Lecture 12

Oxides and oxoacids and salts of carbon group elements. Structure, properties,
chemical reactions, production, practical applications. Carbon dioxide and the
greenhouse effect.

C-N and C-S bond contining derivatives. Hydrogen cyanide, cyanic and isocyanic
acid, dicyane, carbon sulfides, thioacids and thiobases.

Carbides: structure, types, properties, reactions, applications.

Oxides and oxoacids of carbon
Two high-stability oxides: CO, CO2
Three low-stability oxides: C3O2 – C5O2;
Formal oxide: C12O9
Nem jól definiált oxid: C2O, C2O3
Graphite oxide: contains hydrogen atoms,
thus it is not a pure oxide. It is a
nonstoichiometric compound in which the
Structure of one layer of
hydrogen and oxygen content is varied. It was graphite oxide
called graphitic acid, due to the presence of
carboxylic groups. Explosive material,
decomposes above 350 °C.

C3O2 (carbon suboxide): O=C=C=C=O (sp hibrid state)

Formal oxide: C12O9 (it is the anhydrate of mellitic acid)

O
COOH O
O
HOOC COOH O
-3H2O
O
HOOC COOH O
O
COOH O
O
Mellitic acid Mellitic anhydride
 Carbon monoxide, CO

Colorless, flammable gas with no odor. Poisonous gas, it forms

a 300 times higher stability complex with the iron ion in
haemoglobine than oxygen.

CO is the anhydride of formic acid. Although it does not react

with water directly, it reacts with sodium hydroxide solution
under pressure resulting in sodium formiate from which formic
acid is prepared by a strong acid.

10bar +H+
CO + NaOH HCOONa HCOOH
>100˚C

cc.H2SO4
Laboratory preparation: HCOOH CO
-H2O

Industrial production is in the water gas reaction or syngas reaction (see

previous slides at hydrogen production).

C + H2O 1000˚C CO+H2

CH4 + H2O heat. CO + 3H2
Complex formation properties of CO
Both atoms are in the sp hibrid state. Both electrons of one bond of the tripple
bond are donated entirely by the oxygen atom. The carbon is partially negatively
charged, and the oxygen is partially positively charged in the molecule.
- +
C O
CO is a good complexing ligand. In the complexes it is a σ(sigma)-donor and
π(pi)-akceptor species. It donates the HOMO electron pair located on the carbon
atom to the metal ion (σ), and accepts electrons from the overlapping d-orbitals to
the empty π*-antibonding LUMO orbital of the CO molecule. Thus, a back-and-
forth coordination bond is generated, which is stronger then a simple coordinative
bond.

HOMO orbital

LUMO orbital
Although in most of the complexes the carbon atom is coordinating to the metal
ions (terminal coordination), CO may form complexes as a bridging ligand
occupying a bridge-position in between two metal ions.In some of the
complexes, the oxygen atom also takes place in the coordination.

terminális híd

Cr(CO)6 Fe2(CO)9
CO is a reducing agent
CO + PdCl2 + H2O = Pd + CO2 + 2HCl

Determination of CO
5CO + I2O5 = 5CO2 + I2

can be titrated by an iodometric method

APractical applications of CO:

Methanol snthesis CO+H2 300˚C 100 bar CH3OH

Acetic acid production CH3OH+CO 190˚C, 30 bar CH3COOH

Methane production CO + 3H2 Ni kat., T, P CH4 + H2O

Metallurgy Fe2O3+3CO 500-900˚C 2Fe+3CO2

 Carbon dioxide CO2, and carbonic acid

CO2 is a colorless, sour-smelling gas. It may suffocate

in higher concentration. At low concentration it has no
health issues. CO2 is „heavier” than air, thus it fills the
lowest regions (accidents with fermenting wines).

It can be liquified at 55 bar pressure at room

temperature. Liquid CO2 is a solvent similar in
properties to n-hexane.

Phase diagram of CO2 Dry ice (compressed, solid CO2)

It freezes at -78 °C and sublimes

at atmospheric pressure. Solid
carbon dioxide is called dry ice, as
it looks like ice in the compressed
form.
standard
állapot

*
Chemical properties
High thermal stability, decomposes only 2% of the total amount at 1700 °C.
2CO2 ⇌ 2CO + O2

Metals (i.e. Mg) having oxides of very high standard enthalpy of formation can
reduce carbon dioxide to carbon and keep burnign in a CO2 atmosphere.

CO2 + 2Mg = 2MgO + C

Demo video: burning of magnesium in CO2

CO2 is the real anhydride of carbonic acid, which is formed directly in the reaction
of CO2 with water. In the first step, carbon dioxide dissolves in water (simple
physical process). The second step is the formation of hydrated carbon dioxide
molecules. (Carbon dioxide hydrate CO2·8H2O can be crystallized from ice-cold
water.)
In the very slow third step, hydrated carbon dioxide is trasformed to carbonic acid.
Carbonic acid dissociates rapidly to bicarbonate (hydrogen carbonate) ion and H+
ion, which reacts immediately with the equilibrium hydroxide ions of water or with
the hydroxide ions of bases (depending on the pH). The concentration of the
undissociated carbonic acid is fairly low.
[CO2]
≈ 600
[H2CO3]
CO2 + H2O ⇌ H2CO3 slow pH<8
H2CO3 + OHˉ ⇌ HCO3ˉ + H2O fast

CO2 + OHˉ ⇌ HCO3ˉ slow

pH>10
HCO3ˉ + OHˉ ⇌ CO32ˉ + H2O fast
Apparent dissociation constant of H2CO3 calculated from the
total dissolved concentration of CO2: K1= 4,45·10-7

Real dissociation constant of H2CO3 calculated from the

total concentration of H2CO3: KS1=2,5·10-4, KS2=4,8·10-11
H4CO4 orthocarbonic acid: it does not exists as a free acid, but their esters are known

Salts of carbonic acid: bicarbonates and carbonates.

HCO3ˉ: bicarbonates, water soluble, thermally labile (baking powder)
CO32ˉ: forms precipitate with many cations (ie. Ca, Mg)
alkali earth carbonates decompose on heating to oxides.
alkali metal carbonates are stable on heating
(Check out in previous slides: hardness of water)

Preparation of CO2 in the laboratory: CaCO3 + 2HCl = CaCl2 + H2O + CO2

kat.
Production of CO2: side product in NH3 synthesis: CH4 + 2H2O = CO2+ 4H2

Applications: Solvay soda process, urea production, cooling, fire exting., extractions.
CO2+NH3+H2O⇌NH4HCO3
NH4HCO3+NaCl=NaHCO3+NH4Cl
2NaHCO3 heat Na2CO3+H2O+CO2
Urea production (2 steps): 2NH3(l)+ CO2 = CO(NH2)2 + H2O (150 bar, 160 °C)

Extraction:
making decaffeinated coffee,
extraction of herbs, spices and drugs
Occurence: The highest amount of free CO2 is in the atmosphere, the rest is
dissolved in sea water and underground water. It can be found as a component of
the natural gas, and in some places as an independent earth gas deposit.

Most scientists think that anthropogenic CO2 emmission is responsible for the
global warming. Others dispute that. What is your opinion?

CO2 conc. In the

atmosphere:
1750 270 ppm
1850 280 ppm
1958 314 ppm
2006 381 ppm
2019 415 ppm
Yearly CO2 release per capita
 Greenhouse effect
The greenhouse effect is the ability of a planet to catch and entrap heat in the
atmosphere. The normal greenhouse effect is our friend. The average
temperature of planet Earth is 14 °C. Without the greenhouse effect, the
temperature would be as low as -16 °C. (Overrun greenhouse effect makes the
surface temperature 500 °C on the planet Venus.)
Natural greenhous gases in the atmosphere are: H2O, CO2, CH4, NOx.
The anthropogenic contribution to the natural greenhouse gases is significant in
the last centuries, and especially in the last decades (CO2, CH4). Production and
release of very efficient artificial greenhouse gases (ie. freons, SF6) increased
the emount of heat entrapped in the atmosphere, resulting in an increase in the
global temperature.

Beside IR absorption, the planet’s surface absorbs

UV and visible light and converts them to IR
radiation (and heat). A part of IR is radiated out to
the space, but the rest is either reflected back by
the clouds to the surface or absorbed by gases in
the atmosphere. Both process results in the
warming of the surface and the atmosphere.
Yearly release of greenhouse gases, per capita

Recommended reading (a novel):

Frank Schätzing: Raj (Athenaeum Kiadó, Budapest, 2005)
Change of the area of artic ice since 1978.
 Visible signs of global warming
Whitechuck glacier (USA, WA), 1973 és 2006 Upsalla glacier (Sveden), 1928 és 2004

Rhone glacier (Oberwald, Switzerland), 1859 és 2001

 Oxohalides of carbon
Phosgen COCl2
COF2 Very toxic and reactive
COCl2 Increasing stability CO+Cl2 C cat. COCl2
COBr2
Hydrolysis: COCl2+H2O=CO2+2HCl

Phosgen attack in WV1

Oxides and oxoacids of silicon
SiO2: Very stable, it has 22 crystalline forms. α-quartz is the most abundant one,
but occuring as common sand or rocks/pebbles at most. Rare and colored quartz
crystals are used for inexpensive jewelry making. Diatomaceous earth (diatomite,
kieselguhr) is the fossilized silicate residue of diatomites.

Kvarc Rózsakvarc Citrin

Physical properties: density depends on the crystal form (4.287-1.97 g/cm3)
Quartz has one of the lowest coefficient of thermal expansion. Hard material,
with a Mohs hardness of 7.
Melting point is very high, can be melted by a hydrogen flame only. Dificult to
work with it, thus quartz instruments are very expensive.

Quartz is transparent in the UV region, thus it a very favoured material in making

photometric cuvettes.
Chemical properties of crystalline SiO2
Very resistant material, can be dissolved in HF. It is even resistant to strong bases.
In molten NaOH or Na2CO3 it dissolves very slowly.

HF gas : SiO2+4HF=SiF4+2H2O
HF solution: SiF4 + 2HF = H2SiF6

In NaOH solution: SiO2 + 2NaOH(l) = Na2[SiO2(OH)2]

It is an acidic oxide. With basic oxides, it forms a salt:

SiO2 + CaO = CaSiO3 (slug formation in metallurgy)
Burns (!) in fluorine gas: SiO2 + 2F2 = SiF4 + O2

Silicic acids
In the normal laboratory practice, we work only with the derivatives of
orthosilicic acid H4SiO4. It cannot be prepared in the pure form under
aqueous solutions becuse it polymerize under such acidic conditions that
would be necessary to have undissociated molecules.However, it can be
prepared in nonaqueous solvents. Its salts and esters can be synthesized.
In many aspects, the properties of orthosilicic acid are very similar to those of
orthophosphoric acid.
The main building block of silicic acids is the SiO4 tetrahedron. , All
structures of all silicates can be derived from this building block.
H4SiO4 v. Si(OH)4 orthosilicic acid: Unstable in aqueous solutions. It
rapidly looses water in a condensation reaction and diorthosilicic acid, and
then polysilicic acids.
weak acid, pKa1=9,84, pKa2=13,2 (25 °C)

OH OH OH
HO Si OH HO Si O Si OH — ··· SiO2·nH2O
-H2O -H2O
OH OH HO t -nH2O
Orthosilicic acid diorthosilicic acid SiO2

H2SiO3 methasilicic acid: It does not exists according to the formula.

Commercial waterglass is a very basic aqueous solution, the formula of
which is given as Na2SiO3 . In fact, that is a wrong formula, because silicon
never forms sp2 hybrid state with a trigonal silicon atom. The correct
formula should be as Na2 [SiO2(OH)2] containing tetrahedral silicon atoms.
From waterglass, a gel is precipitated by adding acid to it. It is called silica
gel.
Na2[SiO2(OH)2] + 2HCl → Si(OH)4 + 2NaCl
n Si(OH)4 = n SiO2.H2O + n H2O
 Mesoporous silica, amorphous silica – Silica aerogels
Aerogels: one of the most exciting and special family of solid materials.
They are the lightest solids in the world, with the highest heat insulation property. The most
delicate ones are transparent. Silica aerogels are prepared from alkoxysilanes by chemical
hydrolysis, and dried to a solid under supercritical conditions.
Si(OR)4 + 2 H2O = SiO2 + 4 ROH

Practical applications are in a very wide range. For example, we are preparing artificial
bone materials, catalysts, photocatalysts, special adsorbents, drug carriers, etc. From silica
aerogels. NASA is using them in the space industry. Most recently, the back cover of
mobile phone Google Nexus7 was made of an organic aerogel.

You can do aerogel research in my laboratory, if you wish, as a diploma work, or student science activity.
Silicates are the salts of (poly)silicic acids. They are the main constituents of
Ert’s crust. The most abundant silicates on Earth are aluminosilicates. Main
buildong blocks are the SiO4 tetrahedrons. Electric charge is equilibrated and
electric neutrality is provided by different cations (ie.. Li, Na, K, Be, Mg, Ca, Al, Ti).
Classification of silicates is based on the number of common connecting oxygen
atoms in between the tetrahedrons.

Chain silicate

Layered silicate
Oxides of germanium
GeO, GeO2

GeO2 application: production of Ge and GeH4

Ge oxoacids: they are similar to Si oxoacids. No important application.

Oxides of tin and lead EO; EO2; Pb3O4 SnO + 2HCl = SnCl2 + H2O
Amphoteic oxides
SnO + NaOH + H2O = Na[Sn(OH)3]
SnO, PbO: Soluble in acids and bases
SnO2, PbO2: more soluble in bases PbO + 2NaOH + H2O = Na2[Pb(OH4)]
PbO2
Pb(IV) oxidizer: Mn(II) MnO4ˉ PbO2 + 2NaOH + H2O = Na2[Pb(OH)6]
Most frequently used oxides of lead:
PbO2 (dark brown), strong oxidizer, used in rechargable batteries
Pb3O4 (orange red), (old name: minium, red lead), in corrosion inhibitor paint

O O

Pb Pb Pb

O O
Pb3O4 PbO2
 Compounds containing C-N bonds
HCN, (CN)2, cyanides, HOCN, HNCO

Hydrogen-cyanide, HCN
It is in equilibrium with the hyrogen isocyanide, but the equilibrium is shifted left
HCN ⇌ HNC
Very toxic gas, with a mild smell of almond.
(Peoples Temple: 1978 Jonestown,
Guayana, Jim Jones cult leader, 909 death)
Preparation: Zn(CN)2 + H2SO4 = 2HCN + ZnSO4

Ionic cyanides – with alkali metals

Covalent cyanides – with transition metals

HCN is a weak acid (pK = 9), aqueous solution of alkali metal cyanides are very
basic, due to hydrolysis:
CNˉ + H2O ⇌ HCN + OHˉ

Cyanide solutions absorb carbon dioxide from the air and liberate hydrogen
cyanide (volatile), and transform into carbonates.
In hot solutions cyanide ion hydrolyzes to formiate and ammonia:
CNˉ + 2H2O = HCOOˉ + NH3
Cyanide ion is a good complexing ligand, it forms very stable complexes.
Similarly to CO, The CN– ion is also a σ-donor, and π-acceptor ligand in the
complexes (for an explanation, please find slides at CO). It can be both a
terminal and a bridge ligand. It stabilizes metal ions in the low oxidation states.
M-CN M-C≡N-M

Applications of cyanides
Electroplating: Electrolytic deposition of thin metal layers
CN ion decreses the standard potential by complexation
Electrostatic
potencial map
Gold extraction – the cyanide process (MacArthur-Forrest process).
4Au + 8NaCN + O2 + 2H2O = 4Na[Au(CN)2] + 4NaOH

The cyanide process is very dangerous to the environment!

HOMO
 The Bai Mare Cyanide Spill
A hard two weeks for the people…
(River Tisza cyanide poisoning)
And a hard two years for Mother Nature
January 30, 2000 Bai Mare, Romania.
Due to heavy precipitation, design and
operation failures, the dam of a cyanide
waste disposal lake collapsed and
100,000 m3 of highly toxic water
(containing cyanides, copper, lead)
poured into river Szamos, then to River
Tisza. At least 1240 t of fish and an
unknow number of water birds died in
Hungary.
Industrial production:
CH4 + NH3 Pt, 1200˚C HCN + 3H2 600 e.t/év

Old industrial process:

2Na + C + 2NH3 750˚C 2NaCN + 3H2

Applications: production of the starting material of Nylon, production of

methyl methachrylate, insecticides, EDTA production

Dicyan (aka cyanogen), (CN)2 N≡C-C≡N delocalized electrons

Preparation: Hg(CN)2 heating (CN)2+Hg

Formation: 2Cu2+ + 4CNˉ = 2Cu(CN)2 spontaneously 2CuCN+(CN)2

Endothermic compound →very high temperature can be reached (purple flame)

It is considered a pseudohalogen: (CN)2 + 2KOH = KCN + KOCN + H2O

Cyanic acid, Isocyanic acid: HOCN, HNCO

They are in an equilibrium with each other, but the equilibrium is shifted to the
isocyanic form: H-O-C≡N ⇌ H-N=C=O

Thio analogues: H-S-C≡N H-N=C=S

O→S exchange thiocyanic acid isothiocyanic acid
Hg(NCO)2 Mercury isocyanate (mercury fulminate): very sensitive primary explosive
KSCN Potassium thiocyanate (potassium rhodanide), analytical reagent

Cyanamide, H2N-CN
Weak diprotic acid, with two resonance forms. The calcium salt is used as a
fertilizer, because it releases urea when gets hydrolized.
CaCN2 + 3H2O = Ca(OH)2 + CO(NH2)2

Production: CaC2+N2 1000˚C CaCN2 +C

Compounds with C-S bonds

Carbon disulfide, CS2
Toxic liquid with a very strong odor of rotted raddish. Mp and bp is low. It forms
an explosive mixture with the air.
C + S2 800˚C CS2
It is a thioacid anhydride: K2S + CS2 = K2CS3

Carbonyl sulfide, COS

This compound is responsible for the special odor of some sulfur-containing
mineral waters. It was identified first by the Hungarian analytical chemist
Károly Than. It hydrolyze very slowly to hydrogen sulfide, which gives the
characteristic smell of such waters:
COS + H2O ⇌ HS-CO-OH → H2S + CO2
Silicon disulfide SiS2 (a white, fibrous material)

Prepared by synthesis: Si + S2 100˚C SiS2

It hydrolyze readily with water, and undergoes ammonolysis
with liquid ammonia.
SiS2 + (2+n)H2O = SiO2·nH2O + 2H2S
SiS2 + 4NH3 → Si(NH)2 + 4NH4SH

SnS (brown), SnS2 (yellow), PbS (black)

Thay occur as sulfide minerals in the nature, and used to prepare the metals.
In the classical analytical chemistry, their colored sulfides help to identify the
metal ions in solutions.

SnS SnS2

PbS
 Carbides
1) Covalent carbides: only with Si and B. Chemically they are very stable.
SiC diamond-type covalent solid
B4C icosahedral B12 units + C3 chains High hardness
Uses: B4C: protecting layer on cutting tools
SiC: grinding, electric heating elements
2) Ionic carbides: with alkali and alkali earth metals, and Al
Acetylides: Cu2C2; Ag2C2; Au2C2; Hg2C2 Very explosive materials!

They hydrolyze readily: Al4C3 + 12H2O = 4Al(OH)3 + 3CH4

CaC2 + 2H2O = Ca(OH)2 + C2H2

3) Intersticial carbides: nonstoichimetric compounds, carbon is embedded in the

lattice of the transition metal.

When the radius of the metal ion is larger than 130 pm (Group IV és V): carbon is
smoothly embedded and reinforcing the lattice. Mp is increasing, hardness is
increasing.

When the radius of the metal ion is less than 130 pm (Group VII és VIII):
embedded carbon atoms deform the lattice and form longer carbon chains inside.
Hydrolysis of such carbides give longer-chained alkanes. (reading: the theory of
abiogenic formation of petroleum, abiogenic oil reserves).