carbides
 Reactions with transition metals. The metals
occupy tetrahedral holes in the close packed
arrays of metal atoms.
 Materials are very hard, conducting, and have
high melting points (3000-4800 deg C).
 WC is hard, used for machining steel.
 Cr,Mn,Fe,Co,Ni are between ionic and
interstitial. Hydrolysed by watere and dilute
acids.
 Covalent Carbides:
 Si, B form SiC B4C hard, chemically inert. SiC
has diamond like structure in which C and Si
are tetrahedrally surrounded by four of the
other kind of atoms.
 Carbon Monoxides

 A mixture of CO and Hydrogen is used as

synthesis gas in the synthesis of Methanol.
 Carbon monoxide is formally the anhydride of
formic acid (HCO2H).
 Most important property is its ligand towards
transition metals.
 Only Fe and Ni react directly with CO (toxic).
 Carbon dioxide
 Found in the atmosphere, volcanic gases and in
some spring water.
 Large scale released from fermentation
processes, limstone calcination, combustion of
C and Carbon compounds.
 Involved inn Photosynthesis.
 Solid CO2 (-78.5 deg C)
 Carbonic acid
 Carbonic acid:
 Hydration occurs pH<8 direct hydration
 pH>10 direct attack with OH-
 Cyanides and Related Compounds
 Most important inorganic cemistry is the C-N
bonds.
 The most important species are Cyanide,
Cyanate, Thiocyanate ions.
 Cyanogen (CN)2
 Flammable gas
 Cu catalysed production of Cyanogen

 Dry (CN)2 is made from

 Hydrogen cyanide
 HCN is a covalent molecule
 Can dissociate in aqueous solution
 Poisonous colourless gas
 High dielectric constant
 Due to hydrogen bonding
 Liquid HCN can polymerize
 Aqueous solutions polymerize inducer is UV light.
 HCN, water, Ammonia  pentamerizes to adenine.
 Production of HCN
 Cyanides

 Transition metal cyanides are water insoluble

 Ag and Au cyanides are of importance. Others
are used analytically.
 Compounds with C-S bonds
 CS2 is a very reactive molecule, is a liquid and is
toxic.

 Carbon disulfide is one of the samll molecules that

readilyundergo insertion reactions.
 Si, Ge, Sn,Pb
 Si most abundant element in Nature afdter O
 Ge, Sn, Pb are rare elements
 Sn,Pb have been known since long time,
because they can be just melted out of their
minerals
 Ge was discovered after its existance has been
predicted.
 It is purified from coal and zinc ore
concentrates
 Multiple bonding
 It has been long thought that Si and the other
elements of group IV do not form multiple
bonds
 But:

 At 500 degC
 Although compounds are similar in
stoichiometry they do not share structural or
chemical similarity.
 CO2 is a gas, SiO2 is a network forming
molecule with each Si atom bonded to four O.
 Silane alcohols when dehydrated give
polymers, not like the alkenes from carbon.
 Compounds having oxidation state IV form
tetrahedral compounds
 But valence shell expansion using outer d-
orbitals can occur (dsp3 or d2sp3)
 5 and 6 coordinate compounds are common.
 5 coordination:
 Si is obtained by reductionof SiO2 with carbon
or CaC2 in an electric furnace.
 Ge is prepared by reduction with C or H2.
 Si and Ge are mainly used in semiconductirs.
 The element is first converted to a tetra
chloride, reduced back to the metal by
hydrogen at high temperatures.
 After casting into rods it is refined by zone
melting.
 Sn and Pb are made by the reduction of the
oxide or sulfide with carbon.
 Si is rather ureactive. It reacts with halifdes and
alkali giving silicates.
 It is only attack by HF acid.
 Ge is a bit more reactive. Dissolves in conc
H2SO4 and HNO3.
 Sn,Pb dissolve in several acids, react with
halogens. Slowly react with cold alkali, fast
with hot alkali.
 Colorless gases.
 Only SiH4 is of importance. It is used in the
reaction for precursors of silicones.
 Chlorides:
 MCl4 gives colorless liquids
 Exception Pb-- yellow.
 The tetrachlorides are hydrolysed by water
 To hydrous oxides
 SiCl4 and GeCL4 are used in the synthesis of
pure Si and Ge and in organic chemistry.
 SiO2 occurs as
 Quartz and cristobalite.
 Si is always tetrahedrally bound to 4 oxygens.
 Quartz and criustobalite can be interconverted
by heat.
 Slow cooling of molten SiO2 will result in glass.
 Basic character of the dioxides increases from
Si to Pb.
 No true hydroxiudes exist.
 Anionic complexes

 The other F anions are readily hydrolysed by

bases.
 Cationic complexes
 Their main application is in organic chemistry
and will not be discussed here.
 Si
 Divalent Si species are thermally unstable
 But at 1100 degC:

 In the frozen state it is stable, when thawing it

gives fluorosilanes up to Si16F34
 Ge:
 GeF2 is a crystalline solid and stable.
 It is obtained by reacting Ge with HF at 200
degC.
 GeCl2 gives salts similar to the Sn ions.
 Sn:
 The most important compounds are:
 SnF2 and SnCl2
 Only Pb has a well defined low valent cationic
chemistry.

 Most Pb salts are only sparingly soluble in

water, PbSO4 and PbCrO4 are insoluble.